Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
  • C07D493/10—Spiro-condensed systems
• • 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
  • G03C1/675—Compositions containing polyhalogenated compounds as photosensitive substances
• • 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
  • G03C1/685—Compositions containing spiro-condensed pyran compounds or derivatives thereof, as photosensitive substances
• • 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
  • Y10S430/143—Electron beam
• • 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
  • Y10S430/163—Radiation-chromic compound

Definitions

• Preferred recording materials contain a spirodinaphthopyran compound, carbon tetrabromide and/or iodoform and as sensitizing agent Michlers ketone or a 2,2,4-trimethyl '1,2dihydroquinol-ine in polystyrene as binding agent.
• This invention relates to photographic recording and reproduction of information and to materials suited therefor.
• spiropyrans used in the manufacture of photographic recording materials is known e.g. from the US. patent specification 2,953,454 of E. Berman- Nat. Cash Reg, issued Sept. 20, 1960.
• the spiropyrans described therein are characterized as being reversibly transform-able into a colored form by activating electromagnetic energy.
• the starting substances for these radicals are preferably halogenated organic compounds.
• At least one ultra-violet light-sensitive compound capable of producing on exposure with ultraviolet light with said spiropyran compound a dyestutf salt is increased by applying in working relationship with said mixture at least one organic compound belonging to one of the following classes:
• A Organic compounds containing two radicals of different electron-affinity (the term radical includes group as well as atoms) linked to each other through a conjugated system
• B organic compounds containing an aromatic nucleus or aromatic ring system in which two adjacent carbon atoms are common to said nucleus or ring system and to an adjacent ring which has no conjugated character and which at one end is linked to the aromatic nucleus or ring system through a carbon-carbon bond and at the other end is linked to said nucleus or ring system through an electron-donating group such as a secondary or tertiary amino group, said organic compounds include those having said nucleus or ring system in a substituted form.
• Useful sensitizing agents of class (A) are those having one of the following general formulae (1), (II), (III), (IV), (V) or (VI):
• D represents an electron-donating group e.g. an alkyl (preferably C -C alkyl), cycloalkyl or aralkyl substi-- carbazole units, can vary between wide limits, say, e.g. between 20 and 95%, taking into account the properties of the compounds used in the preparation of the copolymers and the required sensitizing and/ or mechanical properties. In general, the best results are attained with copolymers having a content of vinylcarbazole units between 40 and 90%.
• an alkyl preferably C -C alkyl
• cycloalkyl or aralkyl substi-- carbazole units can vary between wide limits, say, e.g. between 20 and 95%, taking into account the properties of the compounds used in the preparation of the copolymers and the required sensitizing and/ or mechanical properties. In general, the best results are attained with copolymers having a content of vinylcarbazole units between 40 and 90%.
• the poly-'N-viny1 indoles are described in the published German patent application 1,906,831 filed Feb. 12, 1969 and 1,917,747 filed Apr. 5, 1969 by I.B.M. Corp.
• the poly-N-vinyl diphenylamine is described in the published German patent application 2,007,692 filed Mar.
• Halogen-substituted poly-N-vinyl carbazoles are described in the published Japanese patent applications 21,875/67 filed June 18, 1964, 25,230/67 filed Oct. 13, 1864, 7,592/ 68 filed Nov. 27, 1964, 19,751/ 67 filed June 18, 1964 and 7,591/68 filed Nov. 18, 1964, all by Matsushita Elecric Industrial Co. Ltd.
• 01311151101 polymer of N-vinylcarbazole and polyethyl acry a 8 copoiymer oi N-vinylcarbazole and n-butyiacrylate..;... copolymer of N-vinylcarbazoie and 2-ethyihexylacrylate.
• copolymer of N -vinylcarbazole and acryioxyethyidiethylmnlnn copoiymer o1 N-vinylcarbazole and vinylcinnamate copolymer of N-vinylcarbazole and methyimethacrylate copotlymer oi N-vinylcarbazole and isobutylmethacrye... copolymer of N-vinylcarbazole and laurylmethacrylate.
• copolymer of N-vinylcarbazole and 4-viny1pyridine copolymer 0! N-vinylcarbezole and N-vinylpyrrolidine.
• heterocyclic compounds having the following tautomeric general formulae:
• Preferred compounds falling within the scope of class (Q) are e.g.:
• H20 C S H, NH
• Preferred compounds falling within the scope of formula (V) are merocyanines e.g. those described in the United Kingdom patent specification 1,131,238 filed Nov. 16, 1965 by Eastman Kodak Co. Representatives thereof are e.g.:
• Preferred compounds belonging to class (B) are described e.g. in the Belgian patent specification 727,433 filed Jan. 27, 1969 by Gevaert-Agfa N.V. corresponding with the US. patent application Ser. No. 793,881. Representatives thereof are e.g.:
• n is a positive integer of at least 2
• R represents hydrogen or an alkyl group including a substituted alkyl group.
• the pyran rings the condensed benzo, the condensed higher aromatic rings as well as the 1,3,3- trimethylindolino ring may be substituted.
• Suitable substituents therefore are e.g. hydrocarbon groups such as alkyl groups, e.g. lower alkyl groups such as methyl, substituted alkyl groups e.g. halogen, or phenyl substituted alkyl groups, alkylene ester groups e.g. a CH-COOC H group, alkylene carboxyl groups e.g. a -CH COOH group, earbonamide groups or substituted carbonamide groups e.g. a
• halogen nitro, hydroxy, alkoxy, aryloxy or a substituent linking the carbon atoms in 3,3'-position in the spiropyran system together e.g. a (CH -chain wherein n is 2 or 3.
• R, R R' R R' R and R' represent hydrogen, an aliphatic group including a substituted aliphatic group e.g. a (C -C alkyl group including such an alkyl group in substituted form, more particularly a methyl, ethyl, propyl, amyl or hexadecyl group or halogen substituted alkyl group, halogen, nitro, hydroxy, an alkoxy or aryloxy group, a phenyl group or a substituted phenyl group, piperidyl, an alkylene ester group e.g. a substituted aliphatic group e.g. a (C -C alkyl group including such an alkyl group in substituted form, more particularly a methyl, ethyl, propyl, amyl or hexadecyl group or halogen substituted alkyl group, halogen, nitro, hydroxy, an alkoxy or aryloxy group
• an alkylene carboxyl group e.g. a --CH COOH group
• a carbonamide group or a substitutel carbonamide group e.g. a
• Preferred spiropyran compounds are spirodinaphthopyrans and spirobenzonaphthopyrans including such compounds wherein the naphthoand/or benzo ring(s) is (are) substituted.
• the formed pyrylium salt is separated by suction, is washed with ethanol and thereupon brought into suspension in 300 ml. of ethanol.
• the obtained crystalline product is separated by suction, washed with water and dried.
• the spiran compound is recrystallized from 15 ml. of hexane.
• the compound capable of producing a dye salt with a spiropyran on exposure to activating electromagnetic radiation is for use according to the present invention preferably an organic polyhalogen compound of which a halogen containing radical can be photolytically separated.
• Compounds possessing that property are within the scope of the following general formula:
• each of A, B, X and Y are halogen atoms of the group of chlorine, bromine or iodine, or
• one of said radicals A, B, X or Y represents an alkyl group, including a substituted alkyl group e.g. a halogen substituted alkyl radical, a hydroxylalkyl radical or an aralkyl radical e.g. a benzyl radical, an aryl group, a substituted aryl group or an aroyl group and the other radicals chlorine, bromine or iodine, or wherein at least two of said radicals A, B, X or Y represent an aromatic acyl group e.g. a benzoyl group and the other radicals chlorine, bromine or iodine.
• a substituted alkyl group e.g. a halogen substituted alkyl radical, a hydroxylalkyl radical or an aralkyl radical e.g. a benzyl radical, an aryl group, a substituted aryl group or an aroyl group and the other radicals chlorine, bro
• Suitable representatives falling within the scope of that general formula are organic halides such as carbon tetrabromide bromoform, iodoform, hexachloroethane, hexabromoethane, pentabromoethane, l,1,2,2-tetrabromoethane, a ,a-tribromoacetophenone and tribromoethanol.
• organic halides such as carbon tetrabromide bromoform, iodoform, hexachloroethane, hexabromoethane, pentabromoethane, l,1,2,2-tetrabromoethane, a ,a-tribromoacetophenone and tribromoethanol.
• the amount of sensitizing agent is not critical.
• sensitizing agent with respect to the spiropyran compound may be used e.g. 0.0005 g. to 0.10 g. of sensitizing agent to 0.005 g. to 0.2 g. of spiropyran compound.
• the spiropyran compound(s) are further preferably used in admixture with a 5- to 20-fold amount by weight of photosensitive organic halogen compound such as carbon tetrabromide.
• photosensitive organic halogen compound such as carbon tetrabromide.
• This ratio is, however, not limitative since useful results can be obtained with e.g. the spiropyran and photosensitive polyhalogen compound in a ratio by weight in the range of 1:1 to 1:50.
• sensitizing agents used according to the present invention may be applied as the sole sensitizing agents or in combination with one or more sensitizing compounds belonging to one of the following classes:
• A represents a single bond or a divalent hydrocarbon group e.g. a -CH group
• R represents hydrogen or a lower alkyl radical, e.g. a
• R represents hydrogen or a lower alkyl radical, e.g. a
• Q and Q each represent a hydrogen atom or together the necessary atoms to close an adjacent carbocyclic ring or ring system including such ring or ring system in substituted form, preferably an aromatic ring (e.g. a benzene ring) including a substituted aromatic ring e.g. a halogen substituted (chlorine, bromine or iodine substituted) benzene ring,
• Q, and Q each represent a hydrogen atom or together the necessary atoms to close an adjacent carbocyclic nucleus or ring system including such a ring or ring system in substituted form, preferably an aromatic ring (e.g. a benzene ring) including a substituted aromatic ring e.g. a halogen substituted (chlorine, bromine or iodine substituted) benzene ring, and
• n 1 or 2.
• the N-vinyl polymers and copolymers of class (P) can be prepared by application of one of the various known polymerization procedures, e.g., by pearlor emulsion polymerization or by polymerization in solution, whereby the initiation of the polymerization can occur by free radical, by ion formation, or by radiation e.g., with actinic light.
• the polymerization degree is not critical and can vary between wide limits.
• the content of groups corresponding to the general formula given hereinbefore is not critical and, as shown furtheron in the table of copolymers containing N-vinylcarbazole units, can vary between wide limits, say, e.g.
• copolymers having a content of vinylcarbazole units between 40 and 90%.
• the poly-N-vinyl indoles are described in the published German patent application 1,906,831 filed Feb. 12, 1969 and 1,917,747 filed Apr. 5, 1969 by I.B.M. Corp.
• the poly-N-vinyl diphenylamine is described in the published German patent application 2,007,692 filed Mar.
• Halogen-substituted poly-N-vinyl car is described in the published Japanese patent applications 21,875/67 filed June 18, 1964, 25,230/67 filed Oct. 13, 1864, 7,592/68 filed Nov. 27, 1-964, 19,751/ 67 filed June 18, 1964 and 7,591/ 68 filed Nov. 18, 1964, all by Matsushita Elecric Industrial Co. Ltd.
• heterocyclic compounds having the following tautomeric general formulae:
• X represents oxygen, sulphur, selenium or the group in which R is hydrogen or an organic group e.g. an alkyl group including a substituted alkyl group, preferably a C -C -alkyl group, and
• Z represents the necessary atoms to close a 5- or 6-membered heterocyclic nitrogen containing ring or ring system including such ring or ring system in substituted form e.g. a benzthiazole, benzselenazole, benzoxazole, or benzimidazole ring.
• Preferred compounds falling within the scope of class (Q) are e.g.:
• H20 C S H; NH
• H20 C S H1 ---NH Imidazolidine-4-on-2-thiones, e.g.:
• Tetrahydroand dihydro-oxazine-Z-thiones and thiazine-Z-thiones e.g.:
• CHI fi Thioamides e.g.:
• the recording layer contains preferably from 5 to 50 parts by weight of zinc oxide dispersed in 100 parts by weight of binding agent containing the spiropyran compound(s) preferably in an amount of 1 to 50 parts by weight and the photosensitive reactant for forming the dyestuff salt e.g. a photosensitive organic halogen compound such as carbon tetrabromide and/or iodoform in an amount of to 250 parts by weight.
• the photosensitive reactant for forming the dyestuff salt e.g. a photosensitive organic halogen compound such as carbon tetrabromide and/or iodoform in an amount of to 250 parts by weight.
• the photosensitive recording layer according to the present invention may contain a film-forming binder.
• a film-forming binder preferably hydrophobic polymers are used that shield as much as possible the ingredients from a direct contact with the atmosphere and more especially from oxygen.
• Particularly suitable binders for use in the present invention are hydrophobic polymers and copolymers e.g. containing styrene, vinyl acetate, acrylonitrile, acrylic acid ester, methacrylic acid ester, N-vinylcarbazole or butadiene units, hydrophobic cellulose derivatives, phenoxy resins or polycondensates of the polyester type e.g. polycarbonates.
• These polymers can be used in a mixture for improvement of the mechanical strength or adhering power of the recording layer to its support when no self-supporting layer is produced.
• anti-foggants may be added to the photosensitive composition.
• Suitable anti-foggants include triaryl compounds of group V elements e.g. triphenylstilbine and sterically hindered phenols e.g. 2,6-di-tert.butyl p-cresol and other reducing or atmospheric oxygen accepting agents.
• Triphenylstilbine and analogous compounds for the purpose of the present invention are described in the United Kingdom patent specification 1,071,104, filed Aug. 14, 1964 by Horizons Inc.
• a dry photographic coating containing the above mentioned ingredients may be formed by dissolving the binding agent(s) in a suitable inert solvent which acts as dispersing or dissolving medium for the other ingredients and which is removed from the coating composition by evaporation leaving a solid photographic recording layer on a properly chosen support.
• the supports may be of any kind encountered in silver halide photographic materials e.g. paper and film supports.
• the photosensitive organic polyhalogen compounds that in exposed state form with a spiropyran compound a dyestutf salt are normally only sensitive in a wavelength range between 400 and 250 nm.
• sensitizing agents of the enumerated classes sensitize the recording composition in its inherent sensitivity range and it is assumed that they may also be considered as chemical sensitizing agents for they may chemically interact with photoradicals formed during the exposure.
• a choice of a proper combination of sensitizing agents that are active for extending the sensitivity in the visible spectrum of the print-out recording composition used in the present invention makes it possible to apply white or colored light in the information-wise exposure.
• organic spectral sensitizing agents e.g. that are within the scope of the definition of class (A) and that have in their structure a conjugated system of sufficient length it is possible to extend the spectral sensitivity into the visible light spectrum and even into the infrared.
• the spectral sensitization over the whole visible spectrum opens the possibility to produce print-out multicolor prints by means of one and same recording material. So, on using a recording material containing superposed recording layers sensitized respectively in the red, green, and blue region of the spectrum and containing the proper dye forming combination superposed cyan, magenta and yellow part images can be produced that offer a full reproduction of the multicolor original used in the information-wise exposure.
• the recording materials sensitized" according to the present invention are suited to produce print-out images of different color according to the type of spiropyran compound applied.
• the stabilization of the obtained prints may proceed by washing out the residual free radical generator with a suitable solvent or sorbent mixture e.g. a hydrocarbon liquid such as petroleum ether optionally mixed with acetone, or by simply evaporating it 'by raising the temperature when the compound involved is sufiiciently volatile.
• a suitable solvent or sorbent mixture e.g. a hydrocarbon liquid such as petroleum ether optionally mixed with acetone
• carbon tetrabromide or a mixture of carbon tetrabromide and iodoform is preferred.
• the information-wise exposure is carried out in such a way that first a latent image is produced which is transformed into a visible dye image by means of a so-called optical development.
• the optical development proceeds by exposing the recording layer containing the latent or barely visible image over its entire surface with visible radiation which lies in the spectral absorption band of the products formed 'by the image-wise exposure and image-wise interaction of the photoexposed ingredients (1) and (2) of the mentioned photosensitive composition.
• no exposure light is applied to which the photosensitive polyhalogen compound is inherently sensitive since thereby the effect of the image-wise exposure is masked by an overall coloration.
• a cut-off filter absorbing all the light corresponding with the wavelength range that is inherently absorbed by the ingredients of the non-previously exposed recording layer.
• the optical development effect is markedly speeded up and the image density increased by applying heat e.g. supplied by contact with a hot body or through infrared radiation during the overall exposure to visible light.
• the optical development speed obtains a particularly high value by the use of Michlers ketone or analogues in combination with the mercapto compounds of class (Q).
• a triarylstibine such as triphenylstibine to that combination intensifies the image density obtained by the optical development procedure.
• the recording material is first overall exposed to electromagnetic radiation to produce non-differentially over the whole recording layer latent dyestuff centres that are afterwards optically developed information-wise by a sufliciently strong information-wise exposure in the absorption band of the dyestufi centres.
• the information-wise exposure proceeds simultaneously with an overall heating e.g. effected by an overall infra-red light exposure.
• these dyestuffs may be added e.g. applied by imbibition (diffusion) in minor amounts to the recording layer composition to act as optical development nuclei for the dye image formation by image-wise exposure.
• the spiropyrans are formed in the non-exposed recording layer composition in situ" by starting from the corresponding pyrylium and indolinium salts and adapting the pH in a proper way to obtain the spiropyrans that may be considered as the dyestufi precursors of the pyrylium and indolinium salts, respectively.
• the information-Wise exposure applied in the present invention may be a contact exposure of the direct or reflex type and also an optical projection exposure as used e.g. in an optical enlarging apparatus.
• the informationwise exposure need not be simultaneous in all part of the recording material.
• the exposure may be progressive in one continuous step as e.g. in sound track recording or in sucessive intermittent steps provided that the required information-wise change is obtained.
• the recording material may be scanned with an image-wise modulated radiant energy spot of high intensity e.g. a laser beam, or the material may be progressively exposed through a slit, e.g. is exposed to copying light of a tubular lamp that is given a translation movement along the original.
• a recording material of the present invention being suited for the recording of information in the form of modulated ultraviolet radiation can be used in X-ray and electron-beam recording.
• X-ray beams can be absorbed in high energy absorbing substances and create by means of them so-called depoty photons, e.g., of the ultraviolet radiation energy band and photo-electrons that are absorbed by the photosensitive polyhalogen compound forming through its photoradicals a dyestutf salt with the spiropyran.
• Substances for high energy absorption that may be incorporated in the recording element contain the elements, lead, mercury, bismuth, barium and/or tungsten.
• Lead compounds that themselves are photosensitive are preferred e.g. lead monoxide, lead bromide and lead iodide.
• Suitable light sources for use in a recording method of the present invention are ultra-violet light sources, xenon-gas lamps, incandescent bulbs, the light of the sun and flash lamps.
• an infra-red lamp emitting also in the visible spectrum is preferably used.
• Electron beam and laser beam recording proceed with the apparatus suited for that purpose and known to those skilled in the art.
• Recording materials of the present invention are very versatile in that they by the use of a proper sensitizing agent can be applied for continuous tone or halftone reproduction. They can offer very contrasty images so that they are very suited for the reproduction of line and screen type originals and find a successful use in a great variety of graphic art applications.
• the recording materials of the present invention are for their very high resolving power particularly suited for microfilm reproduction and high precision image rendering as e.g. in the production of optical micromask masters used in the manufacturing of microelectronic circuitry.
• the reflex-exposure properties of the present recording materials make them very useful in the document reproduction sector since they offer in a reflex-contact exposure print-out images of a sufiiciently intense spectral density.
• a recording layer as described herein is used in conjunction with a magnetic recording layer and is more particularly applied at the rear side of a fiexible tape support carrying the magnetic recording layer.
• a sound track is formed in the magnetic recording layer and a visual text image corresponding with the sound track photographed on the recording layer of the present invention.
• Such a recording material thus allows the storing of optical and acoustic signals and makes it possible to reproduce both informations simultaneously.
• EXAMPLE 1 Preparation of sample A 500 mg. of carbon tetrabromide and 10 mg. of the spiropyran compound No. l of Table 1 were dissolved in 8 ml. of a 5% solution of polystyrene in methylene chloride. The obtained solution was applied with a layer thickness of 0.1 mm. onto a non-subbed polyethylene terephthalate support.
• the coating was dried for 30 min. at 50 C. in the dark.
• sample B 200 mg. of carbon tetrabromide, 200 mg. of iodoform and 10 mg. of the spiropyran compound No. 1 of Table 1 were dissolved in 8 ml. of a 5% solution of polystyrene in methylene chloride. The obtained solution was coated in the same way as described for sample A.
• sample C 500 mg. of carbon tetrabromide, 10 mg. of spiropyran compound No. .1 of Table 1 and 5 mg. of p,p'-dimethylaminobenzophenone (Michlers ketone) were dissolved in 8 ml. of a solution of polystyrene in methylene chloride. The obtained solution was applied as described for sample A.
• sample D 500 mg. of carbon tetrabromide, 200 mg. of iodoform, mg. of the spiropyran compound No. 1 of Table 1 and 5 mg. of p,p'-dimethylaminobenzophenone were dissolved in 8 ml. of a 5% solution of polystyrene in methylene chloride. The obtained solution was applied as described for sample A.
• the exposed recording layer was stabilized against background coloration by a heat treatment at 120 C. for 10 min.
• sample B was exposed and processed in the same way as sample A.
• sample B The recording layer of sample B was at a distance of 10 cm. for 3 sec. exposed through a negative line image transparency with a HPL lamp-80 w. (trade name). Thereupon the image-wise exposed film was subjected to an overall exposure by means of an infra-red lamp of 250 w. (sold by Rio and Berntsen,'35 Pilestraede, Copenhagen, Denmark) emitting also in the visible part of the spectrum. Between the infrared-lamp and the recording layer a cut-oif filter was placed absorbing all the light with a wavelength smaller than 540 nm. (Corning 0.8. 3-67).
• the latent image formed was optically developed to a visible image by means of an overall exposure of 5 min. effected under the same circumstances as described for sample B.
• the recording layer of sample D was exposed imagewise for 1 sec. under the exposure conditions as described 26 for sample C and thereupon overall exposed in the same way, the overall exposure lasting, however, only 1 min.
• a cyan image of an optical density 1 and free from background coloration (fog) was obtained.
• Photosensitive compositions consisting of an intimate mixture of 500 mg. of carbon tetrabromide, 5 mg. of Michlers ketone, 10 mg. of one of the spiropyran compounds represented in Table l and 8 ml. of a 5% solution of polystyrene in methylene chloride were coated separately at a thickness of 0.1 mm. onto non-subbed polyethylene terephthalate film strips. The thus obtained recording layers containing each a different spiropyran compound were dried during 30 min. at 50 C. in the dark.
• a first relatively short image-wise exposure with the same high pressure mercury vapor bulb as used in the print-out exposure and placed at a distance of 10 cm. was applied.
• the image-Wise exposure being a contact exposure through a line image transparency was of such duration that a latent image or barely visible image was obtained starting from which in the optical development a visible image without significant background coloration was obtained.
• the overall-exposure applied in the optical development was effected by means of a 250 w.-infrared lamp (Bio and Berntsen, Copenhagen, Denmark) through a cut-off filter absorbing substantially all the light with a wavelength smaller than 540 nm.
• the stabilization of the obtained images was effected by heating the exposed recording layers at C. for 5 to 10 min.
• Photosensitive compositions consisting of an intimate mixture of 200 mg. of carbon tetrabromide, 200 mg. of iodoform, 10 mg. of one of the spiropyran compounds represented in Table 1. 5 mg. of Michlers ketone and 8 ml. of a 5% solution of polystyrene in methylene chloride were coated separately at a thickness of 0.1 mm. onto non-subbed polyethylene terephthalate film strips. The thus obtained recording layers were treated as in Example 2. In Table 4 the results of their print-out and optical development characteristics are listed.
• Photosensitive compositions consisting of an intimate mixture of 500 mg. of carbon tetrabromide, 10 mg. of dip-naphthospiropyran (compound 1 of Table 1) and 5 mg. of one of the sensitizing compounds indicated by number in the description and 8 ml. of a 5% solution of polystyrene in methylene chloride were coated separately at a thickness of 0.1 mm. onto non-subbed polyethylene terephthalate film strips. The thus obtained recording layers containing each a different sensitizing agent were dried during 30 min. at 50 C. in the dark.
• Photosensitive compositions of 250 mg. of carbon tetrabromide, 200 mg. of iodoform, 30 mg. of di-fl-naphthospiropyran (compound 1 of Table 1) and 5 mg. of one of the sensitizing compounds indicated by number in the description were dissolved in 8 ml. of a 5% solution of polystyrene in methylene chloride. These compositions were coated separately at a thickness of 0.1 mm. onto non-subbed polyethylene terephthalate film strips.
• Photosensitive compositions of 250 mg. of carbon tetrabromide, 250 mg. of iodoform, 30 mg. of spiropyran compound No. 1 of Table 1, and 5 mg. of sensitizing agent indicated by number in the description were dissolved in 8 ml. of 5% solution of polystyrene in methylene chloride. These compositions were coated at a thickness of 0.1 mm. onto unsubbed polyethylene terephthalate film strips.
• the obtained photosensitive recording layers were dried in the dark.
• the recording layers were subjected to a relatively short (see Table 7) image-wise exposure with a 300 w.-tungsten incandescent lamp placed at a distance of 10 cm. hereby forming a latent or barely visible image. Subsequently the image-wise exposed recording layers were subjected to an overall exposure (see Table 7) with a 250 w. infra-red lamp (Bie and Berntsen, Copenhagen, Denmark) placed at a distance of 15 cm. and irradiating the recording layers through a cut-oif filter which absorbs substantially all the light with wavelength below 580 nm.
• Dye images with an optical density (D) of l and corresponding with the exposed portions of the recording layers were obtained.
• optically developed recording layers were stabilized (fixed) by heating at 120 C. for 10 min.
• EXAMPLE 7 A photosensitive composition consisting of 200 mg. of carbon tetrabromide, 200 mg. of iodoform, 10 mg. of spiropyran compound no. 1 of Table 1, 5 mg. of Michlers ketone and 8 ml. of a 5% solution of polystyrene in methylene chloride was coated at a thickness of 0.1 mm. onto an unsubbed polyethylene terephthalate support and dried.
• a contact exposure through a continuous tone blackand-white negative transparency yielded an excellent print-out copy having opposite image values with respect to the original.
• the exposure lasted 2 min. and was carried out with a HP lampw. (trade name) placed at a distance of 10 cm.
• EXAMPLE 8 250 mg. of carbon tetrabromide, 250 mg. of iodoform, 5 mg. of Michlers ketone, and 30 mg. of 2(o-hydroxy naphthavinyl)-fl-naphthopyrilium bromide were dissolved in 8 ml. of a 5% solution of polystyrene in methylene chloride. The addition of some traces of water did almost completely decolourize the obtained solution.
• the images obtained with such recording layer were completely stable against fading by light after fixation (heat-treatment at 120 C.).
• EXAMPLE 9 500 mg. of carbon tetrabromide, 10 mg. of 2(o-hydroxy naphthavinyl)-B-naphthopyrilium chloride, 1 mg. of Michlers ketone and 8 ml. of a 5% solution of polystyrene in methylene chloride were coated at a thickness of 0.1 mm. onto an unsubbed polyethylene terephthalate support.
• EXAMPLE 10 A photosensitive composition of 500 mg. of carbon tetrabromide, 150 mg. of iodoform, 20 mg. of spiropyran compound No. 1 of Table l, 5 mg. of 2,6-ditert.butyl-pcresol, 2 mg. of the sensitizing agent No. 24 dissolved in 8 ml. of a 5% solution of polystyrene in methylene chloride was coated at a thickness of 0.1 mm. onto a non-subbed polyethylene terephthalate film support.
• the dried recording layer was in contact with an opaque line original (printed text on paper) exposed reflectographically for 1 second using as exposure source a 300 w. incandescent tungsten lamp placed at a distance of 10 cm. from the recording layer.
• the optical development was effected by means of an overall exposure carried out with a 250 W.-infrared lamp (Bie and Berntsen, Copenhagen, Denmark) using a cutoif filter absorbing substantially all the light with a wavelength smaller than 540 nm.
• EXAMPLE 11 A photosensitive composition consisting of 200 mg. of carbon tetrabromide, 200 mg. of iodoform, 40 mg. of dinaphthospiropyran, 20 mg. of triphenylstibine, 10 mg. of Z-mercapto-benzthiazole, 0.003 g. of a merocyanine dye and 8 ml. of a 5% by weight solution of poly-N-vinylcarbazole in methylene chloride was coated at a thickness of 0.12 mm. onto a non-subbed polyethylene terephthalate support. The coated layer was dried for 30 min. at 50 C.
• the obtained photosensitive recording layer was contact-exposed for 1 sec. through a transparent line original.
• the exposure was carried out with a 3M Photocopier 179 (trade name) operating with a white light exposure source (setting /2
• a latent image was formed which was developed optically by means of an overall exposure through a cut-01f filter absorbing all the light having a wavelength smaller than 540 nm. and using a 250 w. infra-red lamp placed at a distance of 15 cm.
• the fixation of the obtained visible image proceeded by heating the recording material at 175 C. for 10 sec. under strong air circulation.
• EXAMPLE 12 A photosensitive composition consisting of mg. of iodoform, 50 mg. of 3-phenyl-di-B-naphthospiropyran, 5 mg. of Michlers ketone and 4 ml. of a 5% solution in a butanone/methylene chloride /a by volume) of a phenoXy-polymer prepared from 2,2 bis(4 hydroxyphenyl) propane and l-chloro 2,3 epoxypropane was coated at a thickness of 0.12 mm. onto a non-subbed polyethylene terephthalate film.
• the coating was exposed for 2 minutes through a step wedge having a density increment of 0.15 using a 80 w. high pressure mercury vapor bulb, type HPL of N.V. Philips Gloeilampenfabrieken, Eindhoven (The Netherlands) placed at a distance of 10 cm.
• a photosensitive composition consisting of 100 mg. of carbon tetrabromide, 100 mg. of iodoform, 100 mg. of '3-methyl-di-fl-naphthospiropyran, 10 mg. of Michlers ketone and 10 ml. of a 5% solution of polystyrene in methylene chloride was coated at a thickness of 0.1 mm. onto an unsubbed polyethylene terephthalate film.
• the obtained photosensitive recording layer was dried at 60 C.
• the electron-beam sensitivity of the photosensitive layer was tested in a vacuum of 10" mm. Hg.
• the electron beam recording proceeded with electrons accelerated by a potential difference of 20 kv.
• the charge density measured at the level of the recording layer was 2.10- coulomb per sq. cm.
• the optical density (measured in transmittance) of the area struck by the electron beam was 0.5.
• the measurement was preceded by a thermal stabilization at C.
• a photographic process for forming a visible image in a recording material which comprises in intimate admixture:
• (l-) at least one spiropyran compound of the group consisting of spirodibenzopyran, a spirodinaphthopyran, a l,3,3-trimethylindolino-benzospiropyran, a 1,3, 3-trimethylindolinonaphthospiropyran, or a spiropyran that contains a condensed anthracene or phenanthrene nucleus;
• each of A, B, X and Y is a chlorine, bromine or iodine
• one of said radicals A, B, X or Y is an alkyl group, an aryl group or an aroyl group and the other radicals are each chlorine, bromine or iodine; or two of said radicals A, B, X or Y each is an aromatic acyl group and the other radicals are each chlorine, bromine or iodine; and (3) in working relationship with said mixture (A) an organic compound containing two radicals of different electron-affinity linked to each other through a conjugated system, and having one of the following general Formulae (I), (II), (III), (IV), (V) or (VI):
• D represents an electron-donating group selected from an amino group substituted with alkyl, cycloalkyl or aralkyl, a hydroxy group or a hydroxy group substituted with alkyl, cycloalkyl or aralkyl,
• Z represents a polymethine chain, an azamethine chain, phenylene or naphthalene,
• R represents hydrogen, an alkyl group, an aryl group or the necessary atoms to form a homocyclic ring with an atom of the group Z,
• Q represents the necessary atoms to form with the carbon atom of the group a heterocyclic ring having an electro negative character with respect to the group D,
• Y represents an electron-attracting group selected from the group consisting of C--C, --S-, S, or the group C, ll ll l o o wherein X has the above meaning
• Q represents a heterocyclic nucleus, containing an alkylamino group
• P and Q each represent an electron-attracting cyano group, or P and Q together represent the necessary atoms to close a heterocyclic ring with electronegative character
• each of L and L represent a methine group
• L represents a monovalent chemical bond
• H r r group or a plurality of such group linked to each other, or L L and L represent together a double bond linking the group Q: E) to the group C/ or (B) organic compounds containing an aromatic ring having two adjacent carbon atoms thereof in common with an adjacent ring free of conjugation, said adjacent ring at one end being linked to said aromatic ring through a carbon-carbon bond and at the other end is linked to said ring through an electron-donating group and having one of the following structural formulae:
• n is a positive integer of at least 2
• R is hydrogen or an alkyl group
• a photosensitive recording material for the direct production of a visible image by imagewise exposure to activating electromagnetic radiation which comprises a layer of an intimate mixture consisting essentially of:
• each of A, B, X and Y is a chlorine, bromine or iodine atom; or one of said radicals A, B, X or Y is an alkyl group, an aryl group, or an aroyl group and the other radicals are each chlorine, bromine or iodine; or two of said radicals A, B, X or Y each is an aromatic acyl group and the other radicals are each chlorine, bromine or iodine; and (3) in working relationship with said mixture (A) an organic compound containing two radicals of diiferent electron-affinity linked to each other through a conjugated system, and having one of the following general formulae (1), (II), (HI), (IV), (V) or wherein:
• D represents an electron donating group selected from an amino group substituted with alkyl, cycloalkyl or aralkyl, a hydroxy group or a hydroxy group substituted with alkyl, cycloalkyl or aralkyl,
• Z represents a polymethine chain, an azamethine chain, phenylene or naphthalene,
• R represents hydrogen, an alkyl group, an aryl group or the necessary atoms to form a homocyclic or heterocyclic ring with an atom of the group Z,
• Q represents the necessary atoms to form with the carbon atom of the group a heterocyclic ring having an electronegative character with respect to the group D,
• Y represents an electron-attracting group selected from the group consisting of wherein X has the above meaning
• n is a positive integer of at least 2
• R is hydrogen or an alkyl group.
• a photographic process according to claim 1 wherein the recording material after the formation of a visible 6.
• a photographic material according to claim 2 R wherein said spiropyran compound corresponds to one of the following general formulae: 5 4 3 ,3 4' 5' Q r R1 s B 7' R:
• a process according to claim 1 wherein said ultrap. a y y p, an a y p, an aryl y violet light-sensitive compound is carbon tetrabromide or p a p y g p P P Y y halogen, IlitfO,
• a photosensitive recording material according to agent of the group of styrene, vinyl acetate, acrylonitrile, Claim Containing as an anti-fogging agent a lriaryl acrylic acid ester, methacrylic acid ester, Nvinylcarpound of a group V element and a sterically hindered apelole or butadiene units, a hydrophobic cellulose derivaphenol.
• a photosensitive recording material contains triphenyl stilbine with respect to said photosensitive polyhalogen compound in a ratio by weight in the range of 1: 100 to 2.5:100.
• D is an electron-donating group
• R is hydrogen or a linear or homocyclic hydrocarbon radical

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• 1970
  • 1970-09-01 GB GB4174970A patent/GB1359472A/en not_active Expired
• 1971
  • 1971-08-04 AU AU32011/71A patent/AU3201171A/en not_active Expired
  • 1971-08-06 ZA ZA715241A patent/ZA715241B/xx unknown
  • 1971-08-10 CA CA120,215A patent/CA989236A/en not_active Expired
  • 1971-08-16 IT IT86263/71A patent/IT943534B/it active
  • 1971-08-27 DE DE19712142966 patent/DE2142966A1/de not_active Withdrawn
  • 1971-08-27 BE BE771848A patent/BE771848A/nl unknown
  • 1971-08-27 JP JP6626171A patent/JPS5443368B1/ja active Pending
  • 1971-08-27 FR FR7131276A patent/FR2102042A5/fr not_active Expired
  • 1971-09-01 US US00177114A patent/US3813245A/en not_active Expired - Lifetime
  • 1971-09-01 US US00177119A patent/US3810762A/en not_active Expired - Lifetime
  • 1971-09-01 NL NL7112021A patent/NL7112021A/xx unknown
  • 1971-09-01 US US00177122A patent/US3810763A/en not_active Expired - Lifetime

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