US3810763A - Photochromic composition containing polyhalogenated hydrocarbon,spiropyran compound and zno or pb(ii) oxide and the use thereof - Google Patents

Photochromic composition containing polyhalogenated hydrocarbon,spiropyran compound and zno or pb(ii) oxide and the use thereof Download PDF

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US3810763A
US3810763A US00177122A US17712271A US3810763A US 3810763 A US3810763 A US 3810763A US 00177122 A US00177122 A US 00177122A US 17712271 A US17712271 A US 17712271A US 3810763 A US3810763 A US 3810763A
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group
exposure
compound
image
spiropyran
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U Laridon
Den Houte J Van
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Agfa Gevaert NV
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    • 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

  • spiropyrans used in the manufacture of photographic recording materials is known, e.g. from the United States patent specification 2,953,454 of LB. Berman-Nat. Cash Reg, issued Sept. 20, 1960.
  • the spiropyrans described therein are characterized as being reversibly transformable into a colored form by activating electromagnetic energy.
  • the starting substances for these radicals are preferably halogenated organic compounds.
  • At least one ultraviolet light-sensitive compound capable of producing on exposure with ultraviolet light with said spiropyran compound a dyestulf salt is increased by applying in working relationship with said mixture an inorganic compound producing photoelectrons under the influence of activating electromagnetic radiation and having a basic or amphoteric character.
  • Preferred inorganic compounds for that purpose are photoconductive zinc oxide and lead(II)monoxide.
  • Spiropyran compounds suited for photographic image formation according to the present invention are spiropyrans containing at least one pyran ring having in the orthoand meta-position to the oxygen atom a condensed benzo, naphtho or other higher aromatic polycyclic condensed ring system including these condensed rings or ring systems in substituted state, e.g. an anthraceno or a phenanthreno ring system, e.g.
  • a spirodibenzopyran as present in a spirodibenzopyran, a spirodinaphthopyran, a spirobenzonaphthopyran, a 1,3,3-trimethylindolinobenzospiropyran, a 1,3,3-trimethylindolinonaphthospiropyran or such spiropyrans containing condensed aromatic nuclei of the anthracene or phenanthrene type.
  • 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, carbonamide groups or substituted carbonamide groups, e.g. a
  • R, R R',, R R'g, 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 CH OOOC I-I group, an alkylene carboxyl group, e.g. a CH COOH group, a carbonamide group or a substituted 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 solution is boiled under reflux for a period of 2 hours. Thereupon the mixture is cooled down and filtered.
  • the spiran compound is recrystallized from 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 C8111 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 wherein 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 hydroxyalkyl 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 hydroxyalkyl radical or an aralkyl radical,
  • Suitable representatives falling within the scope of that general formula are organic halides such as carbon tetrabromide, bromoform, iodoform, hexachloroethane, hexahexabromoethane, pentabromoet-hane, 1,1,2,2-tetrabromoethane, 11,,a-tribromoacetophenone and tribromoethanol.
  • organic halides such as carbon tetrabromide, bromoform, iodoform, hexachloroethane, hexahexabromoethane, pentabromoet-hane, 1,1,2,2-tetrabromoethane, 11,,a-tribromoacetophenone and tribromoethanol.
  • the spiropyran compound(s) are preferably used in admixture with a 5- to -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.
  • Z represents a sulphur atom or a single bond
  • 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 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 radicals, 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 further-on in the table of copolymers containing N-vinylcarbazole units, can vary between wide limits, say, e.g.
  • the poly-N-vinyl indoles are described in the published German patent applications 1,906,831 filed Feb. 12, 1969 TABLE 2 Male percent of N-vinyl Copolymer carbazole ccpolymer of N-vinylcarbazole and vinylidene chloride 85. 4
  • Useful sensitizing agents of class (B) are those having one of the following general Formulae I, II, III, IV, V
  • D represents an electron-donating group, e.g. an alkyl (preferably C -C alkyl), cycloalkyl or aralkyl substituted amino or hydroxy group, preferably a monoalkyl amino group, a dialkylamino group or an alkoxy p,
  • alkyl preferably C -C alkyl
  • cycloalkyl or aralkyl substituted amino or hydroxy group preferably a monoalkyl amino group, a dialkylamino group or an alkoxy p
  • Z represents a conjugated system, e.g. a polymethine chain or an azamethine chain including such chain that is substituted or makes part of a ring structure, e.g. a phenylene or a naphthylene ring,
  • R represents hydrogen, a hydrocarbon radical e.g. an alkyl, an aryl or a heterocyclic group preferably a methyl group or a phenyl group, or the necessary atoms to form a homocyclic or heterocyclic ring with an atom of the group Z,
  • X represents oxygen or sulphur
  • Q represents the nonmetallic atoms necessary to complete a ring or ring system wherein the group is linked through a conjugated system to an electronattracting group, e.g. a carbonyl group, a thiocarbonyl group, a sulfonyl group or a dicyanomethylene group, or 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, e.g. a benzoxazole ring, Y represents an electron-attracting group, e.g.
  • Q represents a heterocyclic nucleus, containing an electron-donating group, e.g. a dialkylamino group that is linked through a conjugated system with the group wherein P and Q each represent an electron-attracting substituent, e.g. a cyano group or wherein P and Q together represent the necessary atoms to close a heterocyclic ring with electronegative character, e.g. as present in merocyanine dyes such as a ketomethylene ring of which a rhodanine nucleus is a particular example,
  • each of L and L represent a methine group or a substituted methine group
  • L represents a monovalent chemical bond, an a,p-ethylenically unsaturated bivalent group e.g. a
  • Preferred compounds falling within the scope of For- Preferred compounds falling within the scope of For- 10 male II are: a. c CH N- N ⁇ mc A cm 15 4. EC CH; I
  • nds falling within the scope of Formula IV are styryl dye bases and styryl vinyl dye bases and compounds such as:
  • HO H C N 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.:
  • n is a positive integer of at least 2
  • R represents hydrogen or an alkyl group including a substituted alkyl group.
  • Preferred compounds falling within the scope of class (D) are, e.g.:
  • CHz-CH CH3 1 H2 NH @LlH tetrahydro pyrimidine-Z-thiones, e.g.:
  • thiourea compounds including substituted derivatives preferably N-phenyl thiourea compounds, e.g.:
  • the photosensitive reactant for forming the dyestufi salt e.g. a photosentitive organic halogen compound such as carbon tetrabromide and/or iodoform in an amount of 10 to 250 parts by weight.
  • a photosentitive organic halogen compound such as carbon tetrabromide and/or iodoform in an amount of 10 to 250 parts by weight.
  • the grain size of the inorganic sensitizing agent is in the range applied in electrophotographic materials. Vacuum deposited layers having no graininess are, however, not excluded on condition that a working contact between the sensitizer layer and said mixture of Com pounds 1 and 2 exists.
  • the photosensitive recording layer according to the present invention contains 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.
  • antifoggants may be added to the photosensitive composition.
  • Suitable antifoggants include triaryl compounds of Group V elements, e.g. triphenylstibine and sterically hindered phenols, e.g. 2,6-di-tert.butyl p-cresol and other reducing or atmospheric oxygen accepting agents.
  • Triphenylstibine 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 dyestulf 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 chemi cally 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 (B) 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 photosensitive inorganic compounds applied in the present invention as sensitizing agent for the photochemical formation of the dyestuff salts may itself in a known way be sensitized spectrally by dyes useful for that purpose. So, when photoconductive zinc oxide is used it may be treated with the different types of spectral sensitizing agents known for it form its application in electrophotography.
  • Preferred spectral sensitizing dyes for the photosensitive composition used in the present invention belong to the class of the internally ionized dyes, e.g. merocyanines and the styryl and styryl vinyl dye bases as described, e.g. in Photographic Chemistry vol. II by P. Glafkides. Fountain PressLondon (1960), pp. 844-845 and in the French patent specification 1,574,740 filed Mar. 11, 1968 by Bell & Howell.
  • 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 solvent 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 solvent 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.
  • 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 poly-N-vinyl carbazole or the copolymers containing N-vinyl carbazole units in combination with the mercapto compounds of Class D.
  • a triarylstibine such as triphenylstibine to that combination intensifies the image density obtained by the optical development procedure.
  • Preferred recording layer compositions contain a spiropyran compound or mixture of spiropyran compounds and poly-N-vinylcarbazole in a ratio by weight within the range of :100 to 10: and a photosensitive polyhalogen compound such as carbon tetrabromide or iodoform or a mixture of both said polyhalogen compounds with respect to poly-N-vinylcarbazole in a ratio by weight in the range of 100 to 20:100.
  • photoconductive zinc oxide is preferably used in a ratio by weight of 1:4 with respect to the poly-N-vinyl carbazole.
  • Said recording layer compositions comprise preferably an anti-fogging agent e.g. triphenyl stibine or 2,6-di-tert. butyl-p-cresol.
  • an anti-fogging agent e.g. triphenyl stibine or 2,6-di-tert. butyl-p-cresol.
  • Preferred amounts of anti-fogging agent such as said p-cresol are with respect to photosensitive carbon tetrabromide and/or iodoform within the weight ratio range of 10:100 to 2.5:100.
  • the recording material is first overall exposed to electromagnetic radiation to produce nondilferentially over the whole recording layer latent dyestuif centers that are afterwards optically developed information-wise by a sufficiently strong information-wise exposure in the absorption band of the dyestufl centers.
  • 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 nonexposed 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 dyestuif 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 retflex type and also an optical projection exposure as applied, e.g. in an optical enlarging apparatus.
  • the information-wise exposure need not be simultaneous in all parts of the recording material.
  • the exposure may be progressive in one continuous step as, e.g. in sound track recording or in successive 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 secondary photons, e.g. of the ultraviolet radiation energy band and photoelectrons that are absorbed by the photosensitive polyhalogen compound forming through its photoradicals a dyestulf 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 ultraviolet light sources, xenongas lamps, incandescent bulbs, the light of the sun and flash lamps. In the overall exposure for the optical development an infrared 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 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 flexible 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 An intimate mixture of 500 mg. of carbon tetrabromide, mg. of di-fi-naphthospiropyran, 100 mg. of photoconductive zinc oxide (average grain size 10 micron) and 500 mg. of polystyrene dissolved in 8 ml. of methylene chloride was coated at a thickness of 0.1 mm. onto an unsubbed polyethylene terephthalate film. The coated layer was dried at 50 C.
  • the latent image was optically developed by an overall exposure by means of an infrared lamp of 250 w. (sold by Bie and Bernsten, 35 Pilestraede, Copenhagen, Denmark) emitting also in the visible part of the spectrum. Between the infrared lamp and the recording layer a cutoff filter was placed absorbing all the light with a wavelength smaller than 580 nm. (Corning C.S. 3-63).
  • iodoform 250 mg. of iodoform, 25 mg. of di-p-naphthospiropyran, 30 mg. of 2,6-ditert. butyl-p-cresol and 100 mg. of photoconductive zinc oxide prepared by oxidation of zinc vapor (average grain size 10 micron) 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 film.
  • the image was stabilized at C. and was free from background coloration.
  • EXAMPLE 3 A same photosensitive recording layer as discribed in Example 2 was prepared, but the 2,6-di-tert.butyl-p-cresol was left out of the composition.
  • Example 2 A same print-out exposure as described in Example 2 yielded the reproduction of 10 visible steps with a higher spectral density.
  • a thermal image stabilization was carried out at 120 C. and resulted in a cyan image with faint image background coloration.
  • EXAMPLE 4 A same photosensitive recording layer as described in Example 2 but containing in addition 5 mg. of a merocyanine dye having the following structure:
  • the obtained recording layer was image-wise contactexposed for 2 sec. in a 3M 179 (trade name) Contact Printer Processor using a light source emitting visible light.
  • the obtained latent image was optically developed by means of an overall exposure lasting 2 min. and effected by a 250 w. infrared lamp emitting through a cut-off filter absorbing all the light below 580 nm.
  • the visible image had an optical density of more than 1.
  • EXAMPLE 5 An intimate mixture of 300 mg. of carbon tetrabromide, mg. of iodoform, 30 mg. of di-B-naphthospiropyran,
  • the recording layer was image-wise contact-exposed for 0.5 sec. through a halftone transparency with an ultraviolet lamp type HPL-80 w. (trade name) placed at a distance of 10 cm.
  • a hardly visible image was obtained the density of which was increased by optical development proceeding with an overall exposure lasting 2 sec. and being carried out by means of an infrared lamp of 250 w. placed at a distance of 15 cm. Between the recording layer and the infra-red lamp a cut-off filter absorbing all the light below 540 nm. was placed.
  • the obtained visible image was stabilized by a rinsing treatment in butyl acetate.
  • EXAMPLE 6 A photosensitive composition consisting of 0.5 g. of carbon tetrabromide, 0.1 g. of yellow photoconductive lead(II)monoxide, 0.01 g. of di-fl-naphthospiropyran, and 8 ml. of a solution of polystyrene in methylene chloride was coated at a thickness of 0.10 mm. onto a nonsubbed polyethylene terephthalate support. The coating was dried at 50 C.
  • the latent image was optically developed by means of an overall exposure lasting 3 min. and elfected by means of a 250 w. infrared lamp placed at a distance of 15 cm. Between the infrared lamp and recording material a cutotf'filter (Corning CS 3-67) was placed absorbing all the light with a wavelength smaller than 540 nm.
  • the obtained cyan image having a density of 1.5 was stabilized by heating the recording material for several minutes at 120 C.
  • a same recording material but not containing the lead (II) monoxide needed an image-wise exposure of 2 min. and optical development exposure of 3 min. in order to yield the same image result as described above.
  • a photographic process for forming a visible image in a recording material which comprises in intimate admixture:
  • spiropyran compound of the group consisting of a spirodibenzopyran, a spirodinaphthopyran, a spirobenzonaphthopyran, a 1,3,3-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 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
  • said process comprising the steps of exposing said recording material to activating electromagnetic radiation of an intensity sufficient to produce a visible image directly or a latent image that can be rendered visible by optical development.
  • a photographic process according to claim 1 wherein the recording material after the formation of a visible image is overall heated to bring about image stabilization.
  • R, R R',, R R' R and R' each represent hydrogen, alkyl, alkyl substituted with halogen, alkyl substituted with an ester group, alkyl substituted with a carboxyl group, alkyl substituted with a N-phenylcarbamyl group, a hydroxy group, an alkoxy group, an aryloxy group, a phenyl group, piperidyl, acetyl,
  • said ultraviolet light-sensitive compound is carbon tetrabromide or iodoform.
  • said ultraviolet light-sensitive compound is a mixture of carbon tetrabromide and iodoform is used.
  • n is a positive integer of at least 2
  • R is hydrogen or an alkyl group.
  • said recording material contains as an antifogging agent a triaryl compound of a group V element or a sterically hindered phenol.
  • a process according to claim 1 wherein the exposure is a direct exposure.
  • 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:
  • at least one ultraviolet light-sensitive organic polyhalogen compound capable of producing on exposure with ultraviolet light a dye salt with the spiropyran compound and having the general formula:
  • 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, bromide 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
  • a photographic material according to claim 14 wherein said spiropyran compound corresponds to one of the following general formulae:
  • a material according to claim 14 wherein said ultraviolet light-sensitive compound is carbon tetrabromide or iodoform.
  • a material according to claim 14 wherein said ultraviolet light-sensitive compound is a mixture of carbon tetrabromide and iodoform is used.
  • n is a positive integer of at least 2
  • R is hydrogen or and alkyl group.
  • a photosensitive recording material according to claim 14, wherein the recording material contains said spiropyran compound in admixture with said photosensitive organic polyhalogen compound in a ratio by weight of 1:1-50.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
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US00177122A 1970-09-01 1971-09-01 Photochromic composition containing polyhalogenated hydrocarbon,spiropyran compound and zno or pb(ii) oxide and the use thereof Expired - Lifetime US3810763A (en)

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GB4174970A GB1359472A (en) 1970-09-01 1970-09-01 Photographic recording and reproduction of information

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US00177122A Expired - Lifetime US3810763A (en) 1970-09-01 1971-09-01 Photochromic composition containing polyhalogenated hydrocarbon,spiropyran compound and zno or pb(ii) oxide and the use thereof
US00177114A Expired - Lifetime US3813245A (en) 1970-09-01 1971-09-01 Photochromic composition containing polyhalogenated compound,spiropyran compound and sensitizer and the use thereof
US00177119A Expired - Lifetime US3810762A (en) 1970-09-01 1971-09-01 Photochromic composition containing polyhalogenated hydrocarbon,spiropyran compound and poly-n-vinylcarbazole and the use thereof

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US00177114A Expired - Lifetime US3813245A (en) 1970-09-01 1971-09-01 Photochromic composition containing polyhalogenated compound,spiropyran compound and sensitizer and the use thereof
US00177119A Expired - Lifetime US3810762A (en) 1970-09-01 1971-09-01 Photochromic composition containing polyhalogenated hydrocarbon,spiropyran compound and poly-n-vinylcarbazole and the use thereof

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US (3) US3810763A (enExample)
JP (1) JPS5443368B1 (enExample)
AU (1) AU3201171A (enExample)
BE (1) BE771848A (enExample)
CA (1) CA989236A (enExample)
DE (1) DE2142966A1 (enExample)
FR (1) FR2102042A5 (enExample)
GB (1) GB1359472A (enExample)
IT (1) IT943534B (enExample)
NL (1) NL7112021A (enExample)
ZA (1) ZA715241B (enExample)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4010033A (en) * 1973-08-03 1977-03-01 Agence Nationale De Valorisation De La Recherche (Anvar) Photosensitive layer and method of forming a photographic image therefrom
US4012232A (en) * 1974-12-23 1977-03-15 Nori Y. C. Chu Stabilized photochromic materials
US4029677A (en) * 1974-06-26 1977-06-14 Basf Aktiengesellschaft Spirodipyrans useful as dye precursors for copying processes
US4029506A (en) * 1974-10-21 1977-06-14 E. I. Du Pont De Nemours And Company Universal product code marking composition containing a photosensitive dye former, a pigment and a binder and the use thereof
US4101323A (en) * 1975-03-27 1978-07-18 Hoechst Aktiengesellschaft Radiation-sensitive copying composition
US4110348A (en) * 1976-03-19 1978-08-29 Basf Aktiengesellschaft 7,7'-Diamino derivatives of 2,2'-spirodibenzopyranes
US4207102A (en) * 1974-10-21 1980-06-10 E. I. Du Pont De Nemours And Company Marking transfer sheets and process
US4232108A (en) * 1979-05-01 1980-11-04 E. I. Du Pont De Nemours And Company Marking transfer sheets
US4342696A (en) * 1980-10-08 1982-08-03 Armstrong World Industries, Inc. 7-Dimethylamino-3-substituted-2,2'-spirobi[2H-1-benzopyrans]
US4348508A (en) * 1981-06-25 1982-09-07 Armstrong World Industries, Inc. 3-Substituted-7-alkoxy-2,2'-Spirobi[2H-1-benzopyrans]
US4382134A (en) * 1981-10-22 1983-05-03 Armstrong World Industries, Inc. 3-Substituted-7-alkoxy-spiro(2H-1-benzopyran-2,3'-(3H)-naphtho(2,1-B)pyrans)
US4384094A (en) * 1981-10-22 1983-05-17 Armstrong World Industries, Inc. 3-Substituted-7-dialkylamino-spiro(2H-1-benzopyran-2,3'-(3H)-naphtha(2,1-b)pyrans)
US4394439A (en) * 1981-05-28 1983-07-19 Robillard Jean J Non-silver X-ray recording process
US4845021A (en) * 1985-03-06 1989-07-04 Matsushita Electric Industrial Co., Ltd. Method for recording optical information in optical high density recording mediums

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS511424B1 (enExample) * 1971-04-20 1976-01-17
GB1432771A (en) * 1972-06-26 1976-04-22 Agfa Gevaert Recording method
DE2253637A1 (de) * 1972-11-02 1974-05-16 Licentia Gmbh Strahlungsempfindliches aufzeichnungsmaterial
US4039332A (en) * 1973-09-20 1977-08-02 Agfa-Gevaert N.V. Stabilization of photosensitive recording material
US3907570A (en) * 1974-03-19 1975-09-23 Scott Paper Co Photosensitive material comprising a furfurylidene, a lower haloalkane and poly-n-vinyl carbazole
US4106939A (en) * 1974-07-17 1978-08-15 Energy Conversion Devices, Inc. Imaging and recording of information utilizing a tellurium tetrahalide complex of an aromatic amine
GB1516847A (en) * 1974-11-12 1978-07-05 Agfa Gevaert Free-radical photographic material
JPS5315153A (en) * 1976-07-27 1978-02-10 Canon Inc Hologram
GB1587823A (en) * 1976-11-18 1981-04-08 Agfa Gevaert High intensity photon image recording
US4282309A (en) * 1979-01-24 1981-08-04 Agfa-Gevaert, N.V. Photosensitive composition containing an ethylenically unsaturated compound, initiator and sensitizer
JPS5664335A (en) * 1979-10-29 1981-06-01 Fuji Photo Film Co Ltd Photosensitive composition
US4346186A (en) * 1980-09-22 1982-08-24 Armstrong World Industries, Inc. Process for fixing photo-induced colored derivatives of spiropyrans and compositions therefor
US7147983B1 (en) * 1996-10-07 2006-12-12 Shipley Company, L.L.C. Dyed photoresists and methods and articles of manufacture comprising same
DE10039374A1 (de) * 2000-08-11 2002-02-21 Eml Europ Media Lab Gmbh Holographischer Datenspeicher

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1274655C2 (de) * 1965-12-15 1973-11-15 Speichermaterial zur aufzeichnung hochfrequenter signale

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4010033A (en) * 1973-08-03 1977-03-01 Agence Nationale De Valorisation De La Recherche (Anvar) Photosensitive layer and method of forming a photographic image therefrom
US4029677A (en) * 1974-06-26 1977-06-14 Basf Aktiengesellschaft Spirodipyrans useful as dye precursors for copying processes
US4207102A (en) * 1974-10-21 1980-06-10 E. I. Du Pont De Nemours And Company Marking transfer sheets and process
US4029506A (en) * 1974-10-21 1977-06-14 E. I. Du Pont De Nemours And Company Universal product code marking composition containing a photosensitive dye former, a pigment and a binder and the use thereof
US4012232A (en) * 1974-12-23 1977-03-15 Nori Y. C. Chu Stabilized photochromic materials
US4101323A (en) * 1975-03-27 1978-07-18 Hoechst Aktiengesellschaft Radiation-sensitive copying composition
US4316027A (en) * 1976-03-19 1982-02-16 Basf Aktiengesellschaft 7,7'-Diamino derivatives of 2,2'-spirodibenzopyranes
US4110348A (en) * 1976-03-19 1978-08-29 Basf Aktiengesellschaft 7,7'-Diamino derivatives of 2,2'-spirodibenzopyranes
US4345073A (en) * 1976-03-19 1982-08-17 Basf Aktiengesellschaft 7,7'-Diamino derivatives of 2,2'-spirodibenzopyranes
US4232108A (en) * 1979-05-01 1980-11-04 E. I. Du Pont De Nemours And Company Marking transfer sheets
US4342696A (en) * 1980-10-08 1982-08-03 Armstrong World Industries, Inc. 7-Dimethylamino-3-substituted-2,2'-spirobi[2H-1-benzopyrans]
US4394439A (en) * 1981-05-28 1983-07-19 Robillard Jean J Non-silver X-ray recording process
US4348508A (en) * 1981-06-25 1982-09-07 Armstrong World Industries, Inc. 3-Substituted-7-alkoxy-2,2'-Spirobi[2H-1-benzopyrans]
US4382134A (en) * 1981-10-22 1983-05-03 Armstrong World Industries, Inc. 3-Substituted-7-alkoxy-spiro(2H-1-benzopyran-2,3'-(3H)-naphtho(2,1-B)pyrans)
US4384094A (en) * 1981-10-22 1983-05-17 Armstrong World Industries, Inc. 3-Substituted-7-dialkylamino-spiro(2H-1-benzopyran-2,3'-(3H)-naphtha(2,1-b)pyrans)
US4845021A (en) * 1985-03-06 1989-07-04 Matsushita Electric Industrial Co., Ltd. Method for recording optical information in optical high density recording mediums

Also Published As

Publication number Publication date
FR2102042A5 (enExample) 1972-03-31
DE2142966A1 (de) 1972-03-09
AU3201171A (en) 1973-02-08
BE771848A (nl) 1972-02-28
NL7112021A (enExample) 1972-02-25
CA989236A (en) 1976-05-18
US3810762A (en) 1974-05-14
GB1359472A (en) 1974-07-10
JPS5443368B1 (enExample) 1979-12-19
ZA715241B (en) 1972-04-26
IT943534B (it) 1973-04-10
US3813245A (en) 1974-05-28

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