Classifications

• • 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
  • Y10S430/163—Radiation-chromic compound

Definitions

• At least one ultra-violet radiation-sensitive compound capable of producing on exposure with ultra-violet radiation with the spiropyran compound a dye salt, and in working relationship with said mixture an organic compound, which is an amido, acylamino or ureido compound corresponding to the following general formula:
• R represents an organic group of the type present in a carboxylic acid chloride, at 1 1HR or a 20 Claims, No Drawings PHOTOCHROMIC MATERIAL CONTAINING A SPIROPYRAN COMPOUND, A POLYI-IALOGENATED HYDROCARBON PHOTOACTIVATOR AND AN ACETANILIDE SENSITIZER AND THE USE THEREOF IN PHOTOIMAGING
• This invention relates to photographic recording and reporduction of information and to materials suited therefor.
• spiropyrans used in the manufacture of photographic recording materials is known e.g. from the U.S. Pat. No. 2,953,454 of E. Berman Nat. Cash Reg, issued Sept. 20, 1960.
• the spiropyrans described therein are characterized as being reversibly transformable into a coloured form by activating electromagnetic energy.
• optical development for it operates with an overall exposure in the wavelength range of electromagnetic radiation absorbed by dyestuff traces formed in the image-wise exposure.
• At least one spiropyran compound and 2. at least one ultra-violet radiation-sensitive compound capable of producing an exposure to ultraviolet radiation with said spiropyran compound a dyestuff salt, is increased by using in working'relationship with said mixture an organic compound being: an arnido, acylamino or ureido compound corresponding to the following general formula:
• the starting substances for these radicals are preferably halogenated organic compounds.
• Said method is R represents an organic group e.g. of the type present in a carboxylic acid chloride e.g. an alkyl group, an aryl group or heterocyclic group including these groups in substituted form, or a NHR or the general formula are listed in the following Table 1.
• CHQNH o o Spiropyran compounds suited for photographic group, halogen, nitro, hydroxy, alkoxy, aryloxy or a image formation according to the present invention are substituent linking the carbon atoms in 3,3-position in spiropyrans containing at least one pyran ring having in the spiropyran system together eg a (CH ),,-chain the orthoand meta-position to the oxygen atom a conwherein n is 2 or 3, densed benzo, naphtho or-other higher aromatic polycychc c9ndensed "8 3 mcludmg
• General formulae covering particularly suited spirodensed rings or ring systems in substituted state e.g. an pyrans are the following; anthraceno or a phenanthreno ring system e.g. as present in a spirodibenzopyran, a spirodinaphthopyran, a
• 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 Cl-l -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' R and R' represents hydrogen
• an aliphatic group including a substituted aliphatic group e.g. a (C -C alkyl group including such an alkyl group in substituted fonn, 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 asubstituted phenyl group, piperidyl, an alkylene ester group e.g. a CH -COOC H group, an alkylene carboxyl group e.g. a CH- --COOH group, a carbonamide group or a substituted carbonamide group e.g. a
• R and R together represent a -(Cl-l chain wherein n 2 0r 3 to link the carbon atoms in the 3 and 3' positions.
• Preferred spiropyran compounds are spirodinaphthopyrans and spirobenzonaphthopyrans including such compounds wherein the naphtho-- and/or benzo ring(s) is (are) substituted.
• the pyrylium salt formed is separated by suction, is washed with ethanol, and thereupon suspended 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 preferably an organic polyhalogen compound, from which a halogen-containing radical can be separated photolytically.
• organic polyhalogen compound from which a halogen-containing radical can be separated photolytically.
• each of A, B, X, and Y are halogen atoms of thegroup of chlorine, bromine, or iodine, or wherein one of said groups A, B, X, or Y represents an alkyl group, including a substituted alkyl group
• the amount of the sensitizing agent according to the above general formula may vary within a wide range depending on the intensity of the desired effect.
• Preferred amounts of sensitizing agent are in the weight ratio range of 1:1 to 0.121 with respect to the spiropyran compound(s).
• the spiropyran compound(s) are used preferably 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 not limitative since useful results can be obtained with e.g. the spiropyran and photosensitive polyhalogen compound in a xati bxa jshtip th raqsasilal to
• a sensitizing agent of the above general formula may be used alone grin combination with one or more other 17 sensitiz'ingcompounds belonging to one of the following classes:
• Useful sensitizing agents of class (A) are those having one of the following general formulae (1), (II), (III), W 9st,
• 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 group,
• alkyl preferably C -C alkyl
• cycloalkyl or aralkyl substituted amino or hydroxy group preferably a monoalkyl amino group, a dialkylamino group or an alkoxy group
• 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 group 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 an electronegative atom or group e.g.
• oxygen N-R wherein R is hydrogen or an aromatic group, sulphur, selenium,
• 0 represents the non-metallic atoms necessary to.
• ocarbonyl group a sulf onyl group or a dicyano methylene group, or represents the atoms necessary to form with the carbon atom of the group Y represents anelectron-attracting group e.g.
• vQ represents a heterocyclic nucleus containing an electron-donating group e.g. a dialkylamino group that is linked through a conjugated system with the g up...
• P and Q each represent an electronattracting substituent e. g. a cyano group or wherein P and Q together represent the atoms necessary to close a heterocyclic ring with electronegative character e.g. as present in merocyanine dye-s such as a ketomethylene ring, the rhodanine nucleus being group or a plurality of said groups linked to each other, or L L and L together represent a double bond linkingthe group to the group Preferred compounds falling within the scope of for- 19 20 Preferred compounds falling within the scope of for- Preferred compounds falling within the scope of formula (ll) are:
• O mula (IV) are styryl dye bases and styryl vinyl dye bases and compounds such as:
• H3O CHa /N CH C H0 N ⁇ 3 0, A 3 w s r ,,.r-.
• 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 November 16, 1965 by Eastman Kodak Co. Represenet r es, hsreqf e e. .-a or (lJHa Hg Hg,
• n is a positive integer of at least 2
• R represents hydrogen or an alkyl group including a substituted alkyl group.
• Z represents a sulphur atom or a single bond
• A represents a single bond or a bivalent hydrocarbon group e.g. a CH group
• R represents hydrogen or a lower alkyl group, e.g. a
• R represents hydrogen or alo'wer alkyl group, e.g. a
• each of Q3 and Q4 represent a hydrogen atom or together the atoms necessary 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-vinyl polymers pared 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, it can vary between wide limits, say, e.g.
• N-vinylcarbazole copolymers The preparation of suitable N-vinylcarbazole copolymers is described in the United Kingdom Patent Specification 964,875 filed April 21, 1960 by Gevaert Photo-Producten N.V. which specification also contains a preparation receipt for poly(l ⁇ l-allyl carbazole) (R CH and R H)and for po1y(N-propenyl carbazole) (R, H, R H, A Cl-l
• 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 IBM. Corp.
• the polyN-vinyl diphenylamine is described in the published German Patent Application 2,007,692 filed Mar. 3, 1969 by Xerox corp.
• 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 Electric Industrial Co. Ltd.
• suitable vinyl copolymers' and copolymers can be copolymer of N-vinylcarbazole and n-butyl acrylate Table 2-Cont1nued Copolymer mole of N-vinyl carbazole copolymer of N-vinylcarbazole and 2-ethyl 51.6 hexylacrylate copolymer of N-vinylcarbazole and 76.6 acryloxyethyldiethylamine copolymer of Nvinylcarbuzole and vinyl cinnamate 92.5 copolymer of N-vinylcarbazole and methyl 62.7 methacrylate copolymer of N-vinylcarbazole and isobutyl 51.8 methacrylate copolymer of N-vinylcarbazole and'lauryl 77.4 methacrylate copolymer of N-vinylcarbazole and 9.7 methylacryloxyethyl diethylamine
• benzselenazole benzoxazole, or benzimidazole ring.
• useful sensitizing agents of class (D) are:
• imidazolidine-4-on-2-thiones e. g.:
• thiourea compounds including substituted derivatives preferably N-phenyl thiourea compounds, e.g.:
• thioamides e.g.:
• the recording layer preferably contains from 5 to 50 parts by weight of zinc oxide dispersed in parts by weight of binding agent containing the spiropyran compound(s) preferably in an amount of l 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 10 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 10 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 may be used in admixture for improvement of the mechanical strength or adhesion of the recording layer to its support when no selfsupporting layer is produced.
• antifoggants In order to diminish the rate of spontaneous thermal colour formation over long periods of time as might be encountered during storage of the photographic material and processing of the photographic materials socalled antifoggants maybe added to the photosensitive composition.
• Suitable anti-foggants include tr'raryl compounds of group V elements e.g. triphenylstibine and sterically hindered phenols e.g. 2,6 di-tert.butyl pcresol 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 No. 1,071,104 filed Aug. 14, 1964 by Horizons Inc.
• Preferred amounts of anti-fogging agent such as triphenyl stibine are with respect to photosensitive carbon tetrabromide and/or iodoform within the weight ratio range of 1:100 to 2.51100.
• a dry photographic coating containing the above mentioned ingredients may be formed by dissolving the binding agent(s) in a suitable inert solvent acting as dispersing or dissolving medium for the other ingredients and which is removed from the coating composition byevaporation, thus leaving a solid photographic recording layer on a properly chosen support.
• the supports may be of any kind used 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 dyestuff salt normally are sensitive only in a wavelength range between 400 and 250 nm.
• the recording materials of the present invention containing spirodiarylopyrans and the sensitizing agents of the general formula show especially in combination with polymers and copolymers containing N- vinylcarbazole units and serving as binding agent a remarkable high white and more particularly red light sensitivity.
• This unexpectedly high sensitivity in the visible spectrum range is increased yet,.when during the visible light exposure the temperature of the recording layer composition israised above 40C.
• a very suitable operating temperature is in the range of 4070C.
• the recording materials sensitized according to the present invention are suited to product print-out images of different colour depending on the type of spiropyran compound used.
• the stabilisation 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 evaporatingit by raising the temperature when the compound involved is sufficiently 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 to 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 above-mentioned photosensitive composition.
• 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 above-mentioned photosensitive composition.
• no exposure light is used, to which the photosensitive polyhalogen compound is inherently sensitive since thereby the effect of the image-wise exposure would be masked by an overall colouration.
• a filter absorbing all thelight corresponding with the wavelength range that is inherently absorbed by the ingredients of the non-previously exposed recording layer.
• the optical development effect is speeded up markedly and the image density is 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 poly-N-vinylcarbazole or the copolymers containing N-vinyl carbazole units in combination with the present amido, acylamino, or ureido compounds.
• a triarylstibine such as triphenylstibine to this combination intensifies the image densityobtained by the optical development procedure.
• a mixture of carbon tetrabromide and iodoform yielding a superadditive sensitivity-effect is used.
• the recording material is first overall exposed to electromagnetic radiation to produce non-differentially over the whole recording layer latent dyestuff centres that afterwards are optically developed information-wise by a sufficiently strong information-wise exposure in the absorption bend of the dyestuff centres.
• the information-wise exposure proceeds simultaneously with an overall heating e.g. effected by an overall infra-red radiation 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 imagewise 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 dyestuff 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 likewise an optical projection exposure as used 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 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 transla tion 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 photoelectrons that are absorbed by the photosensitive polyhalogen compound forming through its photoradicals a dyestuff 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 radiation sources, xenon-gas lamps, incandescent bulbs, sunlight and flash lamps.
• an infra-red lamp emitting also in the visible spectrum is used preferably.
• 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 by the use of a proper sensitizing agent they can be applied to continuous tone or halftone re-' production. 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. Due to the very high resolving power of the recording materials (the dyestuffs are formed in molecularly divided form) the recording materials of the present invention are particularly suited formicrofrlm 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 record ing materials make them very useful in the field of document reproduction since in a reflex-contact exposure they offer print-out images of a sufficiently intense spectral density. 1
• a recording layer as described herein is used in conjunction with a magnetic recording layer and is more particularly applied to 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 is photographed on the recording layer of the present invention.
• Such a recording material'thus allows the storing of opticaland acoustic signals and the reproduction of both informations simultaneously.
• the present invention is illustrated by the following examples without, however, limiting it thereto.
• the precentages are by weight unless otherwise indicated.
• EXAMPLE 1 A mixture of 120 mg of carbon tetrabromide, 120 mg I of iodoforrn, mg of 3-methyl-di-B-naphthospiropyran, 60 mg of acetanilide, and 8 ml of a 5 solution of polystyrene in methylene chloride was coated on a non-subbed polyethylene terephthalate support.
• the image obtained was stabilized by heating the recording material for l min.;at 140C.
• EXAMPLE 2 A mixture of mg of carbon tetrabromide, 120 mg if iodoform, 100 mg of 3-methyl-di-B-naphthospiropyran, 20 mg of triphenylstibine, 60 mg of acetanilide, and 8 ml of a 5 percent poly-N-vinylcarbazole solution in methylene chloride was coated at a thickness of 0.1 mm on a non-subbed polyethylene terephthalate support.
• the coating was dried in the dark at room tempera ture.
• V I V 7 The same recording materials were used for the production of print-out images by means of a diazo copying apparatus marketed under the name ACT INA SH by La Cellophane, Paris, France, and operating with the ultraviolet radiation source of 1000 W.
• the stabilization of the images was carried out by heating the recording material for l min. at 180C.
• 120 mg of carbon tetrabromide, 120 mg of iodoform, 100 mg of 3-methyl-di-B-naphthospiropyran, 30 mg of triphenylstibine, and 60 mg of a sensitizing agent indicated by number in the description in Table 1 are dissolved in 8 ml of a percent solution of poly-N- vinylcarbazole in methylene chloride.
• the solutions are coated at a thickness of 0.1 mm.
• the recording layers were dried at room temperature in the dark and exposed for 30 sec. in contact with a grey wedge (constant 015) in a 3M PHOTOCOPIER 179 (trade name).
• the temperature of the exposed recording material was about 50C.
• the stabilization of the images was carried out by heating the recording materials for l min. at 180C.
• EXAMPLE 4 A mixture of 120 mg of carbon tetrabromide, 120 mg f do mi 9 m q -ms -d -flnap p qpyran, 30 mg of triphenylstibine, 60 mg of pisopropylacetanilide and 8 ml of a 5 percent solution of poly-N-vinylcarbazole in methylene chloride were coated at a thickness of 0.1 mm on a non-subbed poly- EXAMPLE 5 A mixture of 120 mg of carbon tetrabromide, 120 mg of iodoform, mg of 3-methyl-di-B-naphthospiropyran, 60 mg of acetanilide, 20 mg of triphenylstibine was dissolved in 8 ml of 5 percent poly-N-vinylcarbazole solution in methylene chloride.
• the solution was coated at a thickness of 0.1 mm on a non-subbed polyethylene terephthalate support.
• the coated layer was dried in the dark at room temperature.
• Print-out processing The recording material was exposed in a a 3M PHO- TOCOPIER 179 (trade name) through a step wedge of constant 0.15. The exposure lasted 30 sec and yielded a print-out image containing 11 visible steps.
• Optical development processing The recording material was exposed in the way de scribed for the print-out processing but through a transparent line original and with an exposure time of only 2 sec, whereby no directly visible image was obtained.
• the image-wise exposed recording layer was then overall exposed with a 250 W-infra-red lamp placed at a distance of 20 cm and irradiating the recording layer for 25 sec through a narrow band filter mainly transmitting light in the wavelength range of 600-610 nm.
• the density of the cyan image obtained was above 1.
• EXAMPLE 6 A mixture of 300 mg of carbon tetrabromide, 100 mg of iodoform, 100 mg of 3-methyl-di-B-naphthospiropyran, 30 mg of triphenylstibine, 60 mg of phenacetine, 5 mg of thio Michlers ketone, and 8 ml of a 5 poly- N-vinylcarbazole solution in methylene chloride was coated at a thickness of 0.1 mm on a non-subbed polyethylene terephthalate support. The resulting layer was dried in the dark at room temperature.
• the dry recording layer was exposed for 3 sec through a transparent line original in a 3M PHOTO- COPIER 179 (trade name). A print-out image of neutral colour tone with a density above I was obtained.
• EXAMPLE 7 A mixture of mg of carbon tetrabromide, 120 mg of iodoform, 100 mg of 3-methyl-di-B-naphthospiropyran, 60 mg of acetanilide, 30 mg of triphenylstibine, and 8 ml of a 5 percent solution of poly-N- vinylcarbazole was coated at a thickness of 0.1 mm on a polyethylene terephthalate support. The layer was dried at room temperature in the dark.
• a photographic process for forming a visible image in a recording material which comprises in intimate admixture:
• At least one ultra-violet radiation-sensitive compound capable of producing on exposure with ultra-violet radiation withthe spiropyran compound a dye salt and having the general formula 34 wherein:
• R is an alkyl group, an aryl group, or a NHR or group in which each of R and R is an alkyl group or an aryl group, and R represents hydrogen, or an alkyl or aryl group,
• said process comprising the steps of imagewise 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.
• said exposure pro prises a latent imageand said latent image is optically developed and comprising the steps of: imagewise exposing the recording material to activating electromagnetic radiation of an intensity sufficient to bring about a latent or barely visible image having an increased spectral sensitivity in a wavelength range outside the inherent sensitivity range of the ultra-violet light sensitive compound, and then uniformly exposing the entire imagewise exposed recording material to light within the wavelength range for which the initially exposed portions are of increased sensitivity relative to the initially non-exposed portions, thereby increasing the visibility of said initially formed image.
• 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 30 a carboxyl group, alkyl substituted with a N- phenylcarbamyl group, a hydroxy group, an alkoxy group, an aryloxy group, a phenyl group, piperidyl, acetyl, halogen, nitro, or R and R, together represent a (CH ),,chain wherein n 2 or 3 to link 35 the carbon atoms in the 3 and 3 positions together.
• 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 (1), (II), (III), (IV), (V)
• D represents an elctron-donating group selected from an amino group substituted with alkyl, cy-
• Z represents a polymethine chain, an azamethine chain, phenylene or naphthaline,
• 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 2,
• Q represents the necessary atoms to form with the V 7 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 V n in X has the above meaning, M
• Q represents a heterocyclic nucleus, containing an alkylamino group
• P and Q each represent an electron-attacting cyano group, or P and Q together represent the necessary atoms to close a heterocyclic ring with electronegative character
• each of L L represent a methine group
• L represents a monovalent chemical bond
• V I wher group or a plurality of such groups linked to each other, or L L and L represent together a double bond linking the group to the group B.
• said ultra- A violet radiation-sensitive compound is carbon tetrabromide, iodoform, or a mixture thereof.
• the recording material contains as anti-fogging agent at least I" CH8 I 10 one of a triaryl compound of a group V element or a J:--o sterically hindered phenol.
• a photosensitive recording material for the direct ,Of h followmg general s e a production of a visible image by imagewise exposure to activating electromagnetic radiation which comprises a l 1 layer of an intimate mixture consisting essentially of:
• cH- I 1. at least one sprropyran compound ofthegroup A conslstlng of a spirodibenzopyran, a spirodinaphl; thopyran, a spirobenzonaphthopyran, a 1,3,3- Qa- Q1 trimethylindolinobenzospiropyran, a 1 ,3 ,3- I trimethylindolino-naphthospiropyran, or a spiropy- Q2 ran that contains a condensed aromatic nucleus of Z anthracene or phenanthrene, 2. at least one ultra-violet radiation-sensitive comwherein. i
• Z represents a sulphur atom or a single bond
• F- capable pr9ducmg exposure with A represents a single bond or a divalent hydrocap tra-vlolet radiation with the spiropyran compound be group
• a dye salt and having the general formula R represents hydrogen or a lower alkyl group
• a X R represents hydrogen or a lower alkyl group
• Q and'Q each represent a hydrogen atom or together the necessary atoms to close an adjacent B Y carbocychc nucleus 40
• each of A, B, X and Y is a chlorine, bromine
• Q and Q4 each represent a hydrog atom or iodine atom
• A, B, X or Y is gether the necessary atoms to close an ad acent an alkyl group, an aryl group or an amy] group and the carbocychc nucleus
• other groups are each chlorine, bromine, or iodine, or n represents

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  • BE BE786973D patent/BE786973A/nl unknown
• 1971
  • 1971-08-27 GB GB4034971A patent/GB1393868A/en not_active Expired
• 1972
  • 1972-07-31 IT IT86267/72A patent/IT968385B/it active
  • 1972-08-04 CA CA148,801A patent/CA991002A/en not_active Expired
  • 1972-08-16 FR FR7229392A patent/FR2150786B1/fr not_active Expired
  • 1972-08-24 JP JP47084961A patent/JPS4832532A/ja active Pending
  • 1972-08-24 DE DE2241563A patent/DE2241563A1/de active Pending
  • 1972-08-25 US US00283756A patent/US3820995A/en not_active Expired - Lifetime

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