US3887808A - Thermoimaging process utilizing a photochromic material containing a spiropyran, a polyhalogenated hydrocarbon, a thiol compound and a polyvinylcarbazole - Google Patents

Thermoimaging process utilizing a photochromic material containing a spiropyran, a polyhalogenated hydrocarbon, a thiol compound and a polyvinylcarbazole Download PDF

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US3887808A
US3887808A US372938A US37293873A US3887808A US 3887808 A US3887808 A US 3887808A US 372938 A US372938 A US 372938A US 37293873 A US37293873 A US 37293873A US 3887808 A US3887808 A US 3887808A
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compound
spiropyran
exposure
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layer
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Den Houte Jozef Willy Van
Royen Freddy Ghisleen Van
Goethem Hugo Vital Van
Edwin Hendrik Hazenbosch
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Agfa Gevaert NV
Agfa Gevaert AG
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • 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

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  • PATENTS be a polymer containing N-vinylcarbazole units. aum .1 3.642.479 2 1972 Van Allen et al. 96/90 PC 15 Claims, 2 Drawing Figures THERMOIMAGING PROCESS UTILIZING A PHOTOCIIROMIC MATERIAL CONTAINING A SPIROPYRAN, A POLYIIALOGENATEI) HYDROCARBON, A THIOL COMPOUND AND A POLYVINYLCARBAZOLE
  • This invention relates to thermographic recording.
  • the Belgian Pat. No. 771,848 relates to a photographic process, wherein a recording material, containing an intimate mixture comprising 1. at least one spiropyran compound,
  • At least one ultraviolet-sensitive compound capable of producing on exposure to ultra-violet radiation with the spiropyran compound a dye salt, and in working relationship with said mixture one or more compounds belonging to one of the following classes:
  • Z represents sulphur or a single bond.
  • A represents a single bond or a divalent hydrocarbon group.
  • each of R, and R represents hydrogen or a lower alkyl radical
  • each of Q. and O represents hydrogen or to gether represent the necessary atoms to cclose an adjacent carbocyclic nucleus including a substituted adjacent carhocyclic nucleus
  • n 1 or 2
  • inorganic compounds producing photoelectrons under the influence of activating electromagnetic radiation and having a basic or amphoteric character
  • the United Kingdom Patent Application No. 40,349/71 being a modification of the United Kingdom Patent Application No. 4] ,749/70, which corresponds with the above-mentioned Belgian Pat. No. 771,848 relates to the use of an amide, acylamino or ureido compound in a photographic process operating with said spiropyran and ultraviolet-sensitive compound.
  • the amido, acylamino, or ureido compound used in admixture with said spiropyran compound and ultraviolet-sensitive compound corresponds to the following general formula:
  • 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 group, in which each of R and R represents an alkyl group or an aryl group, e.g. a phenyl group including these groups in substituted form, and
  • R represents hydrogen or an organic group as is di rectly linked to the NH; group of an organic amino compound, e.g. an alkyl group, an aryl group, or a heterocyclic group including these groups in substituted form.
  • the recording material is exposed with infrared radiation and a minor amount of visible light while being in heat-conductive contact with an original containing infrared-absorbing image markings.
  • the exposure is preferably reflectographical i.e. the in frared radiation is allowed to pass first through the recording material before it strikes the original.
  • the infraredabsorbing image markings of the original are heated and the heat gener ated in these markings is transmitted by conduction to the recording layer.
  • the infrared-absorbing image markings are. e.g.. printed characters the ink of which contains carbon black or a metallic compound.
  • FIG. 1 and HO. 2 Two possible ways of effecting reflectographic exposure are illustrated in the accompanying FIG. 1 and HO. 2.
  • a photosensitive material 1 comprising a photo-sensitive layer 2 applied to a support 3, which is capable of transmitting infrared radiation and visible light is placed between the infrared radiation source 4 and the original 5 bearing infra-red-absorbing indicia 6, during the exposure.
  • the photosensitive layer 7 of the photosensitive material 12 is facing the infrared radiation source 8.
  • the support 9 of the photosensitive layer 7 is in contact with the infrared-absorbing indicia 10 of the original 11.
  • the support 9 of the photosensitive layer 7 is thin and heatconducting.
  • the infrared exposure source emits infra-red radiation and a minor amount. e.g. up to percent of visible light.
  • Spiropyran compounds suited for photothermographic 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 form, e.g. an anthraceno or a phenanthreno ring system as is present e.g. 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 condensed benzo In said spiropyrans the pyran rings, the condensed benzo. the condensed higher aromatic rings as well as the l.3.3 trimeth vlindolino ring may be substituted.
  • Suitable substituents therefor are, erg. hydrocarbon groups such as alkyl groups, e.g. lower alkyl groups such as methyl. substituted alkyl groups. e.g. substituted with halogen. or phenylsubstituted alkyl groups.
  • alkylene ester groups e.g. -CH COOC H alkylene carboxyl groups e.g. CH COOH, carbonamide groups or substituted carbonamide groups e.g.
  • 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-fl -chain wherein n is 2 or 3.
  • Preferred spiropyran compounds are spirodinaphthopyrans and spirobenzonaphthopyrzins including such compounds wherein the naphthoand/or benzo ring(s) is (are) substituted.
  • the pyrylium salt formed is separated by suction, washed with ethanol and thereupon brought into sus pension in 300 ml of ethanol.
  • a l0 percent by weight aqueous solution of ammonium hydroxide is added with stirring until the mixture is definitely alcaline. During this operation the mixture becomes colourless.
  • the obtained crystalline product is separated by suc tion, washed with water, and dried.
  • the compound capable of producing a dye salt with a spiropyran on exposure to activating electromagnetic radiation, for use according to the present invention is preferably an organic polyhalogen compound, from which a halogen-containing radical can be separated photolytically.
  • Compounds posssessing that property are within the scope of the following general formulazwherein:
  • each of A, B, X. and Y is a halogen atom of the group of chlorine. bromine or iodine, or
  • one of said symbols A, B. X, or Y represents an alkyl group, including a substituted alkyl group, e.g. a halogen-substituted alkyl group. a hydroxyalkyl group or an aralkyl group e.g. benzyl. an aryl group, a substituted aryl group. or a heterocyclic group e.g. a quinoxaline or quinaldine group or an aroyl group and the other symbols are chlorine. bromine or iodine, or wherein at least two of said symbols A, B, X or Y represent an aromatic acyl group e.g. benzoyl and the other symbols chlorine, bromine. or iodine.
  • a substituted alkyl group e.g. a halogen-substituted alkyl group.
  • a hydroxyalkyl group or an aralkyl group e.g. benzyl. an aryl group
  • Suitable representatives falling within the scope of that general formula are organic halides such as carbon tetrabromide. bromoform. iodoform, hexachloroethane, hexabromoethane, pentabromoethane. l,l.2.2- tetrabromoethane, a.ma-tribromoacetophenone. and tribromoethanol.
  • the recording materials used according to the pres ent invention containing a spirodiarylopyran compound and said thiol or thione compound in combina tion with poly-N-vinylcarbazole have a remarkably high sensitivity to white light and particularly to red light when spectrally sensitized with acetanilide or acetanilide derivatives.
  • the amount of spectral sensitizing agent may vary within a wide range depending on the intensity of the effect desired.
  • Preferred amounts of sensitizing agent are in the weight ratio range of 1:1 to 0.05:1 with respect to the spiropyran compound(s).
  • Preferred thiol and thione compounds correspond to the following tautomeric structures:
  • Z represents the necessary atoms to close a 5- or 6- membered heterocyclic nitrogen-containing ring or 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'or an aryl group.
  • ring system including such ring or ring system in .1 substituted form e.g. a benzothiazole, benzoselen- 0-5 azole, benzoxazole or benzimidazole ring.
  • Z Particularly useful thiol and thione compounds are listed in the following table 3.
  • N vinylcarbazole polymer or copolymer is preferably used as binding agent so that it is present in a large molar excess with respect to the spiropyran compound.
  • the spiropyran compoundts) is (are) preferably used in admixture with a 5- to -fold amount by weight of photosensitive organic halogen compound such as Carbon tetrabromide.
  • anti-foggants may be added to the photosensitive composition.
  • Suitable antifoggants include triaryl compounds of group V ele merits, e.g. triphenylstibine and sterically hindered phenols, e.g. 2,6-di-terLbutyl-p-cresol and other reducing agents or compounds accepting atmospheric oxygen.
  • Triphenylstibine and analogous compounds for the purpose of the present invention are described in the United Kingdom Pat. No. l,O7l,l04.
  • Preferred amounts of anti-foggant agent such as triphenylstibine are within the weight ratio range of 1:100 to 10:100 with respect to photosensitive carbontetra bromide and/or iodoform.
  • a dry photographic coating containing the above mentioned ingredients may be formed by dissolving the binding agenttsl in a suitable inert solvent that acts as dispersing or dissolving medium for the other ingredients and that is removed from the coating composition by evaporation so that a solid photographic recording layer is left on a properly chosen support.
  • the supports may be of any kind encountered in silver halide photographic materials, e.g. paper and film supports.
  • hydrophobic polymers are used preferably as binding agent. They shield the ingredients from a direct contact with the atmosphere and more especially from oxygen as much as possible.
  • Particularly suitable binders for use in the present invention are hydrophobic polymers and copolymers containing, e.g. styrene, vinyl acetate, acrylonitrile, acrylate, methacrylate, Nw'inylcarbazole or butadiene units, hydrophobic cellulose derivatives, phenoxy resins or polycondensates of the polyester type, eg. polycarbonates.
  • these polymers may be used in admixture for improvement of the mechanical strength or adhering power of the recording layer to its subbed or non-subbed support.
  • subbing layers for photochromic layers containing a spiropyran compound are described in the Belgian Pat. No. 782,026.
  • Said subbing layers applied to a polyester film support are made of a partially saponified copolymer of vinyl chloride and vinyl acetate and/or of a polymer or copolymer of acrylic or methacrylic acid esters of aliphatic or cycloaliphatic alcohols containing from 1 to 8 carbon atoms.
  • polyester resin supports It has been established experimentally that the adherence of recording layers containing poly-N- vinylcarbazole or copolymers containing N- vinylcarbazole units to polyester resin supports can be markedly improved by using in admixture with the N- vinylcarbazole polymer or copolymer a polyester, a phenoxy resin or a phenol-formaldehyde resin.
  • a preferably applied polyester resin is polyethylene isophthal ate.
  • a preferred phenoxy resin is EPONOL 55-8-40 of Shell, the Netherlands.
  • Suited phenolformaldehyde resins are: the polycondensatinn product of a mixture of p-cresol and phenol with formaldehyde (50:50), the polycondensation product of a mixture of ptert.butylphenol and phenol with formaldehyde, the polycondensation product of p-cresol and formaldehyde (used in excess) 2 xylenol-formaldehyde resin like RESlN R of Brit ish Resin Products. Great-Britain.
  • the resins improving the adherence are preferably used in a percentage by weight calculated on the re cording layer of at least 3 percent.
  • the infrared exposure of the recording materials used according to the present invention may proceed in any known thermographic copying apparatus of the reflectographic type.
  • a suitable operating temperature is in the range of 90 to 150C.
  • the recording materials are suited to produce coloured copies of image-wise infrared-absorbing originals, the colour of the dye-image being determined by the type of spiropyran compound used.
  • the prints obtained may be stabilized by washing out the residual free radical generator with a suitable solvent or solvent mixture, e.g. a hydrocarbon liguid such as petroleum ether optionally mixed with acetone, or by simply evaporating the free radical generator by raising the temperature if the compound involved is sufficiently volatile.
  • a suitable solvent or solvent mixture e.g. a hydrocarbon liguid such as petroleum ether optionally mixed with acetone
  • carbon tetrabromide having a high photosensitivity or a mixture of carbon tetrabromide and iodoform is preferred as free radical generator.
  • the stabilization proceeds with increased speed when the recording layer is first overall heated at about 80C in the absence of visible light for at least 5 sec. and then treated with a chlorinated solvent, e.g. perchloroethylene at room temperature (C) for at least l5 sec in order to extract the photosensitive polyhalogen compound.
  • a chlorinated solvent e.g. perchloroethylene at room temperature (C) for at least l5 sec in order to extract the photosensitive polyhalogen compound.
  • Stabilization may proceed very fast by dipping the exposed recording material in a heated organic liquid having a relatively high boiling point, preferably above 200C and not affecting the recording layer.
  • the organic liquid is preferably heated in the range of 145 to 165C and the dipping time is e.g. 5 to 20 sec.
  • Suitable liquids are mineral oil of aliphatic or naph' thenic nature e.g. motor oil and lSOPAR G (trade name).
  • a post-treatment with a solvent, e.g. a chlorinated hydrocarbon solvent may be necessary to remove the residual oil film.
  • a photosensitive composition consisting of:
  • the photosensitive film obtained was exposed reflectographically in a 3M Thermofax copying machine (Model 47) in contact with an opaque original being a black printed text on white paper. A dense blue positive image of the original was obtained.
  • the copy as such was not stable to light and had to be stabilized by heating at 170C.
  • EXAMPLE 2 A same photosensitive composition as in example 1 was used, with the difference, however, that 0.06 g of compound having the following formula:
  • thermographic exposure step as in example l was executed.
  • a photosensitive composition consisting of:
  • a photosensitive composition consisting of:
  • a photosensitive composition consisting of:
  • Reflectographic exposure proceeded according to the arrangement of FIG. 1 in a 3M Thermofax photo copier. model secretary, set at the lowest transport speed and yielded a very dense positive reproduction of the original.
  • a photosensitive composition consisting of:
  • Example 2 The material obtained was exposed and processed as described in Example 1. A deep blue image in a very good adhering scratch-resistant recording layer was obtained.
  • a photosensitive composition consisting of:
  • the stabilization of the image proceeded according to one embodiment by heating the recording layer whilst pressing it for 10 sec. in contact with a metal rol ler heated at C. Subsequently, the recording material was dipped for 15 sec at room temperature (20C) into perchloroethylene. The image thus obtained was stable to daylight and had an optical density of 1.80.
  • the stabilization could equally well be effected according to a second embodiment by dipping the exposed material for 5 sec. in lSOPAR G (trade name of Shell Company. the Netherlands. for a mixture of hydrocarbons boiling in the range of 166-170C) heated at C.
  • lSOPAR G trade name of Shell Company. the Netherlands. for a mixture of hydrocarbons boiling in the range of 166-170C
  • the recording layer containing the stabilized image was scratch-resistant and strongly adhered to its support.
  • N-vinyl polymers and copolymers containing N- vinylcarbazole units which can be used according to the invention can be prepared by application of one of the various known polymerization procedures, e.g., by pearlor emulsion polymerization or by polymerization in solution.
  • 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 may vary between wide limits.
  • the content of groups corresponding to the general formula given hereinbefore is not critical and. as shown hereinafter in the table of copolymers containing N-vinylcarbazole units. it may vary between wide limits, e.g.
  • copolymers having a content of vinylcarbazole units between 40 and 90 percent.
  • N-vinylcarbazole copolymers The preparation of suitable N-vinylcarbazole copolymers is described in the United Kingdom Pat. No. 964.875. which specification also contains a preparation receipt for poly(N-allyl carbazole) (R 2 CH and R H) and for poly(N-propenyl carbazole) (R. H. R H. A CH;).
  • Halogen-substituted poly-N-vinyl carbazoles are de scribed in the published Japanese Patent Applications 21.875/67, 25.230/67. 7.592/68. 19.751/67 and 7.59l/68.
  • a process for forming a dye image comprising applying a heat pattern having a temperature of at least 90C of the image in the presence of minor amounts of about up to 20% of visible light to a recording material including a recording layer containing an intimate mixture comprising:
  • At least one ultraviolet radiation-sensitive polyhalogen compound capable of producing on exposure with ultra-violet radiation with the spiropyran compound a dye salt and having the general formula:
  • each of A. B. X and Y is a chlorine. bromine or iodine atom. or one of said groups A. B. X or Y is an alkyl group. an aryl group or an aroyl group and the other groups are each chlorine. bromine. or iodine. or two of said groups A. B. X or Y each is an aromatic acyl group and the other groups chlorine. bromine. or iodine. and in working relation with said mixture at least one of the following compounds.
  • X represents oxygen. sulphur. selenium or the group in which R is hydrogen. or an alkyl. allyl. or phenyl group.
  • Z represent the necessary atoms to close a or 6- membered heterocyclic nitrogen-containing ring system, and b, a polymer containing N-vinylcarbazolc units.
  • pattern-wise heating olthe recording material proceeds by exposure thereof to infrared radiation and a minor amount of visible light while said layer is in heatconductive contact with an original containing infra red-absorbing image markings.
  • amido, acylamino or ureido compound corresponds to the following general formula:
  • R represents an organic residue of the type present in a carboxylic acid chloride, a l lHR or 12.
  • said process of claim 1 wherein said spiropyran compound corresponds to one of the general formulae:
  • R, R R',, R R R and R each represent hydrogen, alkyl, alkyl substituted with halogen, alkyl sub stituted 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, halogen, nitro, or R, and R together represent a -(CH- chain wherein n 2 or 3 to link carbon atoms in the 3 and 3' positions together.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US372938A 1972-06-26 1973-06-25 Thermoimaging process utilizing a photochromic material containing a spiropyran, a polyhalogenated hydrocarbon, a thiol compound and a polyvinylcarbazole Expired - Lifetime US3887808A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4151748A (en) * 1977-12-15 1979-05-01 Ncr Corporation Two color thermally sensitive record material system
US4184874A (en) * 1974-02-05 1980-01-22 Fuji Photo Film Co., Ltd. Photosensitive composition containing chelate compound
US4960679A (en) * 1985-01-31 1990-10-02 Canon Kabushiki Kaisha Image forming device
US5234798A (en) * 1991-10-04 1993-08-10 Dittler Brothers, Incorporated Thermal reactive structures
US5879866A (en) * 1994-12-19 1999-03-09 International Business Machines Corporation Image recording process with improved image tolerances using embedded AR coatings

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108665A (en) * 1976-10-07 1978-08-22 Minnesota Mining And Manufacturing Company Stabilizers for photothermographic constructions

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3359105A (en) * 1965-03-10 1967-12-19 Horizons Inc Speed-increasing agents for an nu-vinyl amine and organic halogen dye former system
US3451338A (en) * 1964-05-11 1969-06-24 Ncr Co Thermographic recording system
US3642479A (en) * 1970-03-02 1972-02-15 Eastman Kodak Co Photographic element and process
US3785820A (en) * 1972-02-18 1974-01-15 Canon Camera Co Photorecording process and photorecording member
US3810762A (en) * 1970-09-01 1974-05-14 Agfa Gevaert Nv Photochromic composition containing polyhalogenated hydrocarbon,spiropyran compound and poly-n-vinylcarbazole and the use thereof
US3820995A (en) * 1971-08-27 1974-06-28 Agfa Gevaert Nv Photochromic material containing a spiropyran compound a polyhalogenated hydrocarbon photoactivator and an acetanilide sensitizer and the use thereof in photoimaging

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3451338A (en) * 1964-05-11 1969-06-24 Ncr Co Thermographic recording system
US3359105A (en) * 1965-03-10 1967-12-19 Horizons Inc Speed-increasing agents for an nu-vinyl amine and organic halogen dye former system
US3642479A (en) * 1970-03-02 1972-02-15 Eastman Kodak Co Photographic element and process
US3810762A (en) * 1970-09-01 1974-05-14 Agfa Gevaert Nv Photochromic composition containing polyhalogenated hydrocarbon,spiropyran compound and poly-n-vinylcarbazole and the use thereof
US3820995A (en) * 1971-08-27 1974-06-28 Agfa Gevaert Nv Photochromic material containing a spiropyran compound a polyhalogenated hydrocarbon photoactivator and an acetanilide sensitizer and the use thereof in photoimaging
US3785820A (en) * 1972-02-18 1974-01-15 Canon Camera Co Photorecording process and photorecording member

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4184874A (en) * 1974-02-05 1980-01-22 Fuji Photo Film Co., Ltd. Photosensitive composition containing chelate compound
US4151748A (en) * 1977-12-15 1979-05-01 Ncr Corporation Two color thermally sensitive record material system
US4960679A (en) * 1985-01-31 1990-10-02 Canon Kabushiki Kaisha Image forming device
US5234798A (en) * 1991-10-04 1993-08-10 Dittler Brothers, Incorporated Thermal reactive structures
US5879866A (en) * 1994-12-19 1999-03-09 International Business Machines Corporation Image recording process with improved image tolerances using embedded AR coatings
US6309809B1 (en) * 1994-12-19 2001-10-30 International Business Machines Corporation Multi-layer integrated imaging/image recording process with improved image tolerances

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FR2191484A5 (enrdf_load_stackoverflow) 1974-02-01
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GB1432771A (en) 1976-04-22

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