US3852093A - Heat-sensitive copy-sheet - Google Patents

Heat-sensitive copy-sheet Download PDF

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Publication number
US3852093A
US3852093A US00314687A US31468772A US3852093A US 3852093 A US3852093 A US 3852093A US 00314687 A US00314687 A US 00314687A US 31468772 A US31468772 A US 31468772A US 3852093 A US3852093 A US 3852093A
Authority
US
United States
Prior art keywords
reducing agent
sheet material
sheet
color
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00314687A
Other languages
English (en)
Inventor
Leary K O
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
3M Co
Original Assignee
Minnesota Mining and Manufacturing Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to US00314687A priority Critical patent/US3852093A/en
Priority to CA185,752A priority patent/CA981453A/en
Priority to IT7354272A priority patent/IT1000446B/it
Priority to JP48139269A priority patent/JPS4991239A/ja
Priority to FR7344295A priority patent/FR2330260A5/fr
Priority to GB5759873A priority patent/GB1399958A/en
Priority to DE2362377A priority patent/DE2362377B2/de
Application granted granted Critical
Publication of US3852093A publication Critical patent/US3852093A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • B41M5/28—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating
    • B41M5/286—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using thermochromic compounds or layers containing liquid crystals, microcapsules, bleachable dyes or heat- decomposable compounds, e.g. gas- liberating using compounds undergoing unimolecular fragmentation to obtain colour shift, e.g. bleachable dyes
    • 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
    • Y10S430/165—Thermal imaging composition

Definitions

  • thermographic copying wherein a copy of a differentially radiation-absorptive original is made on a heat-sensitive copy-sheet product held in'heat-conductive contact therewith by briefly exposing the original to intense infra-red radiation.
  • the invention relates to novel heat-sensitive copy-sheet products.
  • the invention relates to copy-sheet products useful in making negative color projection transparencies.
  • the present invention employs a different class of color bodies and a different reaction system, and provides a heat-sensitive copy-sheet product which when locally heated, as in the thermographic copying process, is converted from a highly colored to a substantially colorless, and preferably a clear and transparent, form at the heated image areas without release of volatile decomposition products.
  • the heat-sensitive copy-sheet products of the present invention contain p-quinoneimine color bodies which undergo decolorization when heated at thermographically induced temperatures in reactive association with a mild reducing agent.
  • the color body is supplied in a matrix of film-forming binder as a coating on a paper, transparent film or other carrier or as a self-supporting film.
  • the reducing agent may be incorporated in the same matrix, or in an adjacent stratum supported on the carrier or on a separate carrier.
  • a particularly useful structure comprises a transparent flexible film carrier coated with a first stratum of p-quinoneimine color body in a transparent binder and overcoated with a mild reducing agent in a separate binder. Brief heating of the film product causes migration of at least one of the reactants and results in a decolorization of the color body at the heated area.
  • Reducible p-quinoneimine color bodies which are useful in the preparation of heat-sensitive copy-sheets of the invention include those having thestructural formula.
  • Ar is an aromatic radical and the R, R, R"
  • R' substituent radicals may be hydrogen, halogen, alkyl, alkoxy or amido, or wherein substituent radicals on adjacent carbon atoms may complete a fused polycyclic or heterocyclic ring, all as exemplified by 2 2-chloro-2'-methyl-N,N-diethylindoaniline 2-chloro-N(p-diethylamino-2-methylphenyl)-pbenzoquinoneimine 2-acetamido-N,N,-diethylindoaniline 3-methoxy-2'-methyl-N,N-diethylindoaniline N-( l-naphthyl )-p-benzoquinoneimine N-(2-naphthyl)-p-benzoquinoneimine N-(p-acetylphenyl)-p-benzoquinoneimine 2,6-dichloroindophenol sodium salt 2,3',6-trichloroindophenol sodium salt 2,6
  • quinolinoquinoneimine N-(2,4-diamino-5-methylphenyl)-pbenzoquinoneimine trihydrate indoferron N-(p-diethylamino-2-methylphenyl)-2-carboxylic-l 4-naphthoquinoneimine N-(p-dimethylaminophenyl l ,4-
  • Binder systems may include such polymeric materials as polystyrene, styrene-acrylonitrile or sytrene-acrylate copolymers, styrene-butadiene-acrylonitrile terpolymers, polyvinylchloride, vinyl chloride-vinyl acetate copolymers, vinylidene chloride-acrylonitrile or vinylidene chloride-vinyl acetate copolymers, polyacrylates, polyvinyltoluene. These polymers are moistureresistant, being incapable of absorbing more than about one percent of water, and are preferred as contributing to the stability of the sheet materials during prolonged storage both before and after imaging.
  • the concentration of color body in the color stratum must be sufficient to impart a distinctive color but excessive amounts require undesirably large quantities of reducing agent, or excessive heating, or may reduce the transparency of the stratum and accordingly are to be avoided.
  • the amount of reducing agent available per unit area should be sufficient to react with all of the color body but need not be greatly in excess of that amount and, at least for single sheet projection transparencies, should be well within the range of full compatibility with the binder so that the stratum remains clear and non-light-diffusing.
  • EXAMPLE 1 A carrier film of 2 mil (0.05 mm.) ethylene glycol terephthalate polyester film primed with a trace coating of terpolymer primer is supplied with first and second reactant strata, with intermediate and final drying, as follows:
  • EXAMPLE 2 A solution containing 2-chloro-2'-mcthyl-N,N-dimethylindoaniline 0.6 polyvinyl chloride-acetate (VYNS" resin) l2.() methylethyl ketone 96 toluene 12 is applied to thin polyester film and dried in an oven at F. The dried coating is a deep blue in color and weighs 4.7 g./sq. m.
  • a solution containing tertiary butyl hydroquinone l h sec. nitrocellulose l polyamidc (Elvamidc 8061" resin) l methanol 97 is applied over the first coating at approximately the same wet coating thickness and is promptly dried in the 150F. oven.
  • the resulting film is imaged in a thermographic copying machine to provide a negative color projection transparency as in Example 1.
  • EXAMPLE 10 EXAMPLE 7 Coated over first coat at 2 mils (0.05 mm.) and dried.
  • the initial magenta color gradually fading during stor- The solutions are coated on separate sheets of thin age. Some improvement in performance may be polyester film, and the two sheets are combined and achieved by increasing the proportion of binder but processed, as in Example 6, with similar results. these sheets are generally less permanent and hence As an alternate structure a second sheet is prepared less desirable than those in which the 'tWO reactants are from a solution of ten parts of t-butyl hydroquinone in separate strata.
  • Second coat stannous chloride 1 vinyl acrylate latex (Ucar 360) (55% NVM) O Simple contact heating with heated type or stylus is also effective and permits more accurate determination of temperature if desired for comparison or test purposes.
  • Colored sheet material capable of undergoing localized loss of color when thermographically heated in presence of a reducing agent and containing a pquinoneimine color body in a film-forming binder, wherein said color body has the structure wherein Ar is an aromatic radical and the R, R, R and R' substituent radicals may be hydrogen, halogen, alkyl, alkoxy or amido, or wherein adjacent substituent radicals may constitute a fused polycyclic or heterocyclic ring.
  • Sheet material of claim 1 disposed in face-to-face relationship with a second sheet containing said reducing agent.
  • Sheet material of claim 3 wherein said reducing agent is a hydroquinone, catechol, resorcinol or trihydroxy-aromatic mild reducing agent.
  • Sheet material of claim 6 wherein said strata are supported on a thin flexible transparent film carrier.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US00314687A 1972-12-13 1972-12-13 Heat-sensitive copy-sheet Expired - Lifetime US3852093A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
US00314687A US3852093A (en) 1972-12-13 1972-12-13 Heat-sensitive copy-sheet
CA185,752A CA981453A (en) 1972-12-13 1973-11-14 Heat-sensitive copy-sheet
IT7354272A IT1000446B (it) 1972-12-13 1973-12-12 Perfezionamento nei materiali in fogli per riproduzione termogra fica
JP48139269A JPS4991239A (enrdf_load_stackoverflow) 1972-12-13 1973-12-12
FR7344295A FR2330260A5 (fr) 1972-12-13 1973-12-12 Feuilles thermocopiantes et leur procede de fabrication
GB5759873A GB1399958A (en) 1972-12-13 1973-12-12 Heat-sensitive copy-sheet
DE2362377A DE2362377B2 (de) 1972-12-13 1973-12-12 Farbiges thermographisches Blattmaterial

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00314687A US3852093A (en) 1972-12-13 1972-12-13 Heat-sensitive copy-sheet

Publications (1)

Publication Number Publication Date
US3852093A true US3852093A (en) 1974-12-03

Family

ID=23221008

Family Applications (1)

Application Number Title Priority Date Filing Date
US00314687A Expired - Lifetime US3852093A (en) 1972-12-13 1972-12-13 Heat-sensitive copy-sheet

Country Status (7)

Country Link
US (1) US3852093A (enrdf_load_stackoverflow)
JP (1) JPS4991239A (enrdf_load_stackoverflow)
CA (1) CA981453A (enrdf_load_stackoverflow)
DE (1) DE2362377B2 (enrdf_load_stackoverflow)
FR (1) FR2330260A5 (enrdf_load_stackoverflow)
GB (1) GB1399958A (enrdf_load_stackoverflow)
IT (1) IT1000446B (enrdf_load_stackoverflow)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2379833A1 (fr) * 1977-02-07 1978-09-01 Eastman Kodak Co Produit photographique thermodeveloppable
US4187108A (en) * 1977-02-07 1980-02-05 Eastman Kodak Company Heat developable material and process
US4265978A (en) * 1978-09-20 1981-05-05 Mitsubishi Paper Mills, Ltd. Heat-sensitive recording paper improved in keeping quality of ground color
US4594312A (en) * 1983-03-15 1986-06-10 Minnesota Mining And Manufacturing Company Heat bleachable dye systems
US5156709A (en) * 1991-07-30 1992-10-20 Xerox Corporation Fusible white stripe transparency sheets
US5290346A (en) * 1991-08-28 1994-03-01 Brother Kogyo Kabushiki Kaisha Ink for printer
US5314795A (en) * 1992-12-21 1994-05-24 Minnesota Mining And Manufacturing Company Thermal-dye-bleach construction comprising a polymethine dye and a thermal carbanion-generating agent
US5324627A (en) * 1992-12-21 1994-06-28 Minnesota Mining And Manufacturing Company Tetra-alkylammonium phenylsulfonylacetate thermal-dye-bleach agents
US5395747A (en) * 1993-12-20 1995-03-07 Minnesota Mining & Manufacturing Company Stabilized thermal-dye-bleach constructions
US5935758A (en) * 1995-04-20 1999-08-10 Imation Corp. Laser induced film transfer system
US5945249A (en) * 1995-04-20 1999-08-31 Imation Corp. Laser absorbable photobleachable compositions
US6294308B1 (en) 1999-10-15 2001-09-25 E. I. Du Pont De Nemours And Company Thermal imaging process and products using image rigidification
US20160202233A1 (en) * 2015-01-14 2016-07-14 International Business Machines Corporation Recyclate verification

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3524519A1 (de) * 1984-07-11 1986-01-16 Mitsubishi Chemical Industries Ltd., Tokio/Tokyo Farbstoffe fuer die waermeempfindliche sublimations-transferaufzeichnung
JPS6453893A (en) * 1987-08-25 1989-03-01 Fuji Photo Film Co Ltd Thermal transfer material

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3609360A (en) * 1969-09-15 1971-09-28 Joseph A Wiese Jr Negative projection transparencies and method
US3682684A (en) * 1971-03-10 1972-08-08 Minnesota Mining & Mfg Wide latitude heat-sensitive copy-sheet and method of making
US3684552A (en) * 1970-11-16 1972-08-15 Minnesota Mining & Mfg Heat-sensitive sheet material
US3715213A (en) * 1969-02-19 1973-02-06 Mita Industrial Co Ltd Diazo-type multicolor reproduction
US3730677A (en) * 1969-07-08 1973-05-01 Oreal Dyeing keratinous fibers with a quinoneimine and a coupler
US3751249A (en) * 1971-03-15 1973-08-07 Eastman Kodak Co Photothermic silver halide element containing a bis-beta-naphthol reducing agent and a 1, 3-dihydroxy-benzene reducing agent
US3764333A (en) * 1972-05-15 1973-10-09 Nashua Corp Thermographic copy sheet containing 2-phenyl 1,3-indanedione

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3715213A (en) * 1969-02-19 1973-02-06 Mita Industrial Co Ltd Diazo-type multicolor reproduction
US3730677A (en) * 1969-07-08 1973-05-01 Oreal Dyeing keratinous fibers with a quinoneimine and a coupler
US3609360A (en) * 1969-09-15 1971-09-28 Joseph A Wiese Jr Negative projection transparencies and method
US3684552A (en) * 1970-11-16 1972-08-15 Minnesota Mining & Mfg Heat-sensitive sheet material
US3682684A (en) * 1971-03-10 1972-08-08 Minnesota Mining & Mfg Wide latitude heat-sensitive copy-sheet and method of making
US3751249A (en) * 1971-03-15 1973-08-07 Eastman Kodak Co Photothermic silver halide element containing a bis-beta-naphthol reducing agent and a 1, 3-dihydroxy-benzene reducing agent
US3764333A (en) * 1972-05-15 1973-10-09 Nashua Corp Thermographic copy sheet containing 2-phenyl 1,3-indanedione

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2379833A1 (fr) * 1977-02-07 1978-09-01 Eastman Kodak Co Produit photographique thermodeveloppable
US4187108A (en) * 1977-02-07 1980-02-05 Eastman Kodak Company Heat developable material and process
US4265978A (en) * 1978-09-20 1981-05-05 Mitsubishi Paper Mills, Ltd. Heat-sensitive recording paper improved in keeping quality of ground color
US4594312A (en) * 1983-03-15 1986-06-10 Minnesota Mining And Manufacturing Company Heat bleachable dye systems
US5156709A (en) * 1991-07-30 1992-10-20 Xerox Corporation Fusible white stripe transparency sheets
US5290346A (en) * 1991-08-28 1994-03-01 Brother Kogyo Kabushiki Kaisha Ink for printer
US5314795A (en) * 1992-12-21 1994-05-24 Minnesota Mining And Manufacturing Company Thermal-dye-bleach construction comprising a polymethine dye and a thermal carbanion-generating agent
US5324627A (en) * 1992-12-21 1994-06-28 Minnesota Mining And Manufacturing Company Tetra-alkylammonium phenylsulfonylacetate thermal-dye-bleach agents
US5384237A (en) * 1992-12-21 1995-01-24 Minnesota Mining And Manufacturing Company Quaternary-ammonium phenylsulfonylacetate thermal-dye-bleach agents
US5395747A (en) * 1993-12-20 1995-03-07 Minnesota Mining & Manufacturing Company Stabilized thermal-dye-bleach constructions
US5935758A (en) * 1995-04-20 1999-08-10 Imation Corp. Laser induced film transfer system
US5945249A (en) * 1995-04-20 1999-08-31 Imation Corp. Laser absorbable photobleachable compositions
US6171766B1 (en) 1995-04-20 2001-01-09 Imation Corp. Laser absorbable photobleachable compositions
US6291143B1 (en) 1995-04-20 2001-09-18 Imation Corp. Laser absorbable photobleachable compositions
US6294308B1 (en) 1999-10-15 2001-09-25 E. I. Du Pont De Nemours And Company Thermal imaging process and products using image rigidification
US6569585B2 (en) 1999-10-15 2003-05-27 E.I. Du Pont De Nemours And Company Thermal imaging process and products using image rigidification
US20160202233A1 (en) * 2015-01-14 2016-07-14 International Business Machines Corporation Recyclate verification
US9708463B2 (en) 2015-01-14 2017-07-18 International Business Machines Corporation Recyclate verification
US9778244B2 (en) 2015-01-14 2017-10-03 International Business Machines Corporation Recyclate verification
US9783645B2 (en) 2015-01-14 2017-10-10 International Business Machines Corporation Recyclate verification
US9908989B2 (en) * 2015-01-14 2018-03-06 International Business Machines Corporation Recyclate verification

Also Published As

Publication number Publication date
FR2330260A5 (fr) 1977-05-27
DE2362377B2 (de) 1975-12-11
JPS4991239A (enrdf_load_stackoverflow) 1974-08-31
IT1000446B (it) 1976-03-30
CA981453A (en) 1976-01-13
GB1399958A (en) 1975-07-02
DE2362377A1 (de) 1974-07-04

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