US3421894A - Recording process utilizing 6'-nitro-1,3,3 - trimethyl-benzoindolinospiropyran dispersed in heat-meltable wax - Google Patents

Recording process utilizing 6'-nitro-1,3,3 - trimethyl-benzoindolinospiropyran dispersed in heat-meltable wax Download PDF

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Publication number
US3421894A
US3421894A US520325A US3421894DA US3421894A US 3421894 A US3421894 A US 3421894A US 520325 A US520325 A US 520325A US 3421894D A US3421894D A US 3421894DA US 3421894 A US3421894 A US 3421894A
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US
United States
Prior art keywords
wax
sheet
layer
heat
magenta
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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
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US520325A
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English (en)
Inventor
Henry H Baum
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.)
Appvion LLC
NCR Voyix Corp
National Cash Register Co
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NCR Corp
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Assigned to APPLETON PAPERS INC. reassignment APPLETON PAPERS INC. MERGER (SEE DOCUMENT FOR DETAILS). FILED 12/1781, EFFECTIVE DATE: 01/02/82 STATE OF INCORP. DE Assignors: GERMAINE MONTEIL COSMETIQUES CORPORATION (CHANGED TO APPLETON PAPERS), TUVACHE, INC.
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Expired - Lifetime legal-status Critical Current

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    • 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
    • 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
    • B41M5/282—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 thermochromic compounds
    • B41M5/284—Organic thermochromic compounds
    • 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

Definitions

  • PAPER-LIKE- F Q6 3 SENSITIZE comm swam 01- ncs. 1 on 2 mm HEAT SUFFICIENT T0 MELT wAx AND DISSOLVE THE ms 0 MAY BE 40 c. 80 c.
  • This invention relates to a process for using a record sheet sensitized by a layer of heat-meltable wax having dispersed in it the compound 6-nitro-1,3,3,-trimethylbenzoindolinospiropyran, by first heating the layer to fuse it, then subjecting the heated layer to an ultraviolet light pattern, representing the record, to form a precursor image, which image finally is fixed by a further heating step to form a fixed copy of distinctive color in the layer.
  • This invention relates to a printing and copying sheet, a system employing the sheet, and its use; and more particularly pertains to such a system employing as a chromogenic material the compound 6-nitro-1,3,3-trimethv benzoindolinospiropyran, which has the structure and which compound is used dispersed in a wax material taken from the group of waxes consisting of mineral wax, vegetable wax, synthetic fatty ester wax, and animal wax, such wax being characterized by having a solid state in the range of 20 degrees centigrade :20 degrees centigrade and a liquid state above 40 degrees centigrade, preferably in a layer, and is present there at various stages of its selective use either as a dispersed crystalline state (colorless), a heat-induced solute state (colorless), an ultravioletdight-induced activated state (magenta), a fixed state on heating (blue or colorless, according to whether or not it has experienced incident ultraviolet light while in heat-induced solute state), and a colorless state to which the activate
  • FIG. 1 represents a paper substrate coated with a layer of low-melting-point 40 degrees centigrade) wax solid at room temperature (10 degrees centigrade to 35 degrees centigrade) in which are originally dispersed fine crystalline particles of the specified chromogenic material, said crystals pervading the wax layer in amount and distribution so as to be individually detectable visually when colored.
  • FIG. 2 shows a substrate of paper coated with a polymeric material film in which are dispersed wax particles of the composition of the wax layer of FIG. 1, the wax particles, pervading the film, being supplied in large numbers and also being of small enough dimensions to escape individual attention of the eye except when colored, and the particles giving a continuous efiFect in the layer where adjacent particles are colored, so that printing of high visual resolution can be made thereon.
  • FIG. 3 is a flow diagram of the process steps in the preferred utilization of the sheet.
  • FIG. 4 is a structural representation of the dye.
  • This sheet is made by coating onto a substrate, such as paper, a hot melt of a 2%, by weight, solution of the specified chromogenic material in wax of the selected eligible class identified by being solid at room temperature and melting beginning at approximately 40 degrees centigrade, which is above the maximum temperature of use in normal living environment.
  • the cooled, dried, and solidified coating preferably should be about 1 to 3 mils in thickness, but the thickness can be somewhat more or less as desired.
  • the preferred wax is ethylene-glycol-monostearate, which melts at about 60 degrees centigrade.
  • This sheet is made as follows:
  • a solution is made of 50 parts, by weight, of ethylene-glycol-monostearate heated to 60 degree centigrade and 2 parts, by weight, of the specified chromogenic material.
  • the system is kept by any suitable means from assuming an acid condition.
  • the emulsion resulting from step (Hil) is coated on a substrate, such as paper, cooled, and dried, enough being used to leave a solid coating of 1 to 3 mils in thickness.
  • substitutes for the specified wax of sheets (I) and ('11) may be mentioned parafiin wax, micro-crystalline wax, carnauba wax, beeswax, spermaceti, and fatty acid esters.
  • Example I a print-making employing the sheet of BIG. 2 will be specified as Example I.
  • Example I a sheet of paper sensitized with the novel composition shown in 'FIG. 2 is heated for two seconds between the plates of a hot platen press, having a platen temperature of 70 degrees centigrade, and then is subjected through a negative photograph transparency to a linear gas are lamp discharge radiation rich in 3,500 to 4,000 Angstroms.
  • This exposure to ultraviolet light turns the sheet to a magenta color in areas corresponding to the light areas of the negative, tapering off in continuous tone to where the dark areas of the negative leave the sheet unexposed and colorless.
  • the sheet then is subjected to heating in the same hot platen press for five seconds, which turns the magenta areas to a blue of corresponding intensity.
  • This print is a positive in blue on a white background.
  • Example II This is exactly the same process as in Example I but carried out with the sheet of FIG. 1.
  • Example III In this example, certain selected areas of the magenta image of the sheet of Example I are subjected to green light before the layer is fixed to erase a corresponding part thereof, and thereafter the sheet is fixed by heat, as explained.
  • Example IV This example is like Example III, except that the sheet of FIG. 1 is used.
  • Example V This is the same as any of the preceding examples, except that a two-tone negative is used.
  • Example VI The uncolored sheet of FIG. 1 is sensitized in the hot platen press and then converted all over to the magenta sensitized condition by being flooded with the specified ultraviolet light.
  • This sheet may be selectively and differentially erased by green light controlled in any manner, the remaining magenta areas being fixed as in Example I by heating of the whole layer.
  • Example V-II A sheet, like the sheets of FIG. 1 and 2, that bears fixed images may be subjected to heat-sensitization to render the background colorless areas sensitized and then subjected to ultraviolet light patterns to exhibit the added data in magenta color, after which the sheet undergoes the five-second heat treatment to fix the image--in adda-frame manner; that is to say, the addition of data may be made at any time to any unused area.
  • magenta data is present as a two-color image or as a tone variation, in either an exposed FIG. 1 or FIG. 2 sheet-i.e., a variation in intensityits erasure may be made partial as to areas by timing the exposure to green light, the intensely magenta areas persisting in the green light after the weak magenta areas have disappeared.
  • Example lIX The time of exposure of a magenta area through a continuous tone negative determines the part of the area to be sufficiently printed to show blue development on heating. This is one other method of controlling selectively what is to be printed from a light control mask.
  • Example X In this example, using either the sheet of FIG. 1 or that of FIG. 2, the printing with ultraviolet light into magenta-colored areas may be controlled in one area by a negative transparency and in another area by a positive transparency. Obvious combinations are the use of superimposed negative transparencies used in any combination.
  • Example XI The sheet of either FIG. 1 or FIG. 2 may be controlled as to areas of sensitization by thermographic means in which a master sheet bearing data in terms of infrared-radiation-absorbing characters is placed in contact with the wax layer, to form a pair; then the pair is subjected to infrared radiation, which results in the appearance of corresponding magenta-colored sensitive areas in the waxy layer. When subjected to ultraviolet light and heat, the data is fixed in a blue color in the waxy layer.
  • magenta areas of this example are subject to erasure in the before-specified manner, either selectively or totally, and are fixed with the same degree of selectivity by applied heat to bring the layer, or an area thereof, to the fixing temperature for the longer period of time.
  • thermography heating to sensitize the sheet may be accomplished by the reflex technique, if desired, in which the infrared light is first passed through the docu ment to cause the printed data, which is printed in infrared-absorbent ink, to become hot and activate the waxy layer to become magenta in color.
  • thermographic means The application of heat in the examples has been by hot plate or thermographic means, but optically-directed infrared light directed against an absorption converter may be traced in any pattern to produce a corresponding heat pattern against which the novel waxy layer may be positioned in contact to be colored magenta according to the pattern.
  • a branding-iron type-i.e., heated type- may be used to apply heat conductively to the novel sheet.
  • the application of green light may be controllled optically by stationary or moving beam to erase a selected area of the magenta-colored area.
  • Ultraviolet light may be projected in a pattern onto a sheet at the same time it is being heated to sensitize it thereto, and the heating may continue on to fix the print made by the ultraviolet light.
  • step (c) is performed desired portions of the magenta area are erased to a colorless state by application of green light.
  • the process of copying a document bearing data as infra-red-absorptive characters including the steps of (a) heating a copy sheet provided with a Wax layer taken from the group of Waxes consisting of mineral wax, vegetable wax, synthetic fatty ester Wax, and animal wax, such Wax being characterized by having a solid state in the range of 20 degrees centigrade :20 degrees centigrade and a liquid state above 40 degrees centigrade having 6-nitro-1,3,3-trimethylbenzoindolinospiropyran dispersed in it to a temperature at which the Wax is substantially melted;

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US520325A 1966-01-13 1966-01-13 Recording process utilizing 6'-nitro-1,3,3 - trimethyl-benzoindolinospiropyran dispersed in heat-meltable wax Expired - Lifetime US3421894A (en)

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US52032566A 1966-01-13 1966-01-13

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US3421894A true US3421894A (en) 1969-01-14

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Country Status (5)

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US (1) US3421894A (de)
BE (1) BE692252A (de)
CH (1) CH476581A (de)
DE (1) DE1671563B2 (de)
GB (1) GB1109554A (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3715212A (en) * 1970-12-07 1973-02-06 Rca Corp Photochromic display and storage device and method of operation thereof
US4533567A (en) * 1983-05-24 1985-08-06 Ncr Corporation Carbonless paper coating formulation
WO1986003875A1 (en) * 1984-12-21 1986-07-03 Paul Jerome Banks Method and apparatus for handling information
US4960679A (en) * 1985-01-31 1990-10-02 Canon Kabushiki Kaisha Image forming device

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB810401A (en) * 1956-02-06 1959-03-18 Gunther Wagner Verwaltungsgese Improvements in writing and manifolding material
US2949381A (en) * 1958-04-04 1960-08-16 Steinhardt Amos Duplicating sheet coated with a colorless waxy transfer material
US3016308A (en) * 1957-08-06 1962-01-09 Moore Business Forms Inc Recording paper coated with microscopic capsules of coloring material, capsules and method of making
US3042519A (en) * 1960-01-08 1962-07-03 Horizons Inc Latent image photographic system
US3141404A (en) * 1961-04-12 1964-07-21 Columbia Ribbon & Carbon Novel imaging process
US3242122A (en) * 1961-09-18 1966-03-22 Ncr Co Thermo-colorable record copy sheet and coating composition
US3293055A (en) * 1961-10-05 1966-12-20 Ncr Co Heat sensitive coating composition and copy sheet coated therewith
US3328167A (en) * 1959-08-10 1967-06-27 Minnesota Mining & Mfg Copy-paper

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB810401A (en) * 1956-02-06 1959-03-18 Gunther Wagner Verwaltungsgese Improvements in writing and manifolding material
US3293060A (en) * 1956-02-06 1966-12-20 Wagner Guenter Writing and manifolding material
US3016308A (en) * 1957-08-06 1962-01-09 Moore Business Forms Inc Recording paper coated with microscopic capsules of coloring material, capsules and method of making
US2949381A (en) * 1958-04-04 1960-08-16 Steinhardt Amos Duplicating sheet coated with a colorless waxy transfer material
US3328167A (en) * 1959-08-10 1967-06-27 Minnesota Mining & Mfg Copy-paper
US3042519A (en) * 1960-01-08 1962-07-03 Horizons Inc Latent image photographic system
US3141404A (en) * 1961-04-12 1964-07-21 Columbia Ribbon & Carbon Novel imaging process
US3242122A (en) * 1961-09-18 1966-03-22 Ncr Co Thermo-colorable record copy sheet and coating composition
US3293055A (en) * 1961-10-05 1966-12-20 Ncr Co Heat sensitive coating composition and copy sheet coated therewith

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3715212A (en) * 1970-12-07 1973-02-06 Rca Corp Photochromic display and storage device and method of operation thereof
US4533567A (en) * 1983-05-24 1985-08-06 Ncr Corporation Carbonless paper coating formulation
WO1986003875A1 (en) * 1984-12-21 1986-07-03 Paul Jerome Banks Method and apparatus for handling information
GB2179193A (en) * 1984-12-21 1987-02-25 Paul Jerome Banks Method and apparatus for handling information
US4960679A (en) * 1985-01-31 1990-10-02 Canon Kabushiki Kaisha Image forming device

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Publication number Publication date
CH476581A (fr) 1969-08-15
DE1671563B2 (de) 1976-09-30
BE692252A (de) 1967-06-16
DE1671563A1 (de) 1971-09-30
GB1109554A (en) 1968-04-10

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Owner name: APPLETON PAPERS INC.

Free format text: MERGER;ASSIGNORS:TUVACHE, INC.;GERMAINE MONTEIL COSMETIQUES CORPORATION (CHANGED TO APPLETON PAPERS);REEL/FRAME:004108/0262

Effective date: 19811215