US3242122A - Thermo-colorable record copy sheet and coating composition - Google Patents

Thermo-colorable record copy sheet and coating composition Download PDF

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Publication number
US3242122A
US3242122A US138775A US13877561A US3242122A US 3242122 A US3242122 A US 3242122A US 138775 A US138775 A US 138775A US 13877561 A US13877561 A US 13877561A US 3242122 A US3242122 A US 3242122A
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US
United States
Prior art keywords
sheet
coating
thermo
copy sheet
colorable
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
US138775A
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English (en)
Inventor
Cheng James Ke-Jen
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
Original Assignee
NCR Corp
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
Priority to NL127674D priority Critical patent/NL127674C/xx
Priority to BE622029D priority patent/BE622029A/xx
Priority to NL283351D priority patent/NL283351A/xx
Priority to US138775A priority patent/US3242122A/en
Application filed by NCR Corp filed Critical NCR Corp
Priority to GB23468/62A priority patent/GB951507A/en
Priority to SE8399/62A priority patent/SE314301B/xx
Priority to CH959062A priority patent/CH407185A/fr
Priority to FR909195A priority patent/FR1333448A/fr
Priority to DEN22099A priority patent/DE1183918B/de
Application granted granted Critical
Publication of US3242122A publication Critical patent/US3242122A/en
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.
Anticipated expiration legal-status Critical
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
    • 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
    • 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
    • B41M5/323—Organic colour formers, e.g. leuco dyes

Definitions

  • FIG. 2 (BASE WEB OF PAPER) 2
  • FIG. 2 (BASE WEB OF PAPER) 2
  • thermo-icolorab-le record copy sheet consisting of a base web, such as paper, coated with a norm-ally substantially colorless coating that assumes a color where heated to temperatures used in ordinary thermognaphic printing, and to a composition for coating such a sheet.
  • the copy sheet is adapted especially fior use with a master sheet containing data to 'be copied therefrom, which data consists of ink characters which absorb infrared radiation and thereby become heated differentially to the rest of the master sheet, whereby, by placing the novel copy sheet in contact with the master sheet and applying infra-red radiation to such two-sheet system, the data characters are heated directly, or reflexly by transillumihation through the back of the copy sheet and the master sheet, depending on the facing of the sheets, causing the data to appear on the copy sheet.
  • the novel copy sheet utilizes in its preferred form a thin white sheet of paper coated on one side with a binder containing small amounts of heat-coliorable material consisting of a mixture of spirobenzopyran derivatives, benzoyl leuco methylene blue, thiocarbanilide as a color intensifier if desired, a fixing agent, urea, and buffering agents to keep the material at an approximately neutral pH and to eliminate premature fading.
  • a binder containing small amounts of heat-coliorable material consisting of a mixture of spirobenzopyran derivatives, benzoyl leuco methylene blue, thiocarbanilide as a color intensifier if desired, a fixing agent, urea, and buffering agents to keep the material at an approximately neutral pH and to eliminate premature fading.
  • FIGS. 1, 2, and 3 in diagrammatic form, wherein the base web materials, the coating, and the data to be copied are represented.
  • the systems of assembled sheets in FIGS. 1 and 2 are of use particularly with master sheets having data on but one side, whereas FIG. 3 represents a use of the novel copy sheet with a master sheet having data on both sides.
  • the infrared-heated data characters on the master sheet transmit their heat by conduction through the intervening base webs to the thermo-colorable coating of the novel copy sheet.
  • the materials which liorm the color immediately on being heated are substituted spirolbenzopyrans, the parent unsubstituted compounds having the molecular formula 1,3,3-trimethyl 2H-1'-benzcpyran)-2,2-indoline] and having the structure e--7 and benzoyl leuco methylene blue, which develops color in several hours after being heated or on exposure to sunlight; in addition, thiocarbanilide as a color intensifier, and materials, such as urea, which aid in fixing and blllffering the coating, of which examples are thiocarbanilide and N21 HPO .7H O.
  • the preferred coating composition to be applied to the paper consists of about 85 percent water, Spercent colorab'le materials, including intensi- 7 fiers, and 10 percent fixing and buffering materials. Inert thickening materials, in addition, may be added if necessary to produce proper coating consistency. Various other substitutes for the colorable materials will be given after the following preferred coating-composition.
  • the following preferred coating composition is based on a total weight of 99.91 grams, but it may be enlarged upon for commercial batches:
  • Haas Company as a non-ionic surface active under the trade name Triton N- 0.16 (e) H O 55.50 (f) Urea 5.00 (g) Na HPO .7H O 3.00 (:h) Polyvinyl pyrrilidone of 300,000 molecular weight as a 15 percent aqueous solution 10.00 (l) Polyxinyl pyrrilidone of 50,000 molecular weight 1.00
  • This composition is coated on a base web of paper of the desired thickness so that when dried, the coating has a thickness of 0.0005 of an inch more or less.
  • the base web stock of the copy-receiving sheet and the master sheet should be of such a nature as to pass infrared light, if the reflex system of irradiation, as shown in FIG. 2, is used. In the reflex system of FIG. 3, only the base web of the copy-receiving sheet need pass infra-red radiation.
  • Thiourea and its derivatives 1,1-diethyl-2-thiourea 1,1-diallyl-2-thiourea 1,3-dibutyl thiourea 1-allyl-3-phenyl-2-thiourca
  • the binder, the butter, and the thickness for the coating composition are not critical, and their equivalents are many and should be well known to those skilled in the art.
  • the copy sheet base web 20 of paper has the temperature-sensitive coating 21, which is overlaid by a non-infra-red-adsorbing master sheet 22 having thereon data 23 in carbon ink characters, or equivalent, that absorbs infra-red radiation from the source 24 and thereby becomes hot.
  • the ink characters become heated :by the infra-red rays, whereas the base web of the master sheet does not become heated to any great extent, by either reflecting or transmitting the infra-red rays.
  • the heat induced in the characters is proportional to the absorbed energy, and the infra-red source is so adjusted that the characters rise in temperature to a point where the heat is conducted through the sheet 22 in the pattern of the characters to cause coloration of the materials in the coating 21, as copied data 25.
  • FIG. 2 represents the same assembly of master sheet and thermo-sensitive coated sheet 20, 21, with the infrared radiation directed through the assembly from the rear of the copy-receiving sheet.
  • the copy-receiving sheet and the master sheet base web being non-in-fra-red-radiation absorbing, pass the radiation to heat the data characters, with a resultant copy 25 made on the coated side of the copy sheet. It is apparent that, the thinner and more transparent the base paper webs, the more distinct the copied data is.
  • FIG. 3 represents an assembly of a master sheet and the novel copy sheet wherein the master sheet has data on both sides and it is the intent to have a copy of the data of one side only.
  • the back (uncoated side) of the copy sheet 20, 21 is placed against that side of the master sheet to be copied, and the infra-red radiation is passed through the copy sheet to heat the underlying data-representing characters, which become hot and transfer such inducedheat image, by conduction, back through the base web of the copy sheet to form the image on the thermosensitive coating thereof.
  • thermo-sensitive sheet The materials used in the thermo-sensitive sheet are such as to insure stability in storage, either in the dark or in light of normal living environment, both before and after exposure, and the coating is relatively inexpensive compared to those heretofore known.
  • the copy may be a dark blue color which appears on a substantially colorless (white) background, or the green or pink coloring dye may be mixed therewith, in combination from among those mentioned, in any proportions, or any of the dyes may be used alone.
  • a suitable coloration of the master sheet or the data-receiving sheet may be chosen as long as it does not convert the applied infra-red radiation to heat.
  • FIGS. 1, 2, and 3 are exemplary systems only for illustrating the utility of the thermo-sensitive copy sheet, useful in copying data from a master sheet printed on one side or both, according to the mode of assembling the copy sheet with the master sheet and the direction in which the infra-red radiation is applied thereto.
  • thermo-colorable record copy sheet consisting of a supporting web having a substantially colorless coating thereon which turns to a colored form when heated, said coating having as color ingredients a mixture of (a) the 6'NO 8' methoxy derivative of the compound having the structure and (b) benzoyl leuco methylene blue;
  • urea as a color fixer, all carried in a bufi'ered binder holding the coating substantially at a neutral pH.
  • thermo-colorable record sheet consisting of a supporting web having a substantially colorless coating on a surface thereof which turns to a colored form when heated, said coating having as color ingredients (a) at leasttone of the derivatives of the compound 1,3,3 trimethyl spiro[(2H-l'-benzopyran)-2,2 indoline], having the structure wherein said derivatives are compounds represented by said structure-in which selected ring positions are substituted with selected radicals, said radicals being selected from the group consisting of S-chloro, 6- nitro; 8-ethory; 5-chloro, 6'-nitro, 8'-ethoxy; 8'- methoxy; S-chloro, 68'-dinitro; S-chloro, 8-methoxy; 6-nitro, 8'-methoxy; 5-chloro, 6-nitro, 8-methoxy; 8-nitro; 6-nitro; and 4,7,8-trimethoxy;
  • a liquid coating composition consisting of an aqueous vehicle containing at least one derivative of 1,3,3-trimethyl-spiro[(2H-l benzopyran)-2,2' indoline] having the general structure wherein said derivatives are compounds represented by said structure in which selected ring positions are substituted with selected radicals, said radicals being selected from the group consisting of S-chloro, 6'-nitro; 6'-nitro, 8-ethoxy; S-chloro, 6,8'-dinitro; 5-chlor0, 8-methoxy; 6'- nitro, 8-methoxy; S-chloro, 6'-nitro, 8-methoxy; 8'-nitro; 6-nitro; and 4,7,8-trimethoxy; at least one compound selected from the group consisting of benzoyl leuco methylene blue, iso-valeryl leuco methylene blue, iso-butyryl leuco methylene blue, and propionyl leuco methylene blue; and a buffere
  • a liquid coating composition comprising: (a) a major proportion of water, (b) a minor proportion of the temperature-colorable material 1,3,3 trimethyl 6-NO ,8'-methoxy spiro 5 [(2'H-1'-benzopyran)2,2 indoline] having the structural formula H30 c H 3 (c) a minor proportion of a leuco methylene blue compound selected from the group consisting of benzoyl leuco methylene blue, iso-valeryl leuco methyl- 6 ene blue, iso-butyryl leuco methylene blue, and propionyl leuco methylene blue; and a buffered binding material holding the composition at a. substantially neutral pH.
  • MURRAY TILLMAN Primary Examiner. LEON J. BERCOVITZ, Examiner.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
US138775A 1961-09-18 1961-09-18 Thermo-colorable record copy sheet and coating composition Expired - Lifetime US3242122A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
NL127674D NL127674C (da) 1961-09-18
BE622029D BE622029A (da) 1961-09-18
NL283351D NL283351A (da) 1961-09-18
US138775A US3242122A (en) 1961-09-18 1961-09-18 Thermo-colorable record copy sheet and coating composition
GB23468/62A GB951507A (en) 1961-09-18 1962-06-19 Thermo-colourable record copy sheet
SE8399/62A SE314301B (da) 1961-09-18 1962-07-31
CH959062A CH407185A (fr) 1961-09-18 1962-08-14 Feuille de copie thermocolorable
FR909195A FR1333448A (fr) 1961-09-18 1962-09-12 Feuille de copie pour enregistrement
DEN22099A DE1183918B (de) 1961-09-18 1962-09-15 Durch Waermeeinwirkung faerbbares Aufzeichnungskopierblatt

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US138775A US3242122A (en) 1961-09-18 1961-09-18 Thermo-colorable record copy sheet and coating composition

Publications (1)

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US3242122A true US3242122A (en) 1966-03-22

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US138775A Expired - Lifetime US3242122A (en) 1961-09-18 1961-09-18 Thermo-colorable record copy sheet and coating composition

Country Status (7)

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US (1) US3242122A (da)
BE (1) BE622029A (da)
CH (1) CH407185A (da)
DE (1) DE1183918B (da)
GB (1) GB951507A (da)
NL (2) NL283351A (da)
SE (1) SE314301B (da)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3421894A (en) * 1966-01-13 1969-01-14 Ncr Co Recording process utilizing 6'-nitro-1,3,3 - trimethyl-benzoindolinospiropyran dispersed in heat-meltable wax
US3422759A (en) * 1966-06-02 1969-01-21 Xerox Corp Lithographic imaging system using photochromic and thermochromic materials
US3445234A (en) * 1962-10-31 1969-05-20 Du Pont Leuco dye/hexaarylbiimidazole imageforming composition
US3477850A (en) * 1965-07-08 1969-11-11 Itek Corp Light sensitive heat erasable copying system
US3584934A (en) * 1968-04-12 1971-06-15 Itek Corp Nonmechanical shutter
US3642484A (en) * 1968-10-03 1972-02-15 Agfa Gevaert Nv Unsaturated photochromic indolino-spiropyran monomers and polymers prepared therefrom
US3692800A (en) * 1968-10-30 1972-09-19 Fuji Photo Film Co Ltd Photochromic compound
US5234798A (en) * 1991-10-04 1993-08-10 Dittler Brothers, Incorporated Thermal reactive structures

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2880110A (en) * 1954-12-02 1959-03-31 Minnesota Mining & Mfg Heat-sensitive copying-paper
US3020171A (en) * 1960-08-26 1962-02-06 Ncr Co Pressure-sensitive record and transfer sheet material
US3111407A (en) * 1960-02-26 1963-11-19 Ibm Methods for making record materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2880110A (en) * 1954-12-02 1959-03-31 Minnesota Mining & Mfg Heat-sensitive copying-paper
US3111407A (en) * 1960-02-26 1963-11-19 Ibm Methods for making record materials
US3020171A (en) * 1960-08-26 1962-02-06 Ncr Co Pressure-sensitive record and transfer sheet material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3445234A (en) * 1962-10-31 1969-05-20 Du Pont Leuco dye/hexaarylbiimidazole imageforming composition
US3477850A (en) * 1965-07-08 1969-11-11 Itek Corp Light sensitive heat erasable copying system
US3421894A (en) * 1966-01-13 1969-01-14 Ncr Co Recording process utilizing 6'-nitro-1,3,3 - trimethyl-benzoindolinospiropyran dispersed in heat-meltable wax
US3422759A (en) * 1966-06-02 1969-01-21 Xerox Corp Lithographic imaging system using photochromic and thermochromic materials
US3584934A (en) * 1968-04-12 1971-06-15 Itek Corp Nonmechanical shutter
US3642484A (en) * 1968-10-03 1972-02-15 Agfa Gevaert Nv Unsaturated photochromic indolino-spiropyran monomers and polymers prepared therefrom
US3692800A (en) * 1968-10-30 1972-09-19 Fuji Photo Film Co Ltd Photochromic compound
US5234798A (en) * 1991-10-04 1993-08-10 Dittler Brothers, Incorporated Thermal reactive structures

Also Published As

Publication number Publication date
NL283351A (da)
CH407185A (fr) 1966-02-15
NL127674C (da)
GB951507A (en) 1964-03-04
DE1183918B (de) 1964-12-23
SE314301B (da) 1969-09-01
BE622029A (da)

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AS Assignment

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