US3682684A - Wide latitude heat-sensitive copy-sheet and method of making - Google Patents

Wide latitude heat-sensitive copy-sheet and method of making Download PDF

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Publication number
US3682684A
US3682684A US123106A US3682684DA US3682684A US 3682684 A US3682684 A US 3682684A US 123106 A US123106 A US 123106A US 3682684D A US3682684D A US 3682684DA US 3682684 A US3682684 A US 3682684A
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US
United States
Prior art keywords
parts
sheet
soap
silver
heat
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
US123106A
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English (en)
Inventor
Donald J Newman
Donald J Williams
John R Berg
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
Application granted granted Critical
Publication of US3682684A publication Critical patent/US3682684A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/32Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B41PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41MPRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/30Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • B41M5/333Colour developing components therefor, e.g. acidic compounds
    • B41M5/3333Non-macromolecular compounds
    • B41M5/3335Compounds containing phenolic or carboxylic acid groups or metal salts thereof
    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/494Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
    • G03C1/498Photothermographic systems, e.g. dry silver
    • G03C1/4989Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00Stock material or miscellaneous articles
    • Y10S428/913Material designed to be responsive to temperature, light, moisture
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31786Of polyester [e.g., alkyd, etc.]
    • Y10T428/3179Next to cellulosic

Definitions

  • This invention relates to heat-sensitive copy-sheets.
  • the invention relates to copy-sheets in transparent film form with which projection transparencies of halftone originals may be prepared by thermographic copying processes.
  • thermographic process as first described in Miller US. Pat. No. 2,740,896 involves brief exposure to intense radiation of an original in heat-conductive contact with a heat-sensitive copy-sheet.
  • the heat pattern produced at wide lines or blocky image areas may build up more rapidly than at narrow lines of areas of fine detail, resulting in blurring at the former or in partial copy at the latter areas when the copy-sheet employed is deficient in exposure latitude.
  • Copy-sheet constructions based on silver soap reactants as described in Owen US. Pat. No. 2,910,377, produce dense black images but the exposure must be carefully regulated in order to obtain a useful degree of latitude. Increased latitude is obtained with copy-sheet constructions based on ferric soaps as described in Miller et al. U.S. Pat. No. 2,663,654, but even with these sheets it is found difficult to obtain fully satisfactory rendering of both fine and heavy lines or patterns.
  • the silver soap heat-sensitive copy-sheets form a visible image through an oxidation-reduction reaction.
  • a different reaction probably a chelation reaction, occurs in the ferric soap coatings.
  • Separate co-reactants may be employed, but it has been found possible to use the same co-reactant for both of the metal soap reactants.
  • Compounds such as pyrogallic acid, catechol, protocatechuic acid, azelayl pyrogallic acid, azelayl bispyrogallic acid, methyl gallate, behenoyl pyrogallol are particularly effective. Each of these compounds will be seen to a polyhydric phenol. Mixtures of these and other co-reactants for the metal soaps may be used, e.g.
  • Toners such as phthalazinone are known to improve the silver image in copy-sheets based on silver soaps and are found desirable in the prodnets of this invention, e.g. in amounts of about 15-20 percent of the weight of the silver soap.
  • Polymeric filmforrning binders, non-fusing at the temperatures employed in copying, will ordinarily be included in amounts sufficient to form a smooth well-bonded coating.
  • the compositions may be applied to paper or other nontransparent 3,682,684 Patented Aug. 8, 1972 ice backings and when thus employed may contain pigments, fillers and other additives. Particularly desirable results are obtained using clear transparent coatings on transparent film backings, the resulting copies then serving admirably as projection transparencies for use on overhead projectors.
  • a first coating composition is prepared by mixing together 20 parts of a 20% dispersion of ferric stearate in ethanol, 20 parts of a 20% dispersion of silver behenate in ethanol, 0.66 part of phthalazinone, 66.66 parts of a 15% solution of polyvinyl acetate in acetone, and 88.5 parts of acetone. The mixture is coated on two mil polyethylene terephthalate polyester film at a coating Weight, after drying, of 0.55 gram per sq. ft.
  • a second coating composition prepared by dissolving 20 parts of cellulose acetate butyrate and 4 parts of methyl gallate in 180 parts of methylethyl ketone, is applied oer the first coat at a coating weight, after drying, of 0.30 gm./sq. ft.
  • the two coatings provide a thin visibly heatsensitive layer.
  • the coated film is clear and transparent, with a faint buff color. A portion is placed in face-to-face contact with an original having black printed characters on a white paper backing. Brief exposure through the film to intense radiant energy in a thermographic copying machine results in the reproduction of the image areas on the film.
  • the image density is approximately 1.1. Images having a density above about 0.6 are effective in providing projection images which are easily visible when shown in a lighted room.
  • Another portion is used to make a copy of a printed halftone original by a similar procedure,
  • the dark image areas reproduce as a dense black; the reproductions of lighter areas are of much lower density and have a slightly purple cast.
  • a silver soap dispersion is prepared by mixing together 60 parts of silver behenate, 240 parts of ethanol, parts of polyvinyl acetate, 11.25 parts of phthalazinone, and 1089 parts of acetone.
  • a ferric soap dispersion is similarly prepared by mixing together 60 parts of ferrice stearate, 240 parts of ethanol, 75 parts of polyvinyl acetate, and 1100 parts of acetone.
  • the two dispersions are mixed together in different proportions as hereinafter tabulated.
  • the mixtures are coated on one mil polyester film through a coating orifice of four mils, and the coatings are dried in an oven at temperatures not higher than about 200 F.
  • Each sample is then further coated with a composition containing 9.8 parts of cellulose acetate butyrate and 2.0 parts of methyl gallate in 88.2 parts of methylethyl 'ketone, applied through a three mil orifice, and the sheet is again dried.
  • the several samples are imaged thermographically by being placed against an original, printed with both wide and narrow lines, which is then exposed through the sample to intense radiant energy for decreasing periods of time along the length of the lines.
  • the test is conveniently carried out in a thermographic apparatus wherein the rate of movement of the copysheet and printed original past a line source of intense radiation is uniformly increased, thereby providing a graphical representation of exposure latitude. Under unduly prolonged exposure the copy is blurred, the heavy lines in particular being broadened and showing rough wavy edges. With too short an exposure the density of the copy is decreased and the finest lines of the original do not reproduce.
  • EXAMPLE 3 One mil polyester film is provided with a dried first coating of a mixture containing equal proportions of ferric stearate and silver behenate together with toner and binder, as described in connection with Example 1. Portions of the film are then separately coated with compositions containing two parts of different co-reactants and 9.8 parts of cellulose acetate butyrate in 88.2 parts of methylethyl ketone, applied from a three mil coating orifice and again dried. The same coatings are applied over first coatings separately containing the two metal soaps, as controls. The several samples are tested for exposure latitude as previously described, with results as indicated in the following tabulation.
  • a heat-sensitive sheet material including a thin visibly heat-sensitive layer having wide exposure latitude and comprising: a mixture of ferric and silver soaps of long chain fatty acids wherein said silver soap represents between 10 and percent by Weight of said mixture; at toner for the silver image; and a phenolic co-reactant for said soaps.
  • Sheet material of claim 1 wherein said layer contains a polymeric film-forming binder and is supported on a transparent carrier film and wherein said sheet material is clear and transparent.
  • Sheet material of claim 3 wherein said ferric soap is ferric stearate, said silver soap is silver behenate, and said toner is phthalazinone.
  • Sheet material of claim 4 wherein said phenolic coreactant comprises behenoyl pyrogallol.
  • Sheet material including a thin flexible backing and having a first coating comprising a. mixture of 10-80 parts by weight of silver soap of long chain fatty acid and correspondingly -20 parts by weight of ferric soap of long chain fatty acid, and overlying said first coating, a second coating comprising at least one polyhydric phenolic coreactant, heat reactable with said soaps to produce a colored product.
  • Method of making a heat-sensitive copy-sheet having wide exposure latitude comprising blending together, in a solution of a polymeric film-forming binder in a volatile liquid solvent, 10-80 parts by weight of silver soap of long chain fatty acid and correspondingly 90-20 parts by weight of ferric soap of long chain fatty acid, together with about 15-20 parts by weight of phthalazinone for each parts of said silver soap, and applying said blend to a backing, and applying an overlying coating containing at least one polyhydric phenolic co-reactant for said soaps thereto.

Landscapes

  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General 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)
  • Thermal Transfer Or Thermal Recording In General (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
US123106A 1971-03-10 1971-03-10 Wide latitude heat-sensitive copy-sheet and method of making Expired - Lifetime US3682684A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US12310671A 1971-03-10 1971-03-10

Publications (1)

Publication Number Publication Date
US3682684A true US3682684A (en) 1972-08-08

Family

ID=22406745

Family Applications (1)

Application Number Title Priority Date Filing Date
US123106A Expired - Lifetime US3682684A (en) 1971-03-10 1971-03-10 Wide latitude heat-sensitive copy-sheet and method of making

Country Status (22)

Country Link
US (1) US3682684A (de)
JP (1) JPS51454B1 (de)
AR (1) AR194945A1 (de)
AT (1) AT316598B (de)
AU (1) AU438353B2 (de)
BE (1) BE780426A (de)
BR (1) BR7201357D0 (de)
CA (1) CA950670A (de)
CH (1) CH576353A5 (de)
DD (1) DD96046A5 (de)
DE (1) DE2211984C3 (de)
DK (1) DK131900C (de)
ES (1) ES400257A1 (de)
FI (1) FI57072C (de)
FR (1) FR2129536A5 (de)
GB (1) GB1358614A (de)
IL (1) IL38943A (de)
IT (1) IT952180B (de)
NL (1) NL170108C (de)
NO (1) NO136784C (de)
SE (1) SE375943B (de)
ZA (1) ZA72590B (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852093A (en) * 1972-12-13 1974-12-03 Minnesota Mining & Mfg Heat-sensitive copy-sheet
JPS51135540A (en) * 1975-05-20 1976-11-24 Fuji Photo Film Co Ltd Heat sensitive material for recording
US4332872A (en) * 1980-09-19 1982-06-01 Zingher Arthur R Optically annotatable recording film
US4379835A (en) * 1980-12-22 1983-04-12 Minnesota Mining And Manufacturing Company Black image from a thermographic imaging system
US4461496A (en) * 1982-08-17 1984-07-24 Minnesota Mining And Manufacturing Company Soap having improved carbonless imaging properties
US4602265A (en) * 1983-04-11 1986-07-22 Mark Sensing (Aust.) Pty. Limited Non-aqueous compositions for heat-sensitive multi-layer coatings
EP0718795A1 (de) 1994-12-22 1996-06-26 Landis & Gyr Technology Innovation AG Optisch maschinell lesbarer Informationsträger

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6115793U (ja) * 1984-06-30 1986-01-29 日本電気ホームエレクトロニクス株式会社 ヒンジ

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3852093A (en) * 1972-12-13 1974-12-03 Minnesota Mining & Mfg Heat-sensitive copy-sheet
JPS51135540A (en) * 1975-05-20 1976-11-24 Fuji Photo Film Co Ltd Heat sensitive material for recording
US4332872A (en) * 1980-09-19 1982-06-01 Zingher Arthur R Optically annotatable recording film
US4379835A (en) * 1980-12-22 1983-04-12 Minnesota Mining And Manufacturing Company Black image from a thermographic imaging system
US4461496A (en) * 1982-08-17 1984-07-24 Minnesota Mining And Manufacturing Company Soap having improved carbonless imaging properties
US4602265A (en) * 1983-04-11 1986-07-22 Mark Sensing (Aust.) Pty. Limited Non-aqueous compositions for heat-sensitive multi-layer coatings
EP0718795A1 (de) 1994-12-22 1996-06-26 Landis & Gyr Technology Innovation AG Optisch maschinell lesbarer Informationsträger

Also Published As

Publication number Publication date
SE375943B (de) 1975-05-05
IT952180B (it) 1973-07-20
NL170108C (nl) 1982-10-01
DE2211984C3 (de) 1974-07-04
FI57072B (fi) 1980-02-29
FI57072C (fi) 1980-06-10
GB1358614A (en) 1974-07-03
DK131900C (da) 1976-03-01
AR194945A1 (es) 1973-08-30
AT316598B (de) 1974-07-25
CA950670A (en) 1974-07-09
JPS51454B1 (de) 1976-01-08
AU438353B2 (en) 1973-08-09
CH576353A5 (de) 1976-06-15
DE2211984A1 (de) 1972-09-14
BE780426A (fr) 1972-09-11
BR7201357D0 (pt) 1973-06-05
NO136784B (no) 1977-08-01
DE2211984B2 (de) 1973-11-15
IL38943A0 (en) 1972-05-30
NO136784C (no) 1977-11-09
NL7202600A (de) 1972-09-12
IL38943A (en) 1975-02-10
ZA72590B (en) 1972-10-25
DD96046A5 (de) 1973-03-05
AU3982972A (en) 1973-08-09
ES400257A1 (es) 1975-01-01
NL170108B (nl) 1982-05-03
FR2129536A5 (de) 1972-10-27
DK131900B (da) 1975-09-22

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