US3149992A - Heat sensitive sheets - Google Patents

Heat sensitive sheets Download PDF

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Publication number
US3149992A
US3149992A US206186A US20618662A US3149992A US 3149992 A US3149992 A US 3149992A US 206186 A US206186 A US 206186A US 20618662 A US20618662 A US 20618662A US 3149992 A US3149992 A US 3149992A
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US
United States
Prior art keywords
amine
color
developer
sheet
activation temperature
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
US206186A
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English (en)
Inventor
William R Lawton
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.)
Nashua Corp
Original Assignee
Nashua 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 NL294553D priority Critical patent/NL294553A/xx
Priority to BE632833D priority patent/BE632833A/xx
Application filed by Nashua Corp filed Critical Nashua Corp
Priority to US206186A priority patent/US3149992A/en
Priority to US238713A priority patent/US3167445A/en
Priority to GB19904/63A priority patent/GB1029547A/en
Priority to FR936104A priority patent/FR1363501A/fr
Priority to LU43835D priority patent/LU43835A1/xx
Priority to ES288606A priority patent/ES288606A1/es
Application granted granted Critical
Publication of US3149992A publication Critical patent/US3149992A/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
    • B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
    • 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
    • G03C1/52—Compositions containing diazo compounds as photosensitive substances
    • 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
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/913—Material designed to be responsive to temperature, light, moisture
    • 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
    • Y10S430/145—Infrared

Definitions

  • the joint application Serial No. 808,012 describes heat sensitive sheets and compositions containing an indicator material which changes color in the presence of a basic organic amine in combination with a latent developer, which on heating yields an amine effective to give a color reaction.
  • the latent developers employed in those sheets and compositions are the thermally dissociable crystalline molecular compounds consisting of an organic amine in combination with either urea thiourea or a bisphenol. Under normal storage conditions, they are solids which exhibit no substantial basic amine characteristics, and may therefore be intimately associated with the indicator material without causing a color reaction.
  • compositions heretofore developed has, however, been limited by the fact that the molecular compounds of urea, thiourea and the hisphenols are relatively unstable in the presence of moisture. They cannot therefore be applied to the sheet from aqueous systems, and the binder in which they are dispersed must be one that is soluble in an organic liquid in which the latent developer is not soluble. In addition, the sheets employing these complexes have a reducedshelflife when stored at high humidity.
  • the present invention is based on a continuation of the work described in the joint application and provides an improved heat marking sheet having improved stability in the presence of water, which may be coated with aqueous compositions.
  • the invention further provides sheets of generally greater heat sensitivity which may be V marked or developed quicker and at lower temperatures.
  • the latent developer for heat sensitive sheets and compositions is a crystalline adduct formed from a basic organic amine and a hydroxy- 1 phenyl substituted chroman.
  • Adducts of 'this type are known to the art, see e.g., Cramer, Frederick E in gleich für en'(Springer-Verlog, Berlin, 1954), and as a class they are generally useful when selected with reference to their physical characteristics as they relate to in the-presence of abasicorganic amine in combination with an; amine'adduct of a hydroxyphenyl substituted chroman.
  • the indicator may be any of numerous wellknown materials which react with basic organic amines to give a color change, including the photosensitive azodye forming materials which provide photosensitive sheets capable of being developed merely by the application of heat.
  • Heat sensitive sheets are produced by providing a sheet of suitable backing material, such as paper, with a coating containing both the indicator material and crystals of the latent developer adduct in intimate potentially reactive association such that upon dissociation of the adduct, the amine is present throughout the coating.
  • the adduct will generally be retained on the sheet by means of a resin binder, and the components may all be applied together in a single coat in which each is separately dispersed.
  • the latent developer and indicator material may be applied in separate layers.
  • additional material such as pigments, antistatic and anti-friction ingredients may be incorporated in any of the coating compositions.
  • binders which may in turn be such water soluble polymers as glue, starch, polyvinyl alcohol, water soluble gums, carboxymethyl cellulose, hydroxyethylcellulose and the like.
  • water soluble resins themselves is preferable to the organic solvent soluble mate rials heretofore required, as they are less compatible with .the adduct, and therefore do not tend to interact with it.
  • the adduct should be one that is stable under the conditions normally encountered in the manufacture, storage and shipment of materials of this type, which are -referredto in the specification and in the appended claims as normal and may be typified by conditions of temperature less than about 100 F. and a relative humidity less than 99 percent.
  • EXAMPLE 2 Adducts of Cycl0hexanespir0-4-(2'-Hydr0xy-7,4'-Dimethyl-2,3-Tetramethylene) Flavan A mixture of m-cresol (400 g.) and cyclohexanone (240 g.) was'saturated with dry HCl for one hour at 0 C., kept for three days at room temperature and one day at 40-50 C., and was then stirred into 4 liters of an aqueous, 2 N sodium hydroxide solution. The product was extracted with a mixture of 1000 cc. diethylether and400 cc. hexane.
  • p-Cresol (648 g.) dissolved in acetone (232 g.) was cooled to 0 C. in an ice-salt bath and saturated for one hour with gaseous During this period, the'temperature rose to 15 C.
  • the flask was sealed from atmospheric moisture, allowed to reach room temperature slowly and stood at room temperature for two days. "After ⁇ two days, the dark product was stirred into two liters of an" aqueous two i N sodium hydroxide solution during which timelthe mixture became colorless. nioxanemoo g) was added and, theimixture was stiri'edion the water *bath for thirty'minutes and left overnight at. -20 C.
  • the oily decanted layer was shaken with-250 ml. hot ethanol,"chilled'at -20 C. and the ethanol adduct separated 'on a. Buchner funnel and'washed' with cold ethanol.
  • the product- was recrystallized fromethanol to give g. ethanol adduct of Dianins compound, M.P; -166 C.
  • the resulting solid was boiled with water, collected, and dried over phosphoriq'anhydride under "vacuum (M.P.
  • Amine/chrornan adduct 20 Polyvinyl alcohol (Gelvatol 20/60) 2 Water 98
  • the mixture was milled in a ball mill for 24-48 hours and subsequently coated by means of No. 12 Mayer rod onto the paper based stock.
  • the amine/chroman adduct coating was applied to a 45 pound per ream (500 sheets, 24" x 30") Fitchburg direct process diazo paper stock to a dry coating weight of 3-5 pounds per ream.
  • a coating containing the indicator material reactive with a base to give a color change was applied over the amine/chroman adduct coating to a dry weight of 0.5-2 pounds per ream.
  • EXAMPLE 7 A Conventional Diazo Composition Parts by weight The materials were added to the water in the order listed and mixed into solution for coating.
  • the materials were combined and ground for 24-48 hours in a ball mill.
  • the materials were combined and ground for 24-48 hours in a ball mill.
  • pH indicators were employed, by dissolving the indicator in water or in a 50:50 methanol-water mixture at a concentration in the range of 0.52 percent.
  • Heat Sensitive Sheet Employed Commercial Diazo Paper a commercial diazo paper, e.g., Ozalid No. 2088, Was overcoated with the dispersion of amine/ ehroman adduct.
  • Examples 7-20 are set forth as column headings and the amine/chroman adducts (Examples 1-6) are line headings. Combinations which have been actually employed in the manner above are designated by an X in and the Ninhydrm is then added. the approprlate column and lme.
  • those described under Examples 7 and 20, employing diazo indicator systems may be used as a conventional diazo sheet and exposed to ultra violet radiation through a graphic original, Following exposure, heating the sheet to cause dissociation of the amine/chroman adduct, causes the latent diazo image to be developed.
  • the accompanying drawing illustrates schematically a heat-sensitive sheet corresponding to this invention.
  • the sheet is represented as being in cross-section.
  • the indicator materials have been selected as representative of known materials which change color in the presence of a basic organic amine; they include diazo dye forming materials which are typically developed by amines, ninhydrin and quinone compounds which are frequently employed as color indicators for amines, and pH indicators which change color in the presence of the basic conditions provided by the amines.
  • Other indicator materials than those described, which change color in the presence of a basic organic amine, and also the adducts of other hydroxyphenyl substituted chromans and other amines, will be known to the art, those specifically described being given as representative of these classes of materials.
  • Other binders and coating techniques may also be employed, provided they result in the indicator material and the adduct being in intimate potentially reactive association, such that dissociation of the adduct will result in the desired colored change.
  • a heat marking copy sheet responsive to heating to an elevated activation temperature by changing visibly to a contrasting color comprising, in combination, a support carrying indicator material which changes color by chemical reaction with a basic organic amine; and a stable unreactive heat sensitive latent'developer in intimate association with said material for causing a color change upon heating said sheet to an activation temperature between 50 C. and 150 C., said developer being an organic amine in combination with a hydroxyphenyl substituted chroman forminga solid crystalline complex which is stable under normal conditions of temperature and humidity and dissociable at said activation temperature to yield said amine to cause said color change.
  • a heat marking copy sheet responsive to heating to anelevated activation temperature by changing visibly to 'a contrasting color comprising in combination a support carrying indicator material which changes color by chemical reaction with a basic organic amine, a stable unreactive heat sensitive latent developer in intimate association with said material for causing a color change upon heat ing said sheet to an activation temperature between 50 C. and C., and a binder for said developer, said developer being an organic amine in combination with a hydroxyphenyl substituted chroman forming a solid crystalline complex which is stable under normal conditions of temperature and humidity and dissociable at said activation temperature to yield said amine to cause said color change, and said binder being a water soluble resin.
  • a heat marking copy sheet responsive to heating to an elevated activation temperature by changing visibly to a contrasting color comprising, in combination, a support carrying a first layer which comprises indicator ma terial which changes color by chemical reaction with a basic organic amine; and a second layer which comprises a stable unreactive heat sensitive latent developer in intimate association with said material for causing a color change upon heating said sheet to an activation temperature between 50 C. and 150 C., said developer being an organic amine in combination with a hydroxyphenyl substituted chroman forming a solid crystalline complex which is stable under normal conditions of temperature and humidity and dissociable at said activation temperature to yield said amine to cause said color change.
  • the copy sheet defined by claim 5 where the indicator material is an azo dye forming material.
  • a heat marking copy sheet responsive to heating to an elevated activation temperature by changing visibly to a contrasting color comprising, in combination, a support carrying a first layer which comprises indicator material which changes color by chemical reaction with a basic organic amine; and a second layer which comprises a stable unreactive heat sensitive latent developer in intimate association with said material for causing a color change upon heating said sheet to an activation temperature between 50T. C. and 150 C., and a binder for said developer, said developer being an organic amine in combination with a hydroxyphenyl substituted chroman forming a solid crystalline complex which is stable under normal conditions of temperature and humidity and dissociable at said activation temperature to yield said amine to cause said color change, said binder being a water solube resin.

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Color Printing (AREA)
US206186A 1962-06-29 1962-06-29 Heat sensitive sheets Expired - Lifetime US3149992A (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
NL294553D NL294553A (de) 1962-06-29
BE632833D BE632833A (de) 1962-06-29
US206186A US3149992A (en) 1962-06-29 1962-06-29 Heat sensitive sheets
US238713A US3167445A (en) 1962-06-29 1962-11-19 Heat responsive marking sheets
GB19904/63A GB1029547A (en) 1962-06-29 1963-05-20 Heat sensitive sheets
FR936104A FR1363501A (fr) 1962-06-29 1963-05-27 Feuilles sensibles à la chaleur
LU43835D LU43835A1 (de) 1962-06-29 1963-05-29
ES288606A ES288606A1 (es) 1962-06-29 1963-05-31 Perfeccionamientos en hojas para copias, sensibles al calor

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US206186A US3149992A (en) 1962-06-29 1962-06-29 Heat sensitive sheets
US238713A US3167445A (en) 1962-06-29 1962-11-19 Heat responsive marking sheets

Publications (1)

Publication Number Publication Date
US3149992A true US3149992A (en) 1964-09-22

Family

ID=26901127

Family Applications (2)

Application Number Title Priority Date Filing Date
US206186A Expired - Lifetime US3149992A (en) 1962-06-29 1962-06-29 Heat sensitive sheets
US238713A Expired - Lifetime US3167445A (en) 1962-06-29 1962-11-19 Heat responsive marking sheets

Family Applications After (1)

Application Number Title Priority Date Filing Date
US238713A Expired - Lifetime US3167445A (en) 1962-06-29 1962-11-19 Heat responsive marking sheets

Country Status (5)

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US (2) US3149992A (de)
BE (1) BE632833A (de)
GB (1) GB1029547A (de)
LU (1) LU43835A1 (de)
NL (1) NL294553A (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4097288A (en) * 1977-02-25 1978-06-27 Lawton William R Heat sensitive recording composition containing a complexed phenolics and a spiropyran or leuco lactone
US4180405A (en) * 1977-02-25 1979-12-25 Graphic Controls Corporation Heat-sensitive recording composition with mixed color precursors
US4397932A (en) * 1981-10-26 1983-08-09 A. B. Dick Company Electrophotographic composition and elements
WO1986007473A1 (en) * 1985-06-03 1986-12-18 Fairmount Chemical Co., Inc. Contrast enhancement layer
EP0738723A2 (de) * 1995-04-17 1996-10-23 General Electric Company Verfahren zur Herstellung polyalkylierte Xanthenderivate
US8432279B2 (en) 2010-06-23 2013-04-30 Medline Industries, Inc. Multi-stage color activated system to detect unauthorized processing of medical devices

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3645768A (en) * 1968-03-07 1972-02-29 Wyomissing Corp Foamable resinous materials
CA987103A (en) * 1972-02-17 1976-04-13 Kinichi Adachi Dichromatic thermo-sensitive paper
US5441418A (en) * 1993-05-20 1995-08-15 Binney & Smith Inc. Thermochromic drawing device
US5514635A (en) * 1993-12-29 1996-05-07 Optum Corporation Thermal writing surface and method for making the same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2680062A (en) * 1949-07-23 1954-06-01 Keuffel & Esser Co Process for the production of azo dyestuff images
US2681277A (en) * 1953-01-28 1954-06-15 Morrison Montford Heat sensitive recording element
US2732299A (en) * 1952-07-22 1956-01-24 Light sensitive
US2995466A (en) * 1959-08-07 1961-08-08 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US2995465A (en) * 1959-08-07 1961-08-08 Minnesota Mining & Mfg Copy-sheet
US3076707A (en) * 1959-04-22 1963-02-05 Nashua Corp Heat developable copy sheet and compositions useful therefor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2813042A (en) * 1952-10-02 1957-11-12 Dick Co Ab Method of preparing a sensitized thermographic copy sheet and resultant sheet
DE1109712B (de) * 1958-08-09 1961-06-29 Kalle Ag Kopierschichten zur Herstellung von Bildern durch Waerme
US3031329A (en) * 1959-10-26 1962-04-24 Minnesota Mining & Mfg Heat-sensitive copy-sheet and composition therefor

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2680062A (en) * 1949-07-23 1954-06-01 Keuffel & Esser Co Process for the production of azo dyestuff images
US2732299A (en) * 1952-07-22 1956-01-24 Light sensitive
US2681277A (en) * 1953-01-28 1954-06-15 Morrison Montford Heat sensitive recording element
US3076707A (en) * 1959-04-22 1963-02-05 Nashua Corp Heat developable copy sheet and compositions useful therefor
US2995466A (en) * 1959-08-07 1961-08-08 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US2995465A (en) * 1959-08-07 1961-08-08 Minnesota Mining & Mfg Copy-sheet

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4097288A (en) * 1977-02-25 1978-06-27 Lawton William R Heat sensitive recording composition containing a complexed phenolics and a spiropyran or leuco lactone
US4180405A (en) * 1977-02-25 1979-12-25 Graphic Controls Corporation Heat-sensitive recording composition with mixed color precursors
US4397932A (en) * 1981-10-26 1983-08-09 A. B. Dick Company Electrophotographic composition and elements
WO1986007473A1 (en) * 1985-06-03 1986-12-18 Fairmount Chemical Co., Inc. Contrast enhancement layer
EP0738723A2 (de) * 1995-04-17 1996-10-23 General Electric Company Verfahren zur Herstellung polyalkylierte Xanthenderivate
EP0738723A3 (de) * 1995-04-17 1998-10-14 General Electric Company Verfahren zur Herstellung polyalkylierte Xanthenderivate
US8432279B2 (en) 2010-06-23 2013-04-30 Medline Industries, Inc. Multi-stage color activated system to detect unauthorized processing of medical devices

Also Published As

Publication number Publication date
GB1029547A (en) 1966-05-11
NL294553A (de)
BE632833A (de)
LU43835A1 (de) 1964-11-30
US3167445A (en) 1965-01-26

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