US2967785A - Thermographic copying material - Google Patents

Thermographic copying material Download PDF

Info

Publication number
US2967785A
US2967785A US833764A US83376459A US2967785A US 2967785 A US2967785 A US 2967785A US 833764 A US833764 A US 833764A US 83376459 A US83376459 A US 83376459A US 2967785 A US2967785 A US 2967785A
Authority
US
United States
Prior art keywords
heat
sensitive
solution
compound
copying
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
US833764A
Other languages
English (en)
Inventor
Frank D Allen
James A Van Allan
John J Sagura
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.)
Eastman Kodak Co
Original Assignee
Eastman Kodak 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
Priority to BE593980D priority Critical patent/BE593980A/xx
Application filed by Eastman Kodak Co filed Critical Eastman Kodak Co
Priority to US833764A priority patent/US2967785A/en
Priority to FR835508A priority patent/FR1269417A/fr
Priority to GB28248/60A priority patent/GB952187A/en
Application granted granted Critical
Publication of US2967785A publication Critical patent/US2967785A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
    • C07D209/04—Indoles; Hydrogenated indoles
    • C07D209/30—Indoles; Hydrogenated indoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to carbon atoms of the hetero ring
    • C07D209/40—Nitrogen atoms, not forming part of a nitro radical, e.g. isatin semicarbazone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B41M5/327—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • 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

Definitions

  • THERMOGRAPHIC COPYING MATERIAL Filed Aug. 14, 1959 lNDOLE COMPOUND PHENOL COMPOUND SUPPO/P 7' INDOLE COMPOUND PHENOL COMPOUND /0 SUPPORT /0 4 SUPPORT /7 ⁇ ' PR/NTED CHARA arm /64 I ORIGINAL FRANK D. ALLEN JAMES A. VAN ALLAN JOHN J 8/1 GURA ZNVENTORS ATTORNEYS United States Patent '0 THERMOGRAPHIC COPYING MATERIAL Frank D. Allen, James A. Van Allan, and John J. Sagura,
  • thermographic copying materials and methods have been previously described in a number of domestic and foreign patents. These materials frequently have the advantage of simplicity over certain photographic processes in that they produce a direct positive image of the original upon exposing the heat-sensitive or thermographic copying material in heat conductive association with a graphic original to radiant energy (e.g., infrared radiation).
  • radiant energy e.g., infrared radiation
  • certain of these thermographic materials which have been previously used are only slightly sensitive to heat, and, consequently, excessively intense exposures are necessary in order to produce a facsimile copy.
  • Other materials may not suffer from the aforementioned defect, but they are diflicult to use, or handle, in that they contain metallic ions which might stain the material upon which the heat-sensitive layer is coated.
  • thermographic or heat-sensitive materials have the disadvantage of being excessively sensitive to ordinary light.
  • Other heat-sensitive, copying materials exhibit thermotrophy and lose their developed color when the heat-sensitive material is cooled to room temperature. It is immediately obvious that these heat-sensitive materials have only limited use, and, in certain instances, cannot be used at all if one desires to produce facsimile copies on a commercial scale.
  • thermographic methods of reproduction described in the prior art require that the plurality of heat-sensitive ingredients be maintained in physically-distinct relationship, it is not always necessary, according to our invention, to separate physically the heatsensitive components in our compositions from one another.
  • the instant invention provides a convenient means of reproducing graphic originals by exposure of such originals in contact with certain heat-sensitive layers.
  • the heat-sensitive layers useful in practicing our invention contain as an essential ingredient at least one indole derivative selected from those represented by the following general formula:
  • R represents a hydrogen atom or an alkyl group, such as methyl, ethyl, etc.
  • Q and Q each represents the non-metallic atoms necessary to complete a monocyclic nucleus containing only one nitrogen atom, said nucleus containing an unsubstituted carbon atom in the 3-position with respect to said nitrogen atom
  • D represents the atoms necessary to complete a benzene ring, which KIT may be substituted by alkyl (e.g., methyl, ethyl, etc.), alkoxyl (methoxyl, ethoxyl, etc.), etc.
  • Especially useful compounds embraced by Formula I above include those represented by the following general formula:
  • indole compounds embraced by Formula II above include those represented by the following general formula:
  • R R R and R each represents a hydrogen atom or a lower alkyl group, e.g., methyl, ethyl, etc.
  • Z and Z each represents the non-metallic atoms necessary to complete a monocyclic ring containing from 5 to 6 atoms in the ring, only one of said atoms in the monocyclic ring being a nitrogen atom.
  • Typical monocyclic nuclei defined by Q, Q Z and Z include pyrrolidine, piperidine, morpholine, etc., as well as substituted derivatives thereof, including alkyl (e.g., methyl.
  • Figure 1 is a graphic reproduction of a heat-sensitive copying material which can be processed according to our invention
  • Figure 2 is a graphic reproduction of a second type of heat-sensitive material which can be processed according to our invention
  • Figure 3 is a graphic reproduction of one method of exposing the heat-sensitive copying material illustrated in Figure 2, the copying material being in heat-conductive association with an original.
  • Exposure of a copying sheet comprising at least one of the indole compounds represented by Formulas I, II, or Hz: in heat-conductive association with a graphic original as hereinafter described results in a substantially immediate, visible color change.
  • Infrared radiant energy has been found to be particularly useful in practicing our invention, since such energy is readily obtainable from many illuminating sources.
  • indole compounds it these indole compounds ,are associated wtih a compound containing a phenolic hydroxyl group, or an organic compound which contains an enolize able ketomethylene group, including 5pyrazolone compounds containing a hydrogen atom in the 4-position, as well as compounds containing an extracyclic (acyclic) group.
  • a compound containing a phenolic hydroxyl group or an organic compound which contains an enolize able ketomethylene group, including 5pyrazolone compounds containing a hydrogen atom in the 4-position, as well as compounds containing an extracyclic (acyclic) group.
  • R represents a hydrogen atom or an alkyl group such as methyl, ethyl, etc.
  • X represents a hydrogen atom, a halogen atom (e.g., chlorine, bromine, etc.), or a non-basic organic substituent (e.g., methyl, ethyl, etc.).
  • non-basic is intended to define substituentsother than an amino nitrogen-containing group.
  • the heat-sensitive material forming the heat-sensitive areas of the copying sheets of our invention can be coated on any suitable support, especially supports having low thermal conductivity, such as paper.
  • any suitable support especially supports having low thermal conductivity, such as paper.
  • a support which transmits the exposing radiation especially where the graphic original does not transmit such radiation (i.e., at least one of these should transmit radiation).
  • the. indole compounds of Formulas I, II or Ila can be used alone as the heat-sensitive materials, or they can be used in combination with the phenolic compounds, pyrazolone compounds, or compounds containing an acylic ketomethylene group.
  • the heat-sensitive indole compounds are used in combination with the phenolic compounds, pyrazolone compounds or compounds containing an acyclic ketomethylene. group, the ratio of the components in the heatsensitive system can vary, depending upon the particular materials, effects desired, etc.
  • indole compounds in a layer distinct from the layer containing the phenolic compound, pyrazolone compound, or compound containing the acyclic ketomethylene group, since spontaneous color formation may occur if the two components are intimately associated in the same layer.
  • both components can be dispersed in a common solvent and coated onto the support from the same solution without any spontaneous color formation taking place.
  • the heat-sensitive layers useful in our invention can be prepared in several ways depending upon the use to which the heat-sensitive copying sheet is to be put.
  • the invention contemplates the application of a solution of at leastone of the above-formulated indole compounds to the support, followed by evaporation of the solvent from the coating solution.
  • a second solution containing the second component (the phenolic compound, pyrazolone compound, or compound containing an extracyclic ketomethylene group) of the heatsensitive material can be applied to the copying sheet and the solvent evaporated from this second coating solution.
  • this method of operation cannot be employed if the second component undergoes substantially
  • the components of the heat-sensitive system can be incorporated in an inert vehicle by simply adding these components. to a solution of the inert vehicle.
  • useful inert vehicles include esters of cellulose, cellulose ethers (e.g., ethyl cellulose, etc.), polyvinyl resins (e.g., polyvinyl chloride, polystyrene, polymethylmethacrylate, polyvinyl acetate, as well as copolymers of these polymeric materials), etc.
  • the heat-sensitive copying sheets of our invention can be, treated with solutions designed to provide a protective overcoat for the heatsensitive layers. For instance, after application of the heat-sensitive material to. the. copying sheet, a solution of gelatin or other organic material can be applied over the heat-sensitive material.
  • the layers of the heat-sensitive materials can contain inert pigments for the purpose of increasing the contrast of the final copy. For instance, an opaque layer may be applied over the heat-sensitive components, or an opaque layer may be applied on the reverse side of the copying sheet.
  • Typical compounds which can be employed together with the indole compounds of our invention in order to lower the reaction. temperature include the following:
  • indole compounds were prepared'bydissolving isatin or an isatin derivative. ina suitableorganic solvent,
  • thermographic duplicating device of the type described in Miller U.S. Patent 2,740,895, issued December 22, 1953. A copy of the original was obtained as a blue image in a matter of seconds.
  • Example 3 (Formula I) RmgA I Dichlorohydr-oquinone was dissolved in a solution of Vinylite VYLF resin as described in Example 2 and then coated on an ordinary paper support. The dry 9 layer was then overcoated with a methanol solutionof BingB polyvinyl butyral resin containing isatin-3-dipiperidide. N/ The coating was then dried and placed in contact with a graphic original and passed through a thermographic R copying device as described in Example 2. A copy of the TABLE Analysis Indole M.P.,
  • the resulting viscous solution was typewritten characters, developed a heat patternin those then coated on tfaflslucent P p Stoclf and allowed areas containing the line copy and caused the produc- 'Y- pp of i dry coatlng was Placed 111 tion of a blue image in the associated heat-sensitive copywfltact a lq 011811131 and Passed f ing material.
  • thermosraphlc' ps devlce of the yp ed were in contact with areas of the original containing no Patent that the fadlamm typewritten characters did not undergo any visible passed first through the heat-Sensitive ps/ s sheet and h i then to the graphic original.
  • the heat-sensitive material can be p overcoated with a transparent layer containing an ultra- A solution of 1.25 grams of 3-piperidino-3-morphoviolet absorbing compound, such as 9-benzalfluorene, 5- lino isatin in 100 cc. of methanol was added to 1.8 benzal-3-n-cetyl 2 phenylimino 4 thiazolidone, etc., grams of the same phenol used in Example 5, dissolved to achieve greater stability. in 25 cc. of ethanol. To the resulting clear solution Example 2 were then added 100 cc. of a 5% solution of polyvinyl butyral in methanol.
  • 3-piperidino-3-morphoviolet absorbing compound such as 9-benzalfluorene
  • the contrast of the prints was increased considerably by incorporating baryta or titanium dioxide in the polyvinyl butal coatings or by coating a separate solution of polyvinyl butal containing the white pigment over the heat-sensitive layer. Ifdesired, the pigmented layer can be coated beneath the heat-sensitive layer or on the support side of the supporting surface.
  • platsicizers such as butylphthalate, or antioxidants, such as bntylated hydroxyanisole can be added to the solutions in order to lower the triggering temperature of the thermo graphic product.
  • Example 7 The above ingredients were combined as described above in Example 7, and the resulting, clear viscous solution was coated on a translucent paper support and the coating dried.
  • a matting agent such as finely-divided silica or dispersed polyethylene, can be added to the above solutions inorder to improve the surface characteristics of the product.
  • the addition of these materials can conveniently be made at the time of addition of the piperidine.
  • Example 9 Component A.--A solution of 100 grams of 2-(2,4-ditert. amylphenoxyacetamino) 4,6-dichloro-5-methylphenol (Phenol No. 6) in 400 ccs. of ethyl acetate was filtered while hot and added to a solution of 1000 grams of 10% bone gelatin in water. To the solution were added 300 ccs. of distilled water and 160 ccs. of 5% alkanolB dispersing agent (sodiumisobutyl-naphthalene sulfonate) at 40 C. After vigorous stirring, the dispersion was run through the colloid mill three times at a setting of 3 to 5 microns. The dispersion was chill-set at 40 F., noodled and dried on wire screens at 75 F. for two days under a vacuum of inches and for an additional two days at 90 F. under avacuum of inches.
  • alkanolB dispersing agent sodiumisobutyl-na
  • Component B A solution of 40 grams of 3-piperidino- 3-morpholinoisatin in 1600 ccs. of 1,4-dioxane and 400 ccs. of methanol was filtered and poured into 8 liters of distilled'water containing 80 ccs. of piperidine at a temperatnre of- 8 to 10 C. After stirring for /2 hour, the precipitate was filtered by suction and washed three times on a filter with cold, distilled water, the last water wash containing 1% piperidine. The precipitate was then airdried at room temperature leaving fine, creamy-white grams of Component A in 1500 ccs.
  • the reconstituted dispersion was coated on an ordinary onion skin paper, 10 inches wide, at the rate of 21 feet per minute. Best results were obtained with an air knife set a inch. The coating averaged about 9 to 10 grams per square foot of emulsion or about 0.8 gram/square foot of solids. Exposure of the dried coating as described above gave an excellent reproduction of a graphic original as a .blue-on-white image.
  • FIG. 1 is a cross-sectional view of a thermographic copying sheet wherein the heat sensitive components are incorporated in separate layers.
  • Figure l a suitable support 10 is coated with a layer 11 comprising a phenol compound 12. Over layer 11 is coated layer 13 comprising particles of indole compound 14.
  • Figure 2 is a cross-sectional view of a thermographic copying material wherein both heat-sensitive ingredients are incorporated in the same layer.
  • the copying material comprises a support 10 coated with a heat-sensitive layer 15 having dispersed therein a phenol compound 12 and an indole compound 14.
  • FIG 3 there is illustrated an assembly suitable for producing facsimile copies using the particular heatsensitive material depicted in Figure 2.
  • a graphic original 16 having printed material 17 thereon, is placed in contact with the uncoated surface of support 10 having coated thereon a heat-sensitive layer 18.
  • a facsimile copy 19 of the printed character of the original is reproduced as the darkened portion shown in the drawing.
  • the source of infrared radiation can be arranged so that the rear surface of the original receives the infrared radiation, although in such cases it may be convenient to have an insulating surface applied to the rear surface of the original in order to minimize loss of the heat generated in the infrared absorbing graphic pattern in the original.
  • the heat-sensitive layer of the copying material can be placed in contact with the printed characters of the original (i.e., 17 of the drawing), and the assembly then exposed either from the side of the original or the rear side of the copying sheet.
  • a colloidal binding agent When a colloidal binding agent is employed in combination with the iridole compounds of our invention, alone or in combination with a phenol compound or a compound containing an enolizable keto-methylene group, the amount thereof can bevaried in order to control the contrast of the resulting copy.
  • Various esthetic effects can be produced by adding inert pigments or colorants to the colloidal dispersion or to one of the protected layers applied to the supporting surface or over the heat-sensitlve material, as indicated above.
  • ninhydrine compounds can be'employed in place of certain of the indole compounds of our invention to provide excellent thermographic copies.
  • Such ninhydrine derivatives can be prepared by condensing'one of the heterocyclic secondary 9 amines-mentioned above, such as piperidine, etc., together with ninhydrin.
  • the surface temperatures reached on the recording materials used in our invention can vary considerably, depending upon the particular indole compound employed and the presence or absence of an auxiliary color-forming component, such as a phenol compound, or a compound containing an enolizable ketomethylene group.
  • the heat-sensitive materials used in our invention may undergo a color change at a temperature as low as about 45 to 50 C., or a considerably higher temperature, such as 125 C., may be required in order to effect the desired color change.
  • the selection of ingredients should be made so that the desired color change occurs at a temperature below the distortion or charring temperature of the support (which may comprise such materials as cellophane, cellulose acetate film, paper, wood, leather, etc.)
  • a heat-sensitive, copying sheet comprising a support and coated on said support a heat-sensitive area containing a compound selected from the class represented by the following general formula:
  • R represents a member selected from the class consisting of a hydrogen atom and an alkyl g oup
  • Q and Q1 each represents the non-metallic atoms necessary to complete a monocyclic nucleus containing only one nitrogen atom, said nucleus containing an unsubstituted carbon atom in the 3-position with respect to said nitrogen atom
  • D represents the atoms necessary to complete a benzene ring
  • said heat-sensitive area being disposed on said support so that upon exposure of said heat-sensitive area to radiant energy in heat-conductive association with a pattern containing portions highly absorptive of said radiant energy and portions substantially nonabsorptive of said radiant energy, said heat-sensitive area undergoes a rapid color change only in those areas in heat conductive association with those areas highly absorptive of said radiant energy, said heatsensitive, copying sheet being stable at room temperature, being substantially insensitive to visible radiations and being non-sticking at 125 C.
  • a heat-sensitive, copying sheet comprising a support and coated on said support a heat-sensitive area containing (a) a compound selected from those represented by the following general formula:
  • R represents a member selected from the class consisting of a hydrogen atom and an alkyl group
  • Q and Q each represents the non-metallic atoms necessary to complete a monocyclic nucleus containing only one nitrogen atom, said nucleus containing an unsubstituted carbon atom in the 3+position with respect to said nitrogen atom
  • D represents the atoms necessary to complete a benzene ring
  • a heat-sensitive copying sheet comprising a support and coated on said support a heat-sensitive area containing (a) a compound selected from those represented by the following general formula:
  • a heat-sensitive, copying sheet comprising (1) a fibrous support and (2) a heat-sensitive colloid layer having dispersed therein particles of (a) a compound selected from those represented by the'following' general formula:
  • R represents a member selected from the class consisting of a hydrogen atom and an alkyl group
  • Q and Q each represents the non-metallic atoms necessary to complete a monocyclic nucleus containing only one nitrogen atom, said nucleus containing an unsubstituted carbon atom in the 3-position with respect to said nitrogen atom
  • Dre presents the atoms necessary to complete a benzene ring
  • particles of (b) a compound selected from the class consisting of phenols and compounds containing an enolizable keto group said particles (11) and (b) being maintained in a physically-distinct relationship, so that upon exposure of said heat-sensitive, copying sheet to radiant energy in heat-conductive association with a pattern containing portions highly absorptive of said radiant energy and portions substantially nonabsorptive of said radiant energy, said heat-sensitive copying sheet undergoes a rapid color change only in those areas in heat-conductive association with those areas highly absorptive of said radiant energy, saidlheatsensitive copying
  • a heat-sensitive, copying sheet comprising (1). a thin paper support having low thermoconductivity, (2) a colloid layer having dispersed therein discrete particles of a compound selected from those represented by the following general formula:
  • R represents a member selected from the: class consisting of a hydrogen atom and an alkyl group
  • Q andQ each represents, the non-metallic atoms necessary to complete a monocyclic nucleus containing only one nitrogen atom, said nucleus containingan unsubstituted.
  • A- heat-sensitive, copying sheet comprising (1) a thin paper support having low thermoconductivity and (2) a heat-sensitive colloid area having dispersed therein (a) discrete particles of a compound selected from those'represented by the following generalformula:
  • R represents a member selected from the class consisting of ahydrogen atom and an alkyl group
  • Q and Q each represents the non-metallic atoms necessary to complete a monocyclic nucleus containing only one nitrogen atom, said' nucleus containing an unsubstituted carbon atom in the 3-position with respect to said nitrogen atom
  • D represents the atoms necessary to complete a benzene ring
  • R represents a member selected from the class consisting of an alkyl group and an aryl group
  • R represents a member selected from the class consisting of a hydrogen atom and an alkyl group
  • X represents a member selected from the class consisting of a hydrogen atom, a halogen atom, and anon-basic organic substituent
  • B a 5.-pyrazolone compound containing a hydrogen atom in the'4-position
  • C a compound containing an acyclic group, said particles (a) and (b) being maintained in physically-distinct relationship, so that upon exposure of said heat-sensitive copying sheet to infra-red energy in heat-conductive association with a pattern containing portions highly absorptive ofv said infrared energy and portions substantially non-absorptive of said infrared energy, said heat-sensitive copying sheet undergoes a rapid color change only, in those areas in heat-conductive, association with those regions highly absorptive of saidinfrared energy,
  • a heat-sensitive, copying sheet as defined in claim 4; wherein saidparticls (a), comprise isatin-3-dipiperidide and said particles (b) comprise tetrachlorohydroquinone.
  • a heat-sensitive, copying sheet as defined in claim 4, wherein said particles (:2) comprise isatin-B-dipiperidide and said particles (b). comprise dichlorol1ydroquinone.
  • a heat-sensitive, copying sheet as defined in claim 4, wherein said particles- (a) comprise isatin-B-dimorpholide and said particles (1)) comprise 2-(2,4-di-tert.- amylphenoxyacetamino -4,6-dichloro-5-methylphenol.
  • a heat-sensitive, copying sheet as defined in claim 13 14 4, wherein said particles (a) comprise 3-piperidino-3- heat-sensitive at the temperatures employed in producing morpholinoisatin and said particles (b) comprise 2-(2,4- visible copies from said heat-sensitive copying sheet. (ltterti'amylPhenoxyacetammo)4,6 dichlom's'methyl' References Cited in the file of this patent p eno 11.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Indole Compounds (AREA)
US833764A 1959-08-14 1959-08-14 Thermographic copying material Expired - Lifetime US2967785A (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BE593980D BE593980A (fr) 1959-08-14
US833764A US2967785A (en) 1959-08-14 1959-08-14 Thermographic copying material
FR835508A FR1269417A (fr) 1959-08-14 1960-08-10 Nouveau produit de copie thermographique
GB28248/60A GB952187A (en) 1959-08-14 1960-08-15 Thermographic copying materials

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US833764A US2967785A (en) 1959-08-14 1959-08-14 Thermographic copying material

Publications (1)

Publication Number Publication Date
US2967785A true US2967785A (en) 1961-01-10

Family

ID=25265209

Family Applications (1)

Application Number Title Priority Date Filing Date
US833764A Expired - Lifetime US2967785A (en) 1959-08-14 1959-08-14 Thermographic copying material

Country Status (3)

Country Link
US (1) US2967785A (fr)
BE (1) BE593980A (fr)
GB (1) GB952187A (fr)

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3024362A (en) * 1958-08-09 1962-03-06 Kalle Ag Heat sensitive reproduction material and mbthod of using same
US3057999A (en) * 1960-03-31 1962-10-09 Columbia Ribbon & Carbon Thermographic copy paper and process
US3090697A (en) * 1961-02-13 1963-05-21 Nashua Corp Heat sensitive marking papers and methods for making same
US3094619A (en) * 1961-01-03 1963-06-18 Minnesota Mining & Mfg Ultra-violet radiation-desensitizable thermographic copy-sheet and method
US3094417A (en) * 1961-01-03 1963-06-18 Minnesota Mining & Mfg Heat sensitive copy sheet, process of making and using
US3129109A (en) * 1961-09-25 1964-04-14 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US3132039A (en) * 1960-12-22 1964-05-05 Monsanto Chemicals Heat responsive recording sheet
US3149993A (en) * 1962-01-18 1964-09-22 Nashua Corp Heat developable paper
US3149991A (en) * 1962-01-05 1964-09-22 Nashua Corp Heat developable paper
US3166433A (en) * 1962-08-01 1965-01-19 Nashua Corp Heat sensitive copy and recording sheet
US3185086A (en) * 1960-05-18 1965-05-25 Ritzerfeld Wilhelm Method and arrangement for reproducing an image
US3241997A (en) * 1961-12-23 1966-03-22 Schutzner Walter Heat-sensitive copying material
US3274929A (en) * 1962-06-13 1966-09-27 Columbia Ribbon & Carbon Planographic printing plate and processes
US3283708A (en) * 1961-03-10 1966-11-08 Thermographically produced lithographic printing plates
US3293055A (en) * 1961-10-05 1966-12-20 Ncr Co Heat sensitive coating composition and copy sheet coated therewith
US3293061A (en) * 1963-11-21 1966-12-20 Man Res Lab Inc Primary amine modified secondary or tertiary amine-polyketo reaction product in a heat developable copy sheet
US3451338A (en) * 1964-05-11 1969-06-24 Ncr Co Thermographic recording system
US3661586A (en) * 1970-02-20 1972-05-09 Bell & Howell Co Lead iodine film
US3950600A (en) * 1973-07-27 1976-04-13 Ing. C. Olivetti & C., S.P.A. Thermosensitive element, and its employ in the thermographic reproduction or record systems
US4111703A (en) * 1977-02-25 1978-09-05 Graphic Controls Corporation Heat-sensitive coating composition with 4-aromatic and hydroxy substituted piperidine derivative and cyclic polyketo compound
US4675161A (en) * 1982-12-29 1987-06-23 Sakata Shokai, Ltd. Indicator for detection of thermal history

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2740895A (en) * 1950-08-21 1956-04-03 Minnesota Mining & Mfg Thermoprinting apparatus
US2899334A (en) * 1958-05-19 1959-08-11 Heat-sensitive layer

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2740895A (en) * 1950-08-21 1956-04-03 Minnesota Mining & Mfg Thermoprinting apparatus
US2899334A (en) * 1958-05-19 1959-08-11 Heat-sensitive layer

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3024362A (en) * 1958-08-09 1962-03-06 Kalle Ag Heat sensitive reproduction material and mbthod of using same
US3057999A (en) * 1960-03-31 1962-10-09 Columbia Ribbon & Carbon Thermographic copy paper and process
US3185086A (en) * 1960-05-18 1965-05-25 Ritzerfeld Wilhelm Method and arrangement for reproducing an image
US3132039A (en) * 1960-12-22 1964-05-05 Monsanto Chemicals Heat responsive recording sheet
US3094619A (en) * 1961-01-03 1963-06-18 Minnesota Mining & Mfg Ultra-violet radiation-desensitizable thermographic copy-sheet and method
US3094620A (en) * 1961-01-03 1963-06-18 Minnesota Mining & Mfg Copy-sheet and method
US3094417A (en) * 1961-01-03 1963-06-18 Minnesota Mining & Mfg Heat sensitive copy sheet, process of making and using
US3090697A (en) * 1961-02-13 1963-05-21 Nashua Corp Heat sensitive marking papers and methods for making same
US3283708A (en) * 1961-03-10 1966-11-08 Thermographically produced lithographic printing plates
US3129109A (en) * 1961-09-25 1964-04-14 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US3293055A (en) * 1961-10-05 1966-12-20 Ncr Co Heat sensitive coating composition and copy sheet coated therewith
US3241997A (en) * 1961-12-23 1966-03-22 Schutzner Walter Heat-sensitive copying material
US3149991A (en) * 1962-01-05 1964-09-22 Nashua Corp Heat developable paper
US3149993A (en) * 1962-01-18 1964-09-22 Nashua Corp Heat developable paper
US3274929A (en) * 1962-06-13 1966-09-27 Columbia Ribbon & Carbon Planographic printing plate and processes
US3166433A (en) * 1962-08-01 1965-01-19 Nashua Corp Heat sensitive copy and recording sheet
US3293061A (en) * 1963-11-21 1966-12-20 Man Res Lab Inc Primary amine modified secondary or tertiary amine-polyketo reaction product in a heat developable copy sheet
US3451338A (en) * 1964-05-11 1969-06-24 Ncr Co Thermographic recording system
US3661586A (en) * 1970-02-20 1972-05-09 Bell & Howell Co Lead iodine film
US3950600A (en) * 1973-07-27 1976-04-13 Ing. C. Olivetti & C., S.P.A. Thermosensitive element, and its employ in the thermographic reproduction or record systems
US4111703A (en) * 1977-02-25 1978-09-05 Graphic Controls Corporation Heat-sensitive coating composition with 4-aromatic and hydroxy substituted piperidine derivative and cyclic polyketo compound
US4675161A (en) * 1982-12-29 1987-06-23 Sakata Shokai, Ltd. Indicator for detection of thermal history

Also Published As

Publication number Publication date
GB952187A (en) 1964-03-11
BE593980A (fr)

Similar Documents

Publication Publication Date Title
US2967785A (en) Thermographic copying material
US3874946A (en) Photothermographic element, composition and process
US3801321A (en) Photothermographic element,composition and process
US4196002A (en) Photothermographic element containing heat sensitive dye materials
US2995465A (en) Copy-sheet
US3871887A (en) Photothermographic composition, element and process
EP0582144A1 (fr) Matériau d'enregistrement thermosensible adressé par laser
US3856527A (en) Protective layer for photothermographic elements
US4201590A (en) Heat sensitive reactive products of hexaarylbiimidazole and antihalation dyes
US3547648A (en) Copy-sheet
US3852093A (en) Heat-sensitive copy-sheet
DE2415603A1 (de) Waermeempfindliche materialien und ihre verwendung in aufzeichnungsverfahren
US2899334A (en) Heat-sensitive layer
US3856526A (en) Protective layer for photothermographic elements
US5275932A (en) Thermal development accelerators for thermographic materials
US3108896A (en) Heat-sensitive copying-paper
US4081278A (en) Heat sensitive dye layers comprising a benzopinacol
US3143418A (en) Vesicular image-forming coatings comprising a light-sensitive carbazido
US3146348A (en) Heat-sensitive copy-sheet
US3795532A (en) Wide latitude copy sheet
JPS595438B2 (ja) 感熱性記録材料
US3965282A (en) Thermographic recording material
US5306686A (en) Negative-acting thermographic materials
US2950987A (en) Thermally-sensitive recording elements
US3782941A (en) Photothermographic element,composition and process