US2995466A - Heat-sensitive copy-sheet - Google Patents

Heat-sensitive copy-sheet Download PDF

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Publication number
US2995466A
US2995466A US832179A US83217959A US2995466A US 2995466 A US2995466 A US 2995466A US 832179 A US832179 A US 832179A US 83217959 A US83217959 A US 83217959A US 2995466 A US2995466 A US 2995466A
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United States
Prior art keywords
heat
copy
sheet
parts
acid
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US832179A
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English (en)
Inventor
David P Sorensen
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3M Co
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Minnesota Mining and Manufacturing Co
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Publication date
Application filed by Minnesota Mining and Manufacturing Co filed Critical Minnesota Mining and Manufacturing Co
Priority to US832179A priority Critical patent/US2995466A/en
Priority to DEM46166A priority patent/DE1200845B/de
Priority to GB27414/60A priority patent/GB962545A/en
Application granted granted Critical
Publication of US2995466A publication Critical patent/US2995466A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • 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
    • G03C1/54—Diazonium salts or diazo anhydrides

Definitions

  • thermographic reproduction process involves placing a heat-sensitive copy-sheet in heat-conductive pressure-contact with a differentially radiation-absorptive graphic original and subjecting the latter to brief intense irradiation, e.g. with radiation rich in infra-red.
  • the heat-pattern produced in the original transfers to the copy-sheet; there results a corresponding visible change in the latter.
  • a true reproduction of the original is produced directly, without the necessity of subsequent treatment with solutions or vapors to develop a latent image, or of other processing.
  • the present invention likewise provides normally stable heat-sensitive copy-sheets which are useful in the direct thermographic reproduction of graphic originals, solely through the action of radiant energy and without the addition of solutions or vapors or other analogous adjuvants, but which distinguish over the prior art in that the imageforming reaction is caused to occur between exclusively organic interreactant materials, with formation of an organic dye or color-body containing a doubly bonded nitrogen atom as an essential chromophore group.
  • the heat-sensitive copy-paper of this invention ordinarily includes a thin paper support web coated on one surface with a thin layer of a visibly heat-sensitive composition.
  • Various binder materials may be employed where required for maintaining the heat-sensitive reactants in position. Such binders may be applied in monomeric or sub-polymeric form and then polymerized in situ, but are more conveniently handled as solutions of the polymeric material in volatile solvents which are subsequently removed. Additional coatings may be pro vided; for example a white opaque protective surface layer is frequently placed over a heat-sensitive layer on a transparent paper or film support web; Treated or impregnated paper, polymeric film, or other analogous fibrous or non-fibrous webs are useful as support or backing members.
  • the heat-sensitive materials may be applied as a coating or incorporated within the body of the supporting web.
  • Example I This example provides a normally stable heat-sensitive 2,995,466. Patented Aug. 8, 1961 copy-sheet which converts from an olf-white to a greenish black color at image areas under thermographic reproduction procedures through the controlled formation of an oxazine dye.
  • Mixture A consists of 10 parts of gallic acid, 10 parts of polycarbonate resin (Lexan" polycarbonate resin, and parts of dioxan volatile liquid solvent.
  • Mixture B is prepared from 5 parts of 3-methyl-4- nitrosophenol, 10 parts of polycarbonate resin, and parts of dioxan.
  • Mixture C contains 5 parts of p-N- methylacetylaminobenzene diazonium fluoborate, 10 parts of polystyrene resin, and 85 parts of acetone.
  • Mixture C is first applied as a thin uniform coating on flexible transparent polyester film (3-mil Mylar polyester film) by knife coating at an orifice of 2 mils, and dried. Equal weights of mixtures A and B are then blended together and the mixture applied by knife coating at an orifice of 3 mils over the dried first coating.
  • the dried sheet is heat-sensitive and semi-transparent.
  • Color formation occurs sub stantially instantaneously in the dry copy-sheet on heating to or above the decomposition temperature of the diazonium fluoborate complex, i.e. to approximately C.
  • the dye-forming reaction immediately terminates, so that the initial sharp outline of the reproduced image areas is maintained and the background areas remain unaltered.
  • oxazine-dye-forming organic reactants which have likewise given good results in the preparation of heat-sensitive copy-sheets include: 2-hydroxy-3- methyl-S-nitrosobenzoic acid with gallic acid or resorcinol; nitrosothymol with gallic acid or 3-hydroxy-2-naphthoic acid or beta-naphthol; and para-nitrosobenzoic acid with gallic acid.
  • these inter-reactant oxazine dye progenitors are colorless or weakly colored solids which react readily when mixed together in aqueous acetic acid at room temperature or with gentle warming.
  • Example 2 in this example the several components of the heatsensitive layer are supplied from a single coating mixture, while still maintaining excellent stability even under high ambient humidity storage and use conditions.
  • Two mixtures are first separately prepared, e.g. by ball milling.
  • One contains 10 parts of N-carbethoxy-p-nitrosodiphenylamine, 10 parts of methyl methacrylate resin (Lucite 44" resin), and 80 parts of acetone.
  • the second contains 9 parts of gallic acid, one part of (3-chloropropenyl) benzene, 10 grams of the methacrylate resin, and 80 parts of acetone.
  • a blend of two parts of the first and three parts of the second is smoothly coated on 25 lb. map overlay tracing paper at an orifice of 3 mils, and dried at room temperature. The resulting light yellowish sheet forms deep blue heated image areas in the therrnographic reproduction process herein described.
  • Thecolor is due to the formation of an oxazine dye, as in Example 1.
  • Another dye-forming combination employing the same N-carbalkoxy nitroso compound and which has provided useful heat-sensitive copy-sheets in structures as here indicated contains N-carbethoxy-p-nitrosodiphenylamine and 3-hydroxy-2-naphthoic acid.
  • the present example likewisb provides heat-sensitive copy-sheets having excellent stability and light background color, and producing dark blue or blue-black heat-image areas.
  • the composition is coated on map overlay tracing paper using a coating orifice of 3 mils, and the sheet is dried at room temperature.
  • the off-white sheet product converts to intense blue at heated image areas in the thermographic reproduction process.
  • Equally effective copy-sheets are produced on substitution of equivalent amounts of N-nitrosophenylbenzylamine for the N-nitrosodiphenylamine.
  • the principal colorbody produced in the heated copy-sheet is an oxazine dye; and in each instance color formation proceeds by a mechanism involving conversion to reactive form of an initially non-reactive progenitor material in the presence of an acidic component.
  • Example 3 the non-reactive N-nitroso compound first rearranges to a C-nitroso compound; in Example 2 the carbalkoxy group, which initially prevents coupling by steric hindrance, is decomposed and removed; and in each of'Examples 1-3 the nitroso compound as thus formed or as initially present is converted to an intermediate reactive oxime which immediately couples with the aromatic hydroxy compound, producing an oxazine dye wherein a doubly bonded nitrogen atom is an essential chromophore.
  • Example 4 Transparent polyester film is first coated with a two-mil layer of a smooth dispersion of 5 parts of para-aminoacetanilide benzenediazonium fluoborate in a solution of parts of ParapoP' isobutylene-styrene resin in 85 parts of methylcyclohexane.
  • the dried sheet is light yellow in color, stable under all normal ofiice handling and filing, and convertible to deep blue at heat-image areas under thermographic reproduction conditions.
  • the color-body produced is an azo dye, containing doubly bonded nitrogen as an essential chromophore.
  • the two layers may be reversed, the triazene-coupler layer being coated directly on the transparent film; or the components of the two layers may be mixed together and applied simultaneously.
  • the triazene-coupler layer of this example does not form a visible image when subjected to thermographic reproduction processes in commercially available equipment. With the acid-progenitor present, cleavage of the normally stable triazene occurs under the thermographic heating, with formation of an intermediate diazo component which then immediately couples with the azo coupler component.
  • Typical tn'azenes which have been used in producing these stable copy-sheets include l,3-bis(2-carboxyphenyl) triazenc, l-(2-car-boxyphenyl)-3-phenyl-3-ethyltriazene, l- (2-methyl-4-chlorophenyl) 3 (p N methylacetamidophenyl) triazene, N-phenylazoisatoic anhydride, 3,3'-dimethoxy 4,4 diphenylenebis( 3 methyl-B-phenyl-l-triazene), 3 phenyl-4-oxo-3,4-dihydro-l,2,3-benz.otriazine, and 4-hydroxy-1,2,3-naphthotriazine.
  • triazenes which in dry sheet form possess adequate stability and undergo a color-producing reaction with the azo coupler component at or near maximum commercially available thermographic copying conditions even in the absence of acid-progenitors.
  • Typical of such triazenes are 1-(2- carbomethoxyphenyl)-3-phenyltriazene and l-(p-N-methylacetamidophenyl)-3-phenyltriazene.
  • aromatic amine compounds and active methylene compounds known to be useful as azo coupling components are also applicable in the preparation of these copy-sheet materials in many instances, it is preferred to employ the more strongly reactive aromatic hydroxy azo couplers in copy-sheets prepared as in Example 4; and of these, the aryl amides of 3-hydroxy-2-naphthoic acid, known commercially as the Naphtol AS series of azo couplers, are found to be particularly desirable.
  • Exemplary compounds are 3-hydroxy-2-naphthanilide and 3- hydroxy-N-Z-naphthyl-Z-naphthamide.
  • diazonium fluoborates useful in these heat-sensitive copy-sheet formulations include para-acetylaminobenzenediazonium fluoborate, metaand ortho-carboxybenzenediamnium fluoborate, orthophenylbenzenediazonium fluoborate, 3,5-dimethylbenzenediazonium fluoborate, para- (bisbenzenediazonium fluoborate), and ortho-carboxybenzene-diazonium fiuoborate.
  • These compounds may effectively be replaced by analogous benzenediazonium hexafluorophosphates, exemplified by such compounds as para-anilinobenzenediazonium hexafluorophosphate, para- N.- methylacetylaminobenzenediazonium hexafluorophosphate, para-acetylaminobenzenediazonium hexafluorophosphate, and para-chlorobenzenediazonium hexafluorophosphate.
  • analogous benzenediazonium hexafluorophosphates exemplified by such compounds as para-anilinobenzenediazonium hexafluorophosphate, para- N.- methylacetylaminobenzenediazonium hexafluorophosphate, para-acetylaminobenzenediazonium hexafluorophosphate, and para-chlorobenzenediazonium hexafluorophosphate.
  • the dry sheet is pure white and forms a brown heatimage.
  • the reaction involves the formation in the dry heat-sensitive layer of a Schifis base color-body by acidinduced liberation of aldehyde from the polyvinyl formal followed immediately by inter-reaction of the aldehyde and the p-aminoacetanilide.
  • the color-body contains doubly bonded nitrogen as an essential chromophore.
  • the polyvinyl formal resin serves both as a reactant progenitor and as a polymeric binder thus simplifying the preparation of the coating composition.
  • acetal-type binders e.g. polyvinyl butyral (Butvar) resin
  • Inert binders may be included if desired, although simplified formulations as described in the example are much preferred.
  • other equally reactive and otherwise suitable non-polymeric solid acetals may be incorporated together with suitable organic amines in a coating composition including an inert binder component, to provide useful but less desirable heat-sensitive copy-sheet materials.
  • thermographic reproduction process hereinbefore referred to makes difficult the direct measurement of the temperatures attained in the heat-sensitive copy-sheet during said process.
  • An indirect method of temperature determination is therefore ordinarily employed, in which a segment of the copy-sheet is momentarily pressed against a heated metal test bar at a known temperature and any visibile effect on the sheet is noted.
  • Copy-sheets which under such test are converted from colorless or weakly colored to visibly distinct and relatively intensely colored form at temperatures within the range of about 90-150" C. are found to produce excellent results in terms of the thermographic reproduction of typewritten or analogous graphic originals on th'ermographic copy-machines such as the Thermo-Fax" brand Secretary copying machines.
  • Copy-sheets prepared in accordance with each of the examples hereof have been found to be operable within the temperature range indicated and to produce usefully clear and distinct thermographic copies of graphic originals.
  • the process involves brief intense irradiation of the composite from a source 14, and results in formation of visibly distinct converted image areas 15 in the heat-sensitive layer 13.
  • the opaque protective surface coating of Examples 1 and 5 may be omitted, or may be added to the copy-sheets of Examples 24 where the carrier web is transparent.
  • the two coatings forming the heat-sensitive layer of Example 1 may be combined in a single coating, or separately applied in inverse order.
  • the heat-sensitive layer may be made in the form of a self-sustaining film; or the reactant materials may be supported within a fibrous web in the virtual absence of a film-forming binder.
  • the specific compound or class of compounds to be introduced as the acid-progenitor in any particular formulation will depend not only on the temfit perature at which the color-forming reaction is desired to occur but also on the other specific components of the formulation.
  • the fluoborate and fiuophosphate compounds are preferably employed with binders soluble in hydrocarbon solvents, since their activity is reduced when combined in alcohol with binders soluble therein, presumably by some side-reaction.
  • formulations containing reactive amino components which are capable of forming color-bodies with diazonium radicals are preferably prepared with active-halogen-containing acid-progenitors rather than with the fluoborates or the like.
  • the active-halogen-containing acid-progenitors of Examples 2, 3 and 5 and other useful compounds of the same general structure having one or more halogen atoms in activated positions on the skeletal carbon chain or ring may be selected and characterized as being capable of precipitating the corresponding silver halide from an alcoholic aqueous solution of silver nitrate.
  • an alcoholic aqueous solution of silver nitrate As an illustration, the addition of a solution of one part of alphanaphthoylchloride in ten parts of ethanol to a solution of one part of silver nitrate in ten parts of ethanol and ten parts of water produces an immediate copious precipitation of silver chloride.
  • a heat-sensitive copy-sheet adapted for making a clear and sharp reproduction of a graphic original by a dry thermographic process involving brief application of a heat-pattern corresponding to said original, said copysheet being visibly stable under normal storage conditions and being rapidly permanently visibly changed on heating to a conversion temperature within the approximate range of l50 C., said copy-sheet including a visibly heat-sensitive layer containing, in intimate association, 1) weakly colored, normally solid, essentially non-hygroscopic and non-volatile, inter-reactant progenitors of intensely colored organic color-bodies containing doubly bonded nitrogen as an essential chromophore,
  • one of said progenitors being acid-convertible to a modification which under acidic conditions is rapidly visibly irreversibly inter-reactive with another of said progenitors, and (2) acid-progenitor means, stable under said normal storage conditions and liberating a Lewis acid on being momentarily heated at said conversion temperature.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US832179A 1959-08-07 1959-08-07 Heat-sensitive copy-sheet Expired - Lifetime US2995466A (en)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US832179A US2995466A (en) 1959-08-07 1959-08-07 Heat-sensitive copy-sheet
DEM46166A DE1200845B (de) 1959-08-07 1960-08-05 Waermeempfindliches Kopierblatt
GB27414/60A GB962545A (en) 1959-08-07 1960-08-08 Improved thermographic copy-sheets

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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3076721A (en) * 1959-10-19 1963-02-05 Minnesota Mining & Mfg Heat-sensitive copy-paper and method of making
US3129101A (en) * 1961-11-01 1964-04-14 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US3146348A (en) * 1961-09-25 1964-08-25 Minnesota Mining & Mfg Heat-sensitive copy-sheet
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
US3149992A (en) * 1962-06-29 1964-09-22 Nashua Corp Heat sensitive sheets
US3166433A (en) * 1962-08-01 1965-01-19 Nashua Corp Heat sensitive copy and recording sheet
US3167444A (en) * 1962-11-19 1965-01-26 Nashua Corp Heat responsive marking sheets
US3185585A (en) * 1962-11-19 1965-05-25 Nashua Corp Heat responsive marking sheets
US3185583A (en) * 1962-11-19 1965-05-25 Nashua Corp Heat responsive marking sheets
US3185584A (en) * 1962-11-19 1965-05-25 Nashua Corp Heat responsive marking sheets
US3191030A (en) * 1962-11-02 1965-06-22 Dietzgen Co Eugene Process of making and using thermographic reproduction paper
US3194659A (en) * 1961-03-06 1965-07-13 Kalvar Corp Reflex copying method using heat developable light scattering materials
US3194660A (en) * 1961-06-26 1965-07-13 Ibm Reflex copying method
US3224878A (en) * 1961-12-01 1965-12-21 Dietzgen Co Eugene Thermographic diazotype reproduction material, method of making and method of using
US3312551A (en) * 1962-07-25 1967-04-04 Keuffel & Esser Co Heat and light sensitive diazo sulfonate and azo coupler coated sheet
US3367797A (en) * 1961-11-21 1968-02-06 Minnesota Mining & Mfg Heat sensitive copy-sheet
US3463638A (en) * 1965-08-20 1969-08-26 Ibm Heat-fixable light-sensitive compositions and elements
US4055425A (en) * 1975-03-10 1977-10-25 Gaf Corporation Diazotype material and graphic reproduction processes employing the same
FR2368736A1 (fr) * 1976-10-22 1978-05-19 Scott Paper Co Composition photo-sensible pour diazotypie, matiere la comportant et leur procede de mise en oeuvre
US20060290769A1 (en) * 2005-06-23 2006-12-28 Polaroid Corporation Print head pulsing techniques for multicolor printers
US20080225308A1 (en) * 2003-02-25 2008-09-18 Zink Imaging, Llc Image stitching for a multi-head printer
US20080238967A1 (en) * 2001-05-30 2008-10-02 Zink Imaging, Llc Print head pulsing techniques for multicolor printers
US20100087316A1 (en) * 2001-05-30 2010-04-08 Day John C Thermally-Insulating Layers and Direct Thermal Imaging Members Containing Same
US20110063392A1 (en) * 2008-05-15 2011-03-17 Pingfan Wu Generation of color images
US20110121557A1 (en) * 2008-05-15 2011-05-26 Pingfan Wu Multilayer articles capable of forming color images
US8975011B2 (en) 2010-06-30 2015-03-10 3M Innovative Properties Company Multi-layer articles capable of forming color images and method of forming color images
US8975012B2 (en) 2010-06-30 2015-03-10 3M Innovative Properties Company Multi-layer articles capable of forming color images and methods of forming color images

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2180660B (en) * 1985-08-06 1989-08-23 Mitsubishi Chem Ind Heat transfer recording sheet
JPS6290285A (ja) * 1985-10-12 1987-04-24 Fuji Photo Film Co Ltd 感熱記録材料

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2663655A (en) * 1952-05-15 1953-12-22 Minnesota Mining & Mfg Heat-sensitive copying paper
US2663656A (en) * 1952-05-15 1953-12-22 Minnesota Mining & Mfg Heat-sensitive copying paper
US2748024A (en) * 1952-05-13 1956-05-29 Dick Co Ab Transfer sheet for use in a hectograph duplicating process
US2838994A (en) * 1956-04-11 1958-06-17 Dick Co Ab Elements for use in practice of spirit duplication process
US2873668A (en) * 1952-10-25 1959-02-17 Dick Co Ab Azo dye duplicating process
US2899334A (en) * 1958-05-19 1959-08-11 Heat-sensitive layer
US2940812A (en) * 1957-11-21 1960-06-14 Ici Ltd New textile treatment process

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2748024A (en) * 1952-05-13 1956-05-29 Dick Co Ab Transfer sheet for use in a hectograph duplicating process
US2663655A (en) * 1952-05-15 1953-12-22 Minnesota Mining & Mfg Heat-sensitive copying paper
US2663656A (en) * 1952-05-15 1953-12-22 Minnesota Mining & Mfg Heat-sensitive copying paper
US2873668A (en) * 1952-10-25 1959-02-17 Dick Co Ab Azo dye duplicating process
US2838994A (en) * 1956-04-11 1958-06-17 Dick Co Ab Elements for use in practice of spirit duplication process
US2940812A (en) * 1957-11-21 1960-06-14 Ici Ltd New textile treatment process
US2899334A (en) * 1958-05-19 1959-08-11 Heat-sensitive layer

Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3076721A (en) * 1959-10-19 1963-02-05 Minnesota Mining & Mfg Heat-sensitive copy-paper and method of making
US3194659A (en) * 1961-03-06 1965-07-13 Kalvar Corp Reflex copying method using heat developable light scattering materials
US3194660A (en) * 1961-06-26 1965-07-13 Ibm Reflex copying method
US3146348A (en) * 1961-09-25 1964-08-25 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US3129101A (en) * 1961-11-01 1964-04-14 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US3367797A (en) * 1961-11-21 1968-02-06 Minnesota Mining & Mfg Heat sensitive copy-sheet
US3224878A (en) * 1961-12-01 1965-12-21 Dietzgen Co Eugene Thermographic diazotype reproduction material, method of making and method of using
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
US3149992A (en) * 1962-06-29 1964-09-22 Nashua Corp Heat sensitive sheets
US3167445A (en) * 1962-06-29 1965-01-26 Nashua Corp Heat responsive marking sheets
US3312551A (en) * 1962-07-25 1967-04-04 Keuffel & Esser Co Heat and light sensitive diazo sulfonate and azo coupler coated sheet
US3166433A (en) * 1962-08-01 1965-01-19 Nashua Corp Heat sensitive copy and recording sheet
US3191030A (en) * 1962-11-02 1965-06-22 Dietzgen Co Eugene Process of making and using thermographic reproduction paper
US3185583A (en) * 1962-11-19 1965-05-25 Nashua Corp Heat responsive marking sheets
US3185584A (en) * 1962-11-19 1965-05-25 Nashua Corp Heat responsive marking sheets
US3185585A (en) * 1962-11-19 1965-05-25 Nashua Corp Heat responsive marking sheets
US3167444A (en) * 1962-11-19 1965-01-26 Nashua Corp Heat responsive marking sheets
US3463638A (en) * 1965-08-20 1969-08-26 Ibm Heat-fixable light-sensitive compositions and elements
US4055425A (en) * 1975-03-10 1977-10-25 Gaf Corporation Diazotype material and graphic reproduction processes employing the same
FR2368736A1 (fr) * 1976-10-22 1978-05-19 Scott Paper Co Composition photo-sensible pour diazotypie, matiere la comportant et leur procede de mise en oeuvre
US20110050829A1 (en) * 2001-05-30 2011-03-03 Zink Imaging, Llc Print head pulsing techniques for multicolor printers
US8377844B2 (en) 2001-05-30 2013-02-19 Zink Imaging, Inc. Thermally-insulating layers and direct thermal imaging members containing same
US20080238967A1 (en) * 2001-05-30 2008-10-02 Zink Imaging, Llc Print head pulsing techniques for multicolor printers
US20100087316A1 (en) * 2001-05-30 2010-04-08 Day John C Thermally-Insulating Layers and Direct Thermal Imaging Members Containing Same
US7791626B2 (en) 2001-05-30 2010-09-07 Zink Imaging, Inc. Print head pulsing techniques for multicolor printers
US8098269B2 (en) 2001-05-30 2012-01-17 Zink Imaging, Inc. Print head pulsing techniques for multicolor printers
US20110085185A1 (en) * 2003-02-25 2011-04-14 Zink Imaging, Llc Image stitching for a multi-head printer
US20080225308A1 (en) * 2003-02-25 2008-09-18 Zink Imaging, Llc Image stitching for a multi-head printer
US8345307B2 (en) 2003-02-25 2013-01-01 Zink Imaging, Inc. Image stitching for a multi-head printer
US7808674B2 (en) 2003-02-25 2010-10-05 Zink Imaging, Inc. Image stitching for a multi-head printer
US8072644B2 (en) 2003-02-25 2011-12-06 Zink Imaging, Inc. Image stitching for a multi-head printer
US20060290769A1 (en) * 2005-06-23 2006-12-28 Polaroid Corporation Print head pulsing techniques for multicolor printers
US8164609B2 (en) 2005-06-23 2012-04-24 Zink Imaging, Inc. Print head pulsing techniques for multicolor printers
US7830405B2 (en) 2005-06-23 2010-11-09 Zink Imaging, Inc. Print head pulsing techniques for multicolor printers
US20110050830A1 (en) * 2005-06-23 2011-03-03 Zink Imaging, Inc. Print head pulsing techniques for multicolor printers
US8502846B2 (en) 2005-06-23 2013-08-06 Zink Imaging, Inc. Print head pulsing techniques for multicolor printers
US20110121557A1 (en) * 2008-05-15 2011-05-26 Pingfan Wu Multilayer articles capable of forming color images
US20110063392A1 (en) * 2008-05-15 2011-03-17 Pingfan Wu Generation of color images
US8411120B2 (en) 2008-05-15 2013-04-02 3M Innovative Properties Company Generation of color images
US9045654B2 (en) 2008-05-15 2015-06-02 3M Innovative Properties Company Multilayer articles capable of forming color images
US8975011B2 (en) 2010-06-30 2015-03-10 3M Innovative Properties Company Multi-layer articles capable of forming color images and method of forming color images
US8975012B2 (en) 2010-06-30 2015-03-10 3M Innovative Properties Company Multi-layer articles capable of forming color images and methods of forming color images

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GB962545A (en) 1964-07-01
DE1200845B (de) 1965-09-16

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