US3895173A - Dichromatic thermo-sensitive recording paper - Google Patents

Dichromatic thermo-sensitive recording paper Download PDF

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Publication number
US3895173A
US3895173A US332881A US33288173A US3895173A US 3895173 A US3895173 A US 3895173A US 332881 A US332881 A US 332881A US 33288173 A US33288173 A US 33288173A US 3895173 A US3895173 A US 3895173A
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Prior art keywords
color
layer
recording paper
forming
dispersion
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Expired - Lifetime
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US332881A
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English (en)
Inventor
Kinichi Adachi
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Priority claimed from JP47017063A external-priority patent/JPS5119989B2/ja
Priority claimed from JP47077219A external-priority patent/JPS4934842A/ja
Priority claimed from JP47105441A external-priority patent/JPS5119991B2/ja
Priority claimed from JP47105442A external-priority patent/JPS5119992B2/ja
Priority claimed from JP47105440A external-priority patent/JPS5119990B2/ja
Application filed by Matsushita Electric Industrial Co Ltd filed Critical Matsushita Electric Industrial Co Ltd
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Publication of US3895173A publication Critical patent/US3895173A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • 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
    • B41M5/34—Multicolour thermography
    • 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
    • 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
    • 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
    • B41M5/3275—Fluoran compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/423—Intermediate, backcoat, or covering layers characterised by non-macromolecular compounds, e.g. waxes
    • 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
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/42—Intermediate, backcoat, or covering layers
    • B41M5/44—Intermediate, backcoat, or covering layers characterised by the macromolecular compounds
    • 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

  • Mosher 5 7 ABSTRACT Recording paper which forms, for example, a red color when scratched with a thermal pen or head at a certain temperature and which forms, for example, a blue color when scratched with a thermal head at a higher temperature, said dichromatic thermosensitive paper having first and second layers formed from a dispersion in a film-forming binder of discontinuous particles of a leuco base of triphenylmethane or fluoran type dye and a phenolic acidic substance or an organic acid; and, disposed therebetween an inter layer capable of being thermally fused to dilute as well as to exclude the color formed in the first layer.
  • Recording materials which have heretofore been utilized for the above-mentioned uses, are represented by conventional photographic recording papers.
  • inks are used in recording machines employed at present. Accordingly, there have been such disadvantages for users that the recording papers are stained with the inks, or ink-flowing holes of pens are clogged with solids formed by vaporization of solvents of the inks, with the result that figures to be recorded are not recorded clearly or, in extreme cases, cannot be recorded.
  • pressure-sensitive papers have come to be used chiefly. At present, however, these recording papers are limited in uses to copying papers and teletyping papers which are used in place of carbon papers.
  • thermo-sensitive recording materials of various types have been proposed.
  • those which have already been put into practical use and those which will be put into practical use in the near future are as follows:
  • thermo-sensitive recording paper prepared by coating carbon or the like colored pigment or dye powder on a substrate, and then coating a white, opaque thermofusible substance on the resulting pigment or dye powder layer.
  • This recording sheet is of such a type that the thermofusible substance on the surface is scratched with a thermal stylus to expose and make visible the lower colored layer.
  • the recording material of this type has such drawbacks that scums are formed and multi-color recording is impossible.
  • a recording material which forms a color by forming a complex compound of an electron donor with an electron acceptor.
  • This recording material is of such a type that ferric stearate and pyrogallol, for example, are independently dispersed in a binder, and the binder is softened by application of heat, thereby reacting the two compounds with each other to form a visible complex compound.
  • the color formed in this case is dark brown.
  • thermo-softening substance such as polyvinyl alcohol
  • FIG. 1 shows the basic construction of the recording sheet of this invention
  • FIGS. 3, 4 and 5 show the relation between temperature of recording stamp and reflection density of image obtained.
  • FIGS. 6 A and 6 B and 7 A and 7 B show the relation between reflection density and width of lines of image obtained.
  • the color-forming dye reacts with the colorforming agent to form a color different in hue from the first color.
  • the sensitizer 2.3 acts to promote the reaction of the color-forming dye with the color-forming agent.
  • the crystalline organic substance contained in the inter layer fuses to dilute as well as to push aside the dye which has formed the first color in the first layer, and when heat is further applied, the organic substance so acts that the dye, which has formed the second color in the second layer, does not mix with the dye, which has formed the first color in the first layer.
  • the first and second layers form colors, but the dye, which has formed the color in the first layer, is diluted and pushed aside by means of the inter layer and is surrounded by the dye, which has formed the color in the second layer, to be brought into such a state that, apparently, it has formed no color, and only the second layer is made visible, whereby the recording paper can form two brilliant colors.
  • the quantity of heat applied to each of the colorforming layers is dependent on the temperature of a thermal head contacted with the paper surface to give a record on the recording paper, the contact time of the thermal head with the paper surface, and the thermal conductivity of the recording paper from the surface to each layer.
  • the quantity of heat applied to the first color-forming layer 1 is greater than the applied to the second color-forming layer, even if the temperature of the thermal head and the contact time thereof with the paper surface are definite.
  • the temperature of the first colorforming layer is higher than that of the second colorforming layer, and hence is not always required to be made higher than a temperature at which the second color-forming layer forms a color.
  • this kind of color-forming dye and color-forming agent are mixed or contacted with each other either as they are or in the form of solutions, whereby the color-forming dye forms a color due to electron transfer.
  • no color is formed in case the said two components are dispersed individually in a non-solvent therefor by use of a binder and are then contacted with each other. This is ascribable to the fact that the binder separates the two components from each other to inhibit the contact thereof. If the binder which has separated the two components from each other is fused, or either the color-forming agent or the color-forming dye is fused to bring the two into contact with each other, there is formed a color.
  • the first color-forming layer forms a color according to the aforesaid color formation principle
  • the second color-forming layer forms a color.
  • the color-forming dye in the first color-forming layer does not substantially differ in amount from that in the second color-forming layer, and if no inter layer has been disposed between the two layers, the color formed in the first color-forming layer is mixed with the color formed in the second color-forming layer to make it impossible to form two brilliant colors.
  • the recording paper is subjected to a dot printer, two colors, which are to be formed, become mere shade and light, and thus the recording paper cannot be used as a two color recording paper.
  • the color-forming dye in the first color-forming layer is smaller in amount than that in the second colorforming layer, and in case a thermofusible crystalline organic substance is present in the inter layer, the first and second color-forming layers form colors at the same time by application of heat Q
  • the crystalline organic substance present in the inter layer fuses to dilute as well as to push aside the first color formed in the first layer, whereby the recording paper can form two brilliant colors.
  • the aforesaid color-forming dye and colorforming agent form a color according to color formation mechanism based on ionization of the color forming dye due to contact of the said two components with each other. ln preparing the recording paper by use of the said two color-forming components, the two components are separated from each other by means of a binder so as to inhibit the occurrence of color formation reaction at normal temperature. When heat is applied to the recording paper, the two components are swelled or activated and initiate to react with each other. In this case, the density of the formed color reaches maximum when the two components have completely mixed with each other.
  • the recording paper is made greater in 7 value by introduction of a third substance (referred to as sensitizer in the present invention) in addition to the color-forming dye and the colorforming agent, so that the recording paper can form brilliant two colors.
  • the sensitizer is a crystalline organic substance having a sharp melting point, and has such action that when fused by application of heat. it dissolves at least one of the color-forming agent and the color-forming dye to quickly contact and mix the two with each other. Accordingly, the value of 'y can be made greater. Further, when a substance having a suit able melting point is selected as the sensitizer, it is possible to establish the temperature at which the color formation is initiated.
  • the sensitizer used in the present invention is thermofusible by itself, so that it is not'preferable to use as the sensitizer a substance which fuses at the storage temperature of the recording paper or which does not fuse at an ordinary color formation temperature of the color-forming components. in this sense, it is preferable that the sensitizer has a melting point in the range from 70C. to 180C.
  • color forming dyes there are used, in general, leuco bases of triphenylmethane type dyes represented by the general formula (I) or leuco bases of fluoran type dyes represented by the general formula (2).
  • dye bases are effective as the color-forming dyes. They are scarcely soluble in nonpolar or substantially non-polar solvents such as, for example, n-hexane, xylene, ligroin, benzene and toluene, and in water, and can be pulverized to fine particles of less than 10 microns.
  • the sensitizers there are used colorless or palecolored crystalline organic substances having a melting point of 70 to l80C. which, when fused, can dissolve at least one of the color-forming dyes and colorforming agents. Effective as such substances are organic compounds having nitrogen in the molecules of nitro, amino and the like groups. Further, it has been found that acetamide, stearamide, phthalonitrile, mnitroaniline and B-naphthylamine are most suitable as the binders used in the present invention.
  • the substances to be incorporated into the inter layer may be the aforesaid phenolic substances or organic acids.
  • Favorable results are obtained when the said substances are used together with the aforesaid sensitizers.
  • talc, clay, titanium oxide, zinc oxide or calcium carbonate may be incorporated with an aim to improve the recording paper in whiteness and printability and to prevent the paper from adhering to a thermal head.
  • Rhodamine Lactam as a colorforming dye was mixed with 200 parts by weight of a 5 wt% aqueous solution of polyvinyl alcohol (PVA lO7 produced by Kuraray Co., Ltd. and the resulting mixture was ground for at least 2 hours in a ball mill having an inner volume of 500 liters to prepare a dispersion A.
  • the color-forming dye had scarcely dissolved but had dispersed in the form of fine particles of less than several microns.
  • p-hydroxybenzoic acid 35 parts by weight was mixed with 200 parts by weight of a 5 wt% aqueous polyvinyl alcohol solution, and the resulting mixture was ground for at least 2 hours in a ball mill to prepare a dispersion B.
  • the color-forming agent had dispersed in the form of fine particles of less than several microns.
  • stearamide 20 parts by weight was mixed with 200 parts by weight of a 3 wt% aqueous solution of polyvinyl alcohol (PVA 20S produced by Kuraray Co., Ltd.), and the resulting mixture was ground for at least 2 hours in a ball mill to prepare a dispersion F.
  • PVA 20S polyvinyl alcohol
  • the amount of the coated dispersion E after air-drying was 3 g/m.
  • a mixed dispersion comprising 1 part by weight of the dispersion C, 25 parts by weight of the dispersion D and 15 parts by weight of the dispersion F.
  • the amount of the coated mixed dispersion after air-drying was I glm In the above-mentioned manner. a recording paper was obtained.
  • the red component was made invisible by use of a red filter (Kodak Ratten No. 25), while in measuring the density of the second color (FIG. 2-B), the blue component was made invisible by use of a blue filter (Kodak Ratten No. 478).
  • the paper (a) and the paper (b) incorporated with the sensitizer were individually recorded by means of a printer using a silicone resistor having 7 dots per line.
  • the paper (b) incorporated with the sensitizer could be recorded at a speed of 95 cha/sec. to give a blue-free record.
  • the paper (a) incorporated with no sensitizer could not give the same record as in the paper (b) unless it was recorded at a speed of 22 cha./sec.
  • a recording paper (d) was obtained in the same manner as above, except that stearamide having a melting point of I09C. was incorporated as a sensitizer into the first color-forming layer and phthalonitrile having a melting point of l4lC. was incorporated as a sensitizer into the second colorforming layer.
  • the D-max value of the first color is the density measured when the density of the second color became 0.l. (The dens '-s of the first and second colors were measured by use of. respectively, the red and blue filters used in Example I.)
  • FIGS. 6 and 7 show color formation states per dot of the recording papers (c) and (d), respectively, when the recording papers were individually recorded by means of a thermal printer using as a head a silicon resistor having 7 dots (each 0.4 X 0.4 mm. in size) per dot.
  • A shows the color formation state at the time when the first color was formed in the first color-forming layer
  • B shows the color formation state at the time when the second color was formed in the second color-forming layer.
  • the curve 1 represents the color formation state of the blue component of the first color
  • the curve 2 represents the color formation state of the red component of the second color.
  • the color formation state of the recording paper containing no sensitizers is such that at the time of color formation of the first color-forming layer, there is formed a blue color which has been mixed with the second color, i.e. red, (FIG. 6-A), and at the time of color formation of the second color-forming layer, there is formed a red color which has considerably been mixed with the first color, i.e. blue, (FlG. 6-H), whereas the color formation state of the recording paper (d) containing the sensitizers is such that at the time of color formation of each colorforming layer, there is formed a color which has not been mixed with the other component, with the result that a brilliant dichromatic recording can be obtained.
  • Such effect of sensitizers is particularly marked in the case of a dichromatic type recording paper, and a clear record can be obtained by making great the difference in melting point between the two sensitizers to be incorporated into the individual layers.
  • This recording paper was subjected to recording by use of the aforesaid recorder, whereby a red color could be recorded by application of an input energy of 1.8 mj., and a brilliant blue color could be recorded by application of an input energy of 2.8 mj.
  • Areal ratio of The areal ratio of first color component to second color component is the ratio of the area surrounded by the density curve of the first color to the area surrounded by the density curve of the second color. as seen in FIG. 7.
  • thermo-sensitive recording paper according to claim 1, wherein the heat capacity A necessary to form the first color of the first layer, the heat capacity B necessary to form the second color of the second layer, and the heat capacity C necessary to fuse the thermo-fusible inter layer, satisfy the inequality A C S B.
  • a recording paper according to claim 1, wherein the inter layer comprises a dispersion in a film-forming binder of discontinuous particles of a phenolic substance or an organic acid.
  • inter layer comprises a dispersion in a film-forming binder of discontinuous particles of at least one member selected from the group consisting of acetamide, stearamide, phthalonitrile, m-nitroaniline and B-naphthylamine.
  • a recording paper according to claim I wherein the first layer and/or the second layer additionally contain as a sensitizer at least one member selected from the group consisting of stearamide, acetamide, phthalonitrile, nitroaniline and ,B-naphthylamine.

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  • Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
US332881A 1972-02-17 1973-02-15 Dichromatic thermo-sensitive recording paper Expired - Lifetime US3895173A (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP47017063A JPS5119989B2 (US20080094685A1-20080424-C00004.png) 1972-02-17 1972-02-17
JP47077219A JPS4934842A (US20080094685A1-20080424-C00004.png) 1972-07-31 1972-07-31
JP47105441A JPS5119991B2 (US20080094685A1-20080424-C00004.png) 1972-10-20 1972-10-20
JP47105442A JPS5119992B2 (US20080094685A1-20080424-C00004.png) 1972-10-20 1972-10-20
JP47105440A JPS5119990B2 (US20080094685A1-20080424-C00004.png) 1972-10-20 1972-10-20

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US3895173A true US3895173A (en) 1975-07-15

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US (1) US3895173A (US20080094685A1-20080424-C00004.png)
AU (1) AU460361B2 (US20080094685A1-20080424-C00004.png)
CA (1) CA987103A (US20080094685A1-20080424-C00004.png)
DE (1) DE2307774C3 (US20080094685A1-20080424-C00004.png)
FR (1) FR2172386B1 (US20080094685A1-20080424-C00004.png)
GB (1) GB1409831A (US20080094685A1-20080424-C00004.png)
NL (1) NL153479B (US20080094685A1-20080424-C00004.png)

Cited By (23)

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US3981523A (en) * 1975-03-24 1976-09-21 Moore Business Forms, Inc. Carbonless manifold business forms
US4032690A (en) * 1975-01-24 1977-06-28 Mitsubishi Paper Mills, Ltd. Thermosensitive recording material
US4054684A (en) * 1974-12-03 1977-10-18 La Cellophane Composition for forming colored images, new recording material and process using same
US4062567A (en) * 1974-05-03 1977-12-13 Moore Business Forms, Inc. Dual system carbonless paper
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
US4138357A (en) * 1976-05-19 1979-02-06 Fuji Photo Film Co., Ltd. Thermochromic material
USRE30116E (en) * 1975-03-24 1979-10-16 Moore Business Forms, Inc. Carbonless manifold business forms
EP0012587A1 (en) * 1978-12-14 1980-06-25 Ricoh Company, Ltd Thermo-sensitive multi-color recording material and process for preparation thereof
US4255491A (en) * 1978-07-18 1981-03-10 Fuji Photo Film Co., Ltd. Heat-sensitive recording paper
US4283458A (en) * 1978-08-18 1981-08-11 Fuji Photo Film Co., Ltd. Heat-sensitive recording paper containing a novel electron accepting compound
US4477676A (en) * 1976-01-22 1984-10-16 The Hilton-Davis Chemical Co. 4-(3-Indolyl)-2,3-dichloro-4-oxo-2-butenoic acids
US4525428A (en) * 1983-01-25 1985-06-25 Mitsubishi Paper Mills, Ltd. Process for producing multicolor heat-transfer recording paper
US4567019A (en) * 1977-05-11 1986-01-28 Graphic Controls Corporation Color reversing compositions
US5804528A (en) * 1995-11-20 1998-09-08 Oji Paper Co., Ltd. Thermosensitive recording material with a high fog resistance
EP0897809A1 (en) * 1997-08-19 1999-02-24 Nippon Paper Industries Co., Ltd. A spontaneously colour changing type thermal sensitive recording medium
EP1092551A2 (en) * 1999-10-15 2001-04-18 Nippon Paper Industries Co., Ltd. Multi chromatic thermally sensitive recording medium
WO2002096665A1 (en) 2001-05-30 2002-12-05 Polaroid Corporation Thermal imaging system
US20030176281A1 (en) * 2002-03-13 2003-09-18 Hultgren Bror O. Choice of chromophores in two color imaging systems
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
US7830405B2 (en) 2005-06-23 2010-11-09 Zink Imaging, Inc. Print head pulsing techniques for multicolor printers
US9387714B2 (en) 2013-01-10 2016-07-12 Oji Holdings Corporation Multicolor thermal recording material, and method for color formation of said multicolor thermal recording material

Families Citing this family (4)

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Publication number Priority date Publication date Assignee Title
IT991891B (it) * 1973-07-27 1975-08-30 Olivetti & Co Spa Perfezionamenti in un elemento termosensibile e nelle sue condi zioni di impiego nei sistemi di riproduzione e registrazione termo grafica
US4151748A (en) * 1977-12-15 1979-05-01 Ncr Corporation Two color thermally sensitive record material system
US4599630A (en) * 1983-11-15 1986-07-08 Ricoh Company, Ltd. Two-color thermosensitive recording material
JPH0755582B2 (ja) * 1984-07-27 1995-06-14 株式会社リコー 二色感熱記録型ラベル

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US3167445A (en) * 1962-06-29 1965-01-26 Nashua Corp Heat responsive marking sheets
US3427180A (en) * 1965-03-31 1969-02-11 Ncr Co Pressure-sensitive record system and compositions
US3432327A (en) * 1964-03-13 1969-03-11 Pilot Pen Co Ltd Pressure sensitive copying sheet and the production thereof
US3661586A (en) * 1970-02-20 1972-05-09 Bell & Howell Co Lead iodine film
US3715213A (en) * 1969-02-19 1973-02-06 Mita Industrial Co Ltd Diazo-type multicolor reproduction

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US3167445A (en) * 1962-06-29 1965-01-26 Nashua Corp Heat responsive marking sheets
US3432327A (en) * 1964-03-13 1969-03-11 Pilot Pen Co Ltd Pressure sensitive copying sheet and the production thereof
US3427180A (en) * 1965-03-31 1969-02-11 Ncr Co Pressure-sensitive record system and compositions
US3715213A (en) * 1969-02-19 1973-02-06 Mita Industrial Co Ltd Diazo-type multicolor reproduction
US3661586A (en) * 1970-02-20 1972-05-09 Bell & Howell Co Lead iodine film

Cited By (43)

* Cited by examiner, † Cited by third party
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Also Published As

Publication number Publication date
DE2307774A1 (de) 1973-08-23
AU460361B2 (en) 1975-04-24
FR2172386A1 (US20080094685A1-20080424-C00004.png) 1973-09-28
DE2307774C3 (de) 1981-06-11
NL153479B (nl) 1977-06-15
NL7302182A (US20080094685A1-20080424-C00004.png) 1973-08-21
FR2172386B1 (US20080094685A1-20080424-C00004.png) 1974-02-01
DE2307774B2 (de) 1976-01-15
AU5214573A (en) 1974-09-19
CA987103A (en) 1976-04-13
GB1409831A (en) 1975-10-15

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