US3505093A - Heat-sensitive copy-sheet containing bis(triphenylphosphine)borohydridocopper (i) - Google Patents
Heat-sensitive copy-sheet containing bis(triphenylphosphine)borohydridocopper (i) Download PDFInfo
- Publication number
- US3505093A US3505093A US687126A US3505093DA US3505093A US 3505093 A US3505093 A US 3505093A US 687126 A US687126 A US 687126A US 3505093D A US3505093D A US 3505093DA US 3505093 A US3505093 A US 3505093A
- Authority
- US
- United States
- Prior art keywords
- heat
- triphenylphosphine
- borohydridocopper
- copy
- sensitive
- 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
Links
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 title description 19
- 239000000463 material Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 7
- 239000010408 film Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 150000001880 copper compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920006267 polyester film Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005041 Mylar™ Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N phenyl bromide Natural products BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/30—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers
- B41M5/32—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using chemical colour formers one component being a heavy metal compound, e.g. lead or iron
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5045—Complexes or chelates of phosphines with metallic compounds or metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/913—Material designed to be responsive to temperature, light, moisture
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
- Y10S430/165—Thermal imaging composition
Definitions
- a heat-sensitive copy-sheet useful in thermographic copying contains bis(triphenylphosphine)borohydrido copper (I) as the visibly heat-sensitive component.
- This invention relates to the copying of differentially radiation-absorptive graphic originals by thermographic methods involving brief exposure of the original to intense radiant energy while in heat-conductive contact with a heat-sensitive copy-sheet, and has particular reference to novel copy-sheet structures and compositions.
- the copy-sheets of this invention may be white or colorless, or may be made in various pastel colors for purposes of identification or color coding.
- the sheet will comprise a carrier or backing having a coating of the visibly heat-sensitive material, although the latter material may if desired be incorporated directly in the backing.
- the heat-sensitive material may be dispersed or dissolved in an appropriate heat-resistant film-forming binder in liquid form which is then applied to a thin flexible paper or film backing and solidified, e.g. by evaporation of solvent, at a temperature below the conversion temperature of the heat-sensitive material.
- the solution containing the heat-sensitive material may be deposited on a temporary support from which the dried residue is removed as a self-sustaining thin film.
- the heat-sensitive material may be applied directly to a suitably receptive paper or film surface, e.g. from solution in a volatile liquid vehicle, or incorporated in the paper sheet by adding the finely divided material to the paper-forming pulp in the beater or stuffing-box.
- a particular advantage of the present invention is that but a single compound serves as the heat-sensitive material, thereby avoiding such problems as incorrect proportioning of reactants, separation of interreactive layers, pro-reaction during coating, etc.
- the compound is soluble in readily available and inexpensive volatile liquids without deterioration so that solutions may be prepared and stored as desired. It is stable under all normal storage and use conditions, and the copy-sheet remains heatsensitive indefinitely even when stored under such normally adverse conditions as high relative humidity and direct sunlight. However when heated to a relatively high temperature, e.g. to about 165 C., the compound immediately undergoes an irreversible chemical change to form a dark-colored product which in the copy-sheet provides a visible record of the thermographically applied heat-pattern.
- bis(triphenylphosphine)borohydridocopper (I) provides all of the advantages set forth above when employed as the heat-sensitive component in thermographic heat-sensitive copy-sheets.
- the compound may be represented by the structural formula 3,505,093 Patented Apr. 7, 1970 Ice wherein Ph stands for phenyl. It is colorless, decomposes at about C., and is soluble in acetone, benzene, chloroform, tetrahydrofuran, methylene chloride and butanone-Z.
- the phenyl radicals may be substituted, for example with halogen or alkyl, to provide compounds having equally useful freedom from color, solubility, and heatsensitivity, and which are only slightly less resistant to deterioration on aging.
- the substitution of silver for copper produces a more expensive material which gives good images but is much less stable and in particular darkens during continued exposure to light.
- Compounds in which alkyl groups replace the phenyl (or substituted phenyl) radicals decompose to provide a visible change but with liberation of noxious and nauseating decomposition products. Accordingly the bis(triphenylphosphine) borohydridocopper (I) compounds are found to be particularly suitable and are at present greatly preferred.
- the bis(triphenylphosphine)borohydridocopper (I) may be the sole component of the heat-sensitive stratum as hereinbefore indicated. More typicallythere will be included additional components, of which various filmforming binders, opacifying agents, coloring agents, etc., are exemplary. Other reactant materials may also be included for various purposes, in particular including imagestabilizing agents which are reactive with'one or more of the heat decomposition products of the copper compound with formation of secondary image-forming compounds providing increased image density, contrasts, or permanence. An example is p-thiomethyl bromobenzene.
- Example 1 To the blue-colored solution of 2 millimoles of copper sulfate pentahydrate in 25 ml. of anhydrous methanol is added 10 mM. of triphenylphosphine. The solution changes to a straw color, indicating coordination of the phosphine to the cupric ion. Powdered potassium borohydride (10 mM.) is added to the clear solution, with evolution of hydrogen and precipitation of potassium sulfate and bis(triphenylphosphine)borohydridocopper (I). The mixed precipitate is recovered by filtration and the colorless copper compound is removed by extraction with chloroform. The solution is clear and colorless.
- a portion of the chloroform solution is uniformly applied over white bond paper, e.g. by brushing or with a cotton swab, and the solvent removed by evaporation at room temperature.
- the resulting sheet material serves as a heat-sensitive copy-sheet, producing a black image when heated at image areas in the thermographic copying process.
- the solution is similarly applied to a transparent Mylar polyester film and after drying is subjected to the thermographic copying procedure to produce dark image areas on the transparent coated film.
- coated sheets remain visibly unchanged and fully heat-sensitive after prolonged storage at room temperature under all ranges of humidity.
- Example 2 The bis(triphenylphosphine)borohydridocopper (I) is recovered from a separate portion of the saturated chloroform solution by precipitation with anhydrous ethanol,
- the product is a white crystalby weight of the weight of binder, and the solution is uniformly lightly coated on transparent polyester film. The coating is dried. The film is placed in face-to-face contact with a printed original which is then exposed through the film in a thermographic copying machine and at maximum exposure. A clear copy of the printed image is produced which is right-reading when viewed through the film.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Heat Sensitive Colour Forming Recording (AREA)
Description
United States Patent US. Cl. 117-36.8 5 Claims ABSTRACT OF THE DISCLOSURE A heat-sensitive copy-sheet useful in thermographic copying contains bis(triphenylphosphine)borohydrido copper (I) as the visibly heat-sensitive component.
This invention relates to the copying of differentially radiation-absorptive graphic originals by thermographic methods involving brief exposure of the original to intense radiant energy while in heat-conductive contact with a heat-sensitive copy-sheet, and has particular reference to novel copy-sheet structures and compositions.
The copy-sheets of this invention may be white or colorless, or may be made in various pastel colors for purposes of identification or color coding. In most instances the sheet will comprise a carrier or backing having a coating of the visibly heat-sensitive material, although the latter material may if desired be incorporated directly in the backing. As an example the heat-sensitive material may be dispersed or dissolved in an appropriate heat-resistant film-forming binder in liquid form which is then applied to a thin flexible paper or film backing and solidified, e.g. by evaporation of solvent, at a temperature below the conversion temperature of the heat-sensitive material. Alternatively, the solution containing the heat-sensitive material may be deposited on a temporary support from which the dried residue is removed as a self-sustaining thin film. Or the heat-sensitive material may be applied directly to a suitably receptive paper or film surface, e.g. from solution in a volatile liquid vehicle, or incorporated in the paper sheet by adding the finely divided material to the paper-forming pulp in the beater or stuffing-box.
A particular advantage of the present invention is that but a single compound serves as the heat-sensitive material, thereby avoiding such problems as incorrect proportioning of reactants, separation of interreactive layers, pro-reaction during coating, etc. The compound is soluble in readily available and inexpensive volatile liquids without deterioration so that solutions may be prepared and stored as desired. It is stable under all normal storage and use conditions, and the copy-sheet remains heatsensitive indefinitely even when stored under such normally adverse conditions as high relative humidity and direct sunlight. However when heated to a relatively high temperature, e.g. to about 165 C., the compound immediately undergoes an irreversible chemical change to form a dark-colored product which in the copy-sheet provides a visible record of the thermographically applied heat-pattern.
In accordance with the invention it has now been discovered that bis(triphenylphosphine)borohydridocopper (I) provides all of the advantages set forth above when employed as the heat-sensitive component in thermographic heat-sensitive copy-sheets. The compound may be represented by the structural formula 3,505,093 Patented Apr. 7, 1970 Ice wherein Ph stands for phenyl. It is colorless, decomposes at about C., and is soluble in acetone, benzene, chloroform, tetrahydrofuran, methylene chloride and butanone-Z.
The phenyl radicals may be substituted, for example with halogen or alkyl, to provide compounds having equally useful freedom from color, solubility, and heatsensitivity, and which are only slightly less resistant to deterioration on aging. The substitution of silver for copper produces a more expensive material which gives good images but is much less stable and in particular darkens during continued exposure to light. Compounds in which alkyl groups replace the phenyl (or substituted phenyl) radicals decompose to provide a visible change but with liberation of noxious and nauseating decomposition products. Accordingly the bis(triphenylphosphine) borohydridocopper (I) compounds are found to be particularly suitable and are at present greatly preferred.
The bis(triphenylphosphine)borohydridocopper (I) may be the sole component of the heat-sensitive stratum as hereinbefore indicated. More typicallythere will be included additional components, of which various filmforming binders, opacifying agents, coloring agents, etc., are exemplary. Other reactant materials may also be included for various purposes, in particular including imagestabilizing agents which are reactive with'one or more of the heat decomposition products of the copper compound with formation of secondary image-forming compounds providing increased image density, contrasts, or permanence. An example is p-thiomethyl bromobenzene.
The following examples will serve to illustrate but not to limit the invention.
Example 1 To the blue-colored solution of 2 millimoles of copper sulfate pentahydrate in 25 ml. of anhydrous methanol is added 10 mM. of triphenylphosphine. The solution changes to a straw color, indicating coordination of the phosphine to the cupric ion. Powdered potassium borohydride (10 mM.) is added to the clear solution, with evolution of hydrogen and precipitation of potassium sulfate and bis(triphenylphosphine)borohydridocopper (I). The mixed precipitate is recovered by filtration and the colorless copper compound is removed by extraction with chloroform. The solution is clear and colorless.
A portion of the chloroform solution is uniformly applied over white bond paper, e.g. by brushing or with a cotton swab, and the solvent removed by evaporation at room temperature. The resulting sheet material serves as a heat-sensitive copy-sheet, producing a black image when heated at image areas in the thermographic copying process.
The solution is similarly applied to a transparent Mylar polyester film and after drying is subjected to the thermographic copying procedure to produce dark image areas on the transparent coated film.
The coated sheets remain visibly unchanged and fully heat-sensitive after prolonged storage at room temperature under all ranges of humidity.
Example 2 The bis(triphenylphosphine)borohydridocopper (I) is recovered from a separate portion of the saturated chloroform solution by precipitation with anhydrous ethanol,
' filtration, and air drying. The product is a white crystalby weight of the weight of binder, and the solution is uniformly lightly coated on transparent polyester film. The coating is dried. The film is placed in face-to-face contact with a printed original which is then exposed through the film in a thermographic copying machine and at maximum exposure. A clear copy of the printed image is produced which is right-reading when viewed through the film.
What is claimed is as follows:
1. A heat-sensitive copy-sheet adapted for use in the thermographic copying method and wherein the visibly heat-sensitive stratum comprises bis(triphenylphosphine)- borohydridocopper (I).
2. The copy-sheet of claim 1 wherein the bis(triphenylphosphine)borohydridocopper (I) is retained in a polymeric film-forming binder.
3. The copy-sheet of claim 1 wherein the visibly heatsensitive stratum is carried by a thin flexible backing.
4. The copy-sheet of claim 3 wherein the backing is paper.
5. The copy-sheet of claim 3 wherein the backing is a transparent film.
References Cited UNITED STATES PATENTS 10 2,999,035 9/1961 Sahler 11736.8 3,185,583 5/l9 65 Baumann et a1 11736.8 3,178,306 4/1965 Wark 11736.8
MURRAY KATZ, Primary Examiner US. Cl. X.R.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US68712667A | 1967-12-01 | 1967-12-01 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3505093A true US3505093A (en) | 1970-04-07 |
Family
ID=24759169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US687126A Expired - Lifetime US3505093A (en) | 1967-12-01 | 1967-12-01 | Heat-sensitive copy-sheet containing bis(triphenylphosphine)borohydridocopper (i) |
Country Status (1)
| Country | Link |
|---|---|
| US (1) | US3505093A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3628980A (en) * | 1969-10-30 | 1971-12-21 | Minnesota Mining & Mfg | Heat-sensitive copy sheet |
| US3632379A (en) * | 1969-10-30 | 1972-01-04 | Minnesota Mining & Mfg | Heat-sensitive copy sheet |
| US3859092A (en) * | 1973-05-30 | 1975-01-07 | Eastman Kodak Co | Photographic systems based on photosensitive copper (i) complexes |
| US3860501A (en) * | 1973-05-30 | 1975-01-14 | Eastman Kodak Co | Photosensitive copper (i) complexes and the use thereof in photographic development |
| US3860500A (en) * | 1973-05-30 | 1975-01-14 | Eastman Kodak Co | Photosensitive copper (i) complexes and the use thereof in photographic development |
| US3927055A (en) * | 1973-05-30 | 1975-12-16 | Eastman Kodak Co | Photosensitive copper (I) complexes |
| USB518656I5 (en) * | 1973-05-30 | 1976-02-17 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2999035A (en) * | 1958-03-08 | 1961-09-05 | Keuffel & Esser Co | Heat sensitive reproduction sheet, method of making and method of using |
| US3178306A (en) * | 1962-04-12 | 1965-04-13 | Orchard Paper Company | Thermographic copying sheet and heat sensitive composition |
| US3185583A (en) * | 1962-11-19 | 1965-05-25 | Nashua Corp | Heat responsive marking sheets |
-
1967
- 1967-12-01 US US687126A patent/US3505093A/en not_active Expired - Lifetime
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2999035A (en) * | 1958-03-08 | 1961-09-05 | Keuffel & Esser Co | Heat sensitive reproduction sheet, method of making and method of using |
| US3178306A (en) * | 1962-04-12 | 1965-04-13 | Orchard Paper Company | Thermographic copying sheet and heat sensitive composition |
| US3185583A (en) * | 1962-11-19 | 1965-05-25 | Nashua Corp | Heat responsive marking sheets |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3628980A (en) * | 1969-10-30 | 1971-12-21 | Minnesota Mining & Mfg | Heat-sensitive copy sheet |
| US3632379A (en) * | 1969-10-30 | 1972-01-04 | Minnesota Mining & Mfg | Heat-sensitive copy sheet |
| US3859092A (en) * | 1973-05-30 | 1975-01-07 | Eastman Kodak Co | Photographic systems based on photosensitive copper (i) complexes |
| US3860501A (en) * | 1973-05-30 | 1975-01-14 | Eastman Kodak Co | Photosensitive copper (i) complexes and the use thereof in photographic development |
| US3860500A (en) * | 1973-05-30 | 1975-01-14 | Eastman Kodak Co | Photosensitive copper (i) complexes and the use thereof in photographic development |
| US3927055A (en) * | 1973-05-30 | 1975-12-16 | Eastman Kodak Co | Photosensitive copper (I) complexes |
| USB518656I5 (en) * | 1973-05-30 | 1976-02-17 | ||
| US3989732A (en) * | 1973-05-30 | 1976-11-02 | Eastman Kodak Company | Photosensitive copper (I) complexes |
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