US3460964A - Heat-sensitive recording element and composition - Google Patents
Heat-sensitive recording element and composition Download PDFInfo
- Publication number
- US3460964A US3460964A US412332A US3460964DA US3460964A US 3460964 A US3460964 A US 3460964A US 412332 A US412332 A US 412332A US 3460964D A US3460964D A US 3460964DA US 3460964 A US3460964 A US 3460964A
- Authority
- US
- United States
- Prior art keywords
- heat
- nitrate
- sensitive
- acid
- sensitive recording
- 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
- 239000000203 mixture Substances 0.000 title description 57
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 12
- 150000002894 organic compounds Chemical class 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 229920005610 lignin Polymers 0.000 description 11
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 10
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 description 10
- OJPDDQSCZGTACX-UHFFFAOYSA-N 2-[n-(2-hydroxyethyl)anilino]ethanol Chemical compound OCCN(CCO)C1=CC=CC=C1 OJPDDQSCZGTACX-UHFFFAOYSA-N 0.000 description 9
- 150000002823 nitrates Chemical class 0.000 description 9
- UYEMGAFJOZZIFP-UHFFFAOYSA-N 3,5-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC(O)=CC(O)=C1 UYEMGAFJOZZIFP-UHFFFAOYSA-N 0.000 description 8
- 238000005282 brightening Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 229910001960 metal nitrate Inorganic materials 0.000 description 8
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 8
- UIAFKZKHHVMJGS-UHFFFAOYSA-N 2,4-dihydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1O UIAFKZKHHVMJGS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000002562 thickening agent Substances 0.000 description 6
- ZENOXNGFMSCLLL-UHFFFAOYSA-N vanillyl alcohol Chemical compound COC1=CC(CO)=CC=C1O ZENOXNGFMSCLLL-UHFFFAOYSA-N 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229940074391 gallic acid Drugs 0.000 description 5
- 235000004515 gallic acid Nutrition 0.000 description 5
- 229960001867 guaiacol Drugs 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- -1 nitrate compound Chemical class 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- MIJRFWVFNKQQDK-UHFFFAOYSA-N furoin Chemical compound C=1C=COC=1C(O)C(=O)C1=CC=CO1 MIJRFWVFNKQQDK-UHFFFAOYSA-N 0.000 description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- MJHMXBDRUWSJOS-UHFFFAOYSA-N 1,2-bis(4-hydroxy-3-methoxyphenyl)ethane-1,2-dione Chemical compound C1=C(O)C(OC)=CC(C(=O)C(=O)C=2C=C(OC)C(O)=CC=2)=C1 MJHMXBDRUWSJOS-UHFFFAOYSA-N 0.000 description 3
- KWGZRLZJBLEVFZ-UHFFFAOYSA-N 1-nitro-4-[(4-nitrophenyl)disulfanyl]benzene Chemical compound C1=CC([N+](=O)[O-])=CC=C1SSC1=CC=C([N+]([O-])=O)C=C1 KWGZRLZJBLEVFZ-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000003125 aqueous solvent Substances 0.000 description 3
- 229940114055 beta-resorcylic acid Drugs 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000005855 radiation Effects 0.000 description 3
- 229960001755 resorcinol Drugs 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- KCDXJAYRVLXPFO-UHFFFAOYSA-N syringaldehyde Chemical compound COC1=CC(C=O)=CC(OC)=C1O KCDXJAYRVLXPFO-UHFFFAOYSA-N 0.000 description 3
- COBXDAOIDYGHGK-UHFFFAOYSA-N syringaldehyde Natural products COC1=CC=C(C=O)C(OC)=C1O COBXDAOIDYGHGK-UHFFFAOYSA-N 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 3
- 235000012141 vanillin Nutrition 0.000 description 3
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- VZIRCHXYMBFNFD-HNQUOIGGSA-N 3-(2-Furanyl)-2-propenal Chemical compound O=C\C=C\C1=CC=CO1 VZIRCHXYMBFNFD-HNQUOIGGSA-N 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 229910001864 baryta Inorganic materials 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 2
- 229910000464 lead oxide Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000033458 reproduction Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- VGBPIHVLVSGJGR-UHFFFAOYSA-N thorium(4+);tetranitrate Chemical compound [Th+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VGBPIHVLVSGJGR-UHFFFAOYSA-N 0.000 description 2
- QBYIENPQHBMVBV-HFEGYEGKSA-N (2R)-2-hydroxy-2-phenylacetic acid Chemical compound O[C@@H](C(O)=O)c1ccccc1.O[C@@H](C(O)=O)c1ccccc1 QBYIENPQHBMVBV-HFEGYEGKSA-N 0.000 description 1
- ZCJLOOJRNPHKAV-ONEGZZNKSA-N (e)-3-(furan-2-yl)prop-2-enoic acid Chemical compound OC(=O)\C=C\C1=CC=CO1 ZCJLOOJRNPHKAV-ONEGZZNKSA-N 0.000 description 1
- ZCJLOOJRNPHKAV-ARJAWSKDSA-N (z)-3-(furan-2-yl)prop-2-enoic acid Chemical compound OC(=O)\C=C/C1=CC=CO1 ZCJLOOJRNPHKAV-ARJAWSKDSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- RZCJYMOBWVJQGV-UHFFFAOYSA-N 2-naphthyloxyacetic acid Chemical compound C1=CC=CC2=CC(OCC(=O)O)=CC=C21 RZCJYMOBWVJQGV-UHFFFAOYSA-N 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- 229920001817 Agar Polymers 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- 241000206672 Gelidium Species 0.000 description 1
- 229920000084 Gum arabic Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- QLZHNIAADXEJJP-UHFFFAOYSA-N Phenylphosphonic acid Chemical compound OP(O)(=O)C1=CC=CC=C1 QLZHNIAADXEJJP-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- IWYDHOAUDWTVEP-UHFFFAOYSA-N R-2-phenyl-2-hydroxyacetic acid Natural products OC(=O)C(O)C1=CC=CC=C1 IWYDHOAUDWTVEP-UHFFFAOYSA-N 0.000 description 1
- 241000978776 Senegalia senegal Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- 206010057040 Temperature intolerance Diseases 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000000205 acacia gum Substances 0.000 description 1
- 235000010489 acacia gum Nutrition 0.000 description 1
- 235000010419 agar Nutrition 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 229920003086 cellulose ether Polymers 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 230000008543 heat sensitivity Effects 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229960002510 mandelic acid Drugs 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910001987 mercury nitrate Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- DRXYRSRECMWYAV-UHFFFAOYSA-N nitrooxymercury Chemical compound [Hg+].[O-][N+]([O-])=O DRXYRSRECMWYAV-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- KKKDGYXNGYJJRX-UHFFFAOYSA-M silver nitrite Chemical compound [Ag+].[O-]N=O KKKDGYXNGYJJRX-UHFFFAOYSA-M 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/4989—Photothermographic systems, e.g. dry silver characterised by a thermal imaging step, with or without exposure to light, e.g. with a thermal head, using a laser
-
- 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 composition which can be used to prepare heat-sensitive recording elements comprises an aqueous solvent, a metal nitrate, an organic phenolic, furan or lignin compound, and optionally a thickener, a stabilizer, a sensitizer or similar agents.
- This invention relates to an improved heat-sensitive or thermographic copy system based on inorganic salts, and more particularly based on certain metallic nitrates in combination with certain organic compounds that enter into color-forming reactions under the influence of heat.
- thermographic front-printing procedures the graphic original to be copied such as a typewritten letter or document, printed form or page, line drawing, etc., is placed in pressure contact with the heatsensitive surface of a copy-sheet, and the assembly then subjected to a heat source, for example, to infrared radiation.
- a heat source for example, to infrared radiation.
- the copy-sheet thereby becomes colored only in the image areas, thus reproducing the original.
- inorganic salts in combination with certain organic compounds have been proposed.
- one of the proposed methods employs as the heat-sensitive layer a mixture comprising phenolphthalein or aniline hydrochloride with potassium nitrate or nickel nitrate.
- this method has a number of serious shortcomings, which have limited its use to just certain very specific applications.
- the coating solution gives a dark brown precipitate within seconds of mixing the components. Then, on standing, it grows steadily darker and after about 2030 minutes, becomes inactive and does not give a heat-sensitive coating. Furthermore, the papers coated promptly after preparation of the solution, are generally brown in color and tend to have an offensive odor. Moreover, contamination of the original document is quite severe.
- an object of the invention to pro- 3,460,964 Patented Aug. 12, 1969 vide a new and improved heat-sensitive composition which can be readily applied to a support material.
- Another object is to provide an improved heat-sensitive recording element or sheet having at least one layer thereon of the above composition.
- Another object is to provide an improved heat-sensitive recording element or sheet of the above type which reproduces exact copies of original typewritten or printed letters, documents, etc. in dark colors against a nearly white background by a bireflex exposure to a heat source such as infrared radiation.
- Another object is to provide a process for preparing these new heat-sensitive compositions and heat-sensitive recording elements or sheets. Other object will become apparent from the description and examples.
- I prepare my new and improved heat-sensitive compositions and heat-sensitive recording elements by intimately mixing together at least one metal nitrate and at least one reactive organic compound, i.e., capable of entering a color-forming reaction with the nitrate compound under the influence of heat, such as a phenolic compound, a furan compound, a lignin compound, and the like, in a suitable liquid medium which is a solvent for the above mixture of compounds, preferably an aqueous system such as a mixture of Water and a water-soluble organic solvent including lower alkanols, ketones, etc. (e.g., methanol, ethanol, acetone, 1,4-dioxane, etc.).
- a suitable liquid medium which is a solvent for the above mixture of compounds, preferably an aqueous system such as a mixture of Water and a water-soluble organic solvent including lower alkanols, ketones, etc. (e.g., methanol, ethanol, acetone, 1,4-di
- the proportions of water and solvent are not critical, but preferably the mixtures comprise about from 40-90% by weight of water and from 60-10% by weight of the organic solvent.
- the compositions prepared as above are then applied or coated onto fibrous sheet material which is preferably a high grade paper of low lignin content by conventional methods such as spraying, brushing, dipping, using a coating knife, etc.
- the resulting coating is ordinarily allowed to air dry.
- the heat-sensitive recording element thus produced can be used directly for preparing reproductions of original documents, etc. or stored for several weeks or more before using without appreciable loss in activity.
- nitrate compounds give satisfactory or practical heat-sensitive compositions and heat-sensitive recording elements or sheets.
- the nitrates of sodium, potassium, barium, strontium, cerium, lead and lanthanum e.g., NaNO KNO Ba(NO C6(NO3)3, Pb(NO3)2, SI'(NO3)2, LH(NO3)3, etc.
- Ammonium nitrate also is not operable. Salts other than nitrate likewise do not give satisfactory results.
- metal sulfates are not active.
- Metal chlorides such as ZnCl produce images; however, these images are unstable and the background becomes dark quite rapidly.
- operable high quality heat-sensitive compositions and heatsensitive recording elements or sheets are obtained in accordance with the invention with a select group of compounds such as the nitrates of silver, copper, zinc, magnesium, mercury, aluminum, yttrium, thorium, bismuth, chromium, iron, cobalt, and nickel (e.g., AgNO 3)2, a)2 3)2, 3 z, 3)3, 3)a, 3)4, 3)3, 3)2, 0 93, Co(NO and Ni(CO Silver nitrite (AgNO is also operable and produces satisfactory compositions and thermographic recording elements or sheets. Those of the above compounds that also contain water of crystallization in their formulas are also included.
- a select group of compounds such as the nitrates of silver, copper, zinc, magnesium, mercury, aluminum, yttrium, thorium, bismuth, chromium, iron, cobalt, and nickel (e.g., AgNO 3)2, a)2 3)2, 3
- phenolic, furan, lignin, etc. compounds give satisfactory or practical heat-sensitive compositions and heat-sensitive recording elements or sheets with the above-mentioned select group of metal nitrate compounds.
- phenol and catechol are not satisfactory components because they cause poor contrast and inferior keeping qualities.
- furan compounds also are inoperative.
- the types of papers containing sufficient lignin to give even relatively poor images, without need for lignin substitutes are generally lower grade, unsized papers.
- High grade papers are preferably used in my invention and for its reason only certain lignin substitutes in conjunction with the above-mentioned select group of nitrate compounds, are suitable for producing satisfactory heat-sensitive compositions and heat-sensitive recording elements or sheets.
- Suitable reactive organic compounds for practicing the invention are thus strictly limited to a select group including syringaldehyde, lignin sulfonic acid, vanillyl alcohol, vanillin, vanillil, guaiacol, resorcinol, gallic acid, Z-naphthol, 2,4- dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2- naphthyloxy acetic acid, 2-furanacrolein, 2-furanacry 1ic acid, bis(p-nitrophenyl) disulfide and furoin.
- the concentration of the metal nitrate compounds in the heat-sensitive compositions of the invention can vary quite widely, but preferably from 5 to 30% while that of the reactive organic compound can vary about from 2 to 25%, based in each case on the total weight of the solution.
- the usual practice is to dissolve the metal nitrate salt in the aqueous medium and then add thereto the reactive organic compound dissolved in, for example, acetone or methanol.
- One hundred ml. of the solution sufiices to coat on the average of from 50 to 80, 9" x 12 sheets having satisfactory heat-sensitivity and good image recording. This latter result depends somewhat on the paper stock used.
- the sensitivity of the coated paper is sufficiently increased to give dark strong images at a machine setting of 6.
- Acids such as 2,4-dinitrophenylacetic, m-nitrobenzoic, picolinic and 1,23,4- butanetetracarboxylic acids also produce speed increases but of somewhat lower order than that of the aforementioned acids.
- a thickening agent can also be incorporated into the composition to increase the viscosity and improve the coating ease.
- Suitable thickeners include hydrophilic colloids such as gelatin, albumin, agar-agar, gum arabic, alginic acid, etc., or a hydrophilic synthetic resin such as polyvinyl alcohol, polyvinyl pyrrolidone, a cellulose ether, etc.
- concentration of the thickener can range from about 0.5 to 5% depending on'the particular thickening agent and the desired result.
- the heat-sensitive compositions can be also contain other materials that alter or improve the qualities of the heat-sensitive recording elements or sheets produced therewith for example, infrared absorbents to increase sensitivity, humectants or hydrated salts to control the moisture content, stabilizers to improve image permanence and to prevent increase of background color, or activity controlling compounds such as 2,2-(phenylimino)diethanol, aminodietha- 1101, etc. which function to maintain the heat-sensitive recording elements or sheet in a uniformly active condition for several weeks or more, and thereafter for some time still operable at a gradually reduced sensitivity level.
- the activity controlling compound is preferably present in an amount of about from 1-5 based on the total weight of the composition or solution.
- Example I Preparation of heat-sensitized sheet A thin sheet of acid resistant, heat-conducting paper was coated on one side by sprayingwith a brightening composition comprising titanium dioxide, and dried. This coatedsurface was then overcoated by spraying thereover a thin coating ofthe following heat-sensitive composition:
- Aluminum 'nitrate 'g 10.0 a-Resorcyclic acid g 7.0 2,2-(phenylimino)diethanol g 3.0 Acetone ml 28.0 Water to bring total to ml The coating was then allowed to air dry.
- any other of the mentioned brightening agents such as aluminum oxide, baryta, lead oxide, etc.
- the application of the heat-sensitive coat can also be done by brushing, dipping, etc. or by using a coating knife, when the compositions contain a thickening agent such as the mentioned hydrophilic materials.
- Example -II.Pr0duction of image by heat A printed page to be copied was covered with the sensitized sheet prepared as described in Example I, with the unsensitized side of the copy paper in contact with the original. The assembly was then passed through a Thermofax Secretary machine (trade name of a commercial thermographic machine) at a speed in the region of the buff setting. A legible dark brown image of good stability was obtained on a white background. This was repeated with other samples of heat-sensitive sheets prepared as in Example I, excellent images being obtained on freshly coated sheets as well as on sheets aged for one month before exposure.
- a heat-sensitive composition comprising (1) a compound selected from the group consisting of copper nitrate, zinc nitrate, magnesium nitrate, mercury nitrate, aluminum nitrate, yttrium nitrate, thorium nitrate, bismuth nitrate, chromium nitrate, iron nitrate, cobalt nitrate and nickel nitrate, (2) an organic compound selected from the group consisting of syringaldehyde, lignin sulfonic acid, vanillyl alcohol, .vanillin, vanillil, guaiacol, resorcinol, gallic acid, Z-naphthol, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, Z-naphthyloxy acetic acid, Z-furanacrolein, Z-furanacrylic acid, bis(p-nitrophenyl) disulfide and furoin, (3) an a
- a heat-sensitive composition of claim 1 composed of from 5 to 30% by weight of said (1), from 2 to 25% by weight of said (2), from 1 to 5% by weight of said (4), and the remainder to make a total of 100% of said (3).
- a heat-sensitive composition of claim 2 wherein said (1) is aluminum nitrate, said (2) is a-resorcylic acid, said (4) is 2,2'-(phenylimino)diethanol, and said (3) is a mixture consisting of from 40-90% by Weight of water and from 60-10% by Weight of acetone.
- a heat-sensitive composition of claim 2 wherein said 1) is nickel nitrate, asid (2) is a-resorcyclic acid, said (4) is 2,2'-(phenylimino)diethanol, and said (3) is a mixture consisting of from 40-90% by weight of water and from 60-10% by weight of acetone.
- a heat-sensitive composition of claim 2 wherein said (1) is aluminum nitrate, said (2) is gallic acid, said (4) is 2,2'-(phenylimino)diethanol, and said (3) is a mixture consisting of from 40-90% by weight of water and from 60-10% by weight of acetone.
- a heat-sensitive recording element comprising a paper support coated with a heat-sensitive composition
- a heat-sensitive composition comprising (1) a compound selected from the group consisting of silver nitrate, copper nitrate, zinc nitrate, magnesium nitrate, thorium nitrate, bismuth nitrate, chromium nitrate, iron nitrate, cobalt nitrate and nickel nitrate, (2) an organic compound selected from the group consisting of syringaldehyde, lignin sulfonic acid, vanillyl alcohol, vanillin, vanillil, guaiacol, resorcinol, gallic acid,
- Z-naphthol 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, Z-naphthyloxyacetic acid, 2-furanacrolein, 2- furanacrylic acid, bis(p-nitrophenyl)disulfide and furoin, (3) an aqueous solvent system comprising a mixture of water and a water-soluble organic solvent, and (4) an activity controlling compound selected from the group consisting of 2,2-(phenylimino)diethanol and aminodiethanol.
- a heat-sensitive recording element comprising a paper support coated on one surface with at least one layer of heat-sensitive composition of claim 2.
- a heat-sensitive recording element comprising a paper support coated on one surface with at least one layer of the heat-sensitive composition of claim 3.
- a heat-sensitive recording element comprising a paper support coated on one surface with at least one layer of the heat-sensitive composition of claim 4.
- a heat-sensitive recording element comprising a thin sheet of acid resistant, heat-conducting paper support coated on at least one surface with a brightening agent and having at least one surface thereof coated .with a layer of the heat-sensitive composition of claim 5.
- a heat-sensitive recording element comprising a thin sheet of acid resistant, heat-conducting paper support coated on at least one surface with a brightening agent and having at least one surface thereof coated with a layer of the heat-sensitive composition of claim 6.
- a heat-sensitive recording element comprising a thin sheet of acid resistant, heat-conducting paper support coated on at least one surface with a brightening agent and having at least one surface thereof coated with a layer of the heat-sensitive composition of claim 7.
- a heat-sensitive recording element comprising a thin sheet of acid resistant, heat-conducting paper support coated on at least one surface with a brightening agent and having at least one surface thereof coated with a layer of the heat-sensitive composition of claim 8.
- a heat-sensitive recording element comprising a thin sheet of acid resistant, heat-conducting paper support coated on at least one surface with a brightening agent and having at least one surface thereof coated with a layer of the heat-sensitive composition of claim 9.
Description
United States Patent 3,460,964 HEAT-SENSITIVE RECORDING ELEMENT AND COMPOSITION Kenneth Royal Dunham, Rochester, N.Y., assignor to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed Nov. 19, 1964, Ser. No. 412,332 Int. Cl. B41m 5/18, 5/26 US. Cl. 117-369 18 Claims ABSTRACT OF THE DISCLOSURE A heat-sensitive composition which can be used to prepare heat-sensitive recording elements comprises an aqueous solvent, a metal nitrate, an organic phenolic, furan or lignin compound, and optionally a thickener, a stabilizer, a sensitizer or similar agents.
This invention relates to an improved heat-sensitive or thermographic copy system based on inorganic salts, and more particularly based on certain metallic nitrates in combination with certain organic compounds that enter into color-forming reactions under the influence of heat.
In conventional thermographic front-printing procedures, the graphic original to be copied such as a typewritten letter or document, printed form or page, line drawing, etc., is placed in pressure contact with the heatsensitive surface of a copy-sheet, and the assembly then subjected to a heat source, for example, to infrared radiation. The copy-sheet thereby becomes colored only in the image areas, thus reproducing the original. For this purpose, inorganic salts in combination with certain organic compounds have been proposed. For example, one of the proposed methods employs as the heat-sensitive layer a mixture comprising phenolphthalein or aniline hydrochloride with potassium nitrate or nickel nitrate. However, this method has a number of serious shortcomings, which have limited its use to just certain very specific applications. For one thing, the coating solution gives a dark brown precipitate within seconds of mixing the components. Then, on standing, it grows steadily darker and after about 2030 minutes, becomes inactive and does not give a heat-sensitive coating. Furthermore, the papers coated promptly after preparation of the solution, are generally brown in color and tend to have an offensive odor. Moreover, contamination of the original document is quite severe.
I have now found that mixtures comprising a liquid medium or solvent, certain metal nitrates and certain organic compounds are heat-sensitive, becoming deeply colored on exposure to a heat source such as infrared radiation. I have further found that when such mixtures or compositions in unexposed condition are applied to suitable supports, for example, a fibrous sheet material such as paper, and dried, the elements so formed are likewise heat-sensitive and eminently suitable as recording or copy sheets for reproduction of original typewritten letters, documents, printed sheets, line drawings, etc. Furthermore, such heat-sensitive recording elements or sheets are nearly white in appearance, stable under ordinary keeping conditions and cause little or no document contamination even after many passes through a T hermofax machine (trade name for a commercial thenmographic machine). The images reproduced on exposure of an original document in contact with the heat-sensitive recording elements or sheets of my invention are characterized by being, ordinarily, dark brown in color on an essentially white background, sharp in definition and relatively stable.
It is, accordingly, an object of the invention to pro- 3,460,964 Patented Aug. 12, 1969 vide a new and improved heat-sensitive composition which can be readily applied to a support material. Another object is to provide an improved heat-sensitive recording element or sheet having at least one layer thereon of the above composition. Another object is to provide an improved heat-sensitive recording element or sheet of the above type which reproduces exact copies of original typewritten or printed letters, documents, etc. in dark colors against a nearly white background by a bireflex exposure to a heat source such as infrared radiation. Another object is to provide a process for preparing these new heat-sensitive compositions and heat-sensitive recording elements or sheets. Other object will become apparent from the description and examples.
In accordance with the invention I prepare my new and improved heat-sensitive compositions and heat-sensitive recording elements by intimately mixing together at least one metal nitrate and at least one reactive organic compound, i.e., capable of entering a color-forming reaction with the nitrate compound under the influence of heat, such as a phenolic compound, a furan compound, a lignin compound, and the like, in a suitable liquid medium which is a solvent for the above mixture of compounds, preferably an aqueous system such as a mixture of Water and a water-soluble organic solvent including lower alkanols, ketones, etc. (e.g., methanol, ethanol, acetone, 1,4-dioxane, etc.). The proportions of water and solvent are not critical, but preferably the mixtures comprise about from 40-90% by weight of water and from 60-10% by weight of the organic solvent. The compositions prepared as above are then applied or coated onto fibrous sheet material which is preferably a high grade paper of low lignin content by conventional methods such as spraying, brushing, dipping, using a coating knife, etc. The resulting coating is ordinarily allowed to air dry. The heat-sensitive recording element thus produced can be used directly for preparing reproductions of original documents, etc. or stored for several weeks or more before using without appreciable loss in activity.
However, not all nitrate compounds give satisfactory or practical heat-sensitive compositions and heat-sensitive recording elements or sheets. For instance, the nitrates of sodium, potassium, barium, strontium, cerium, lead and lanthanum (e.g., NaNO KNO Ba(NO C6(NO3)3, Pb(NO3)2, SI'(NO3)2, LH(NO3)3, etc.) definitely are not operable in my invention. Ammonium nitrate also is not operable. Salts other than nitrate likewise do not give satisfactory results. Thus metal sulfates are not active. Metal chlorides such as ZnCl produce images; however, these images are unstable and the background becomes dark quite rapidly. In contrast, operable high quality heat-sensitive compositions and heatsensitive recording elements or sheets are obtained in accordance with the invention with a select group of compounds such as the nitrates of silver, copper, zinc, magnesium, mercury, aluminum, yttrium, thorium, bismuth, chromium, iron, cobalt, and nickel (e.g., AgNO 3)2, a)2 3)2, 3 z, 3)3, 3)a, 3)4, 3)3, 3)2, 0 93, Co(NO and Ni(CO Silver nitrite (AgNO is also operable and produces satisfactory compositions and thermographic recording elements or sheets. Those of the above compounds that also contain water of crystallization in their formulas are also included.
In regard to the reactive organic compound component, here too not all phenolic, furan, lignin, etc. compounds give satisfactory or practical heat-sensitive compositions and heat-sensitive recording elements or sheets with the above-mentioned select group of metal nitrate compounds. For example, phenol and catechol are not satisfactory components because they cause poor contrast and inferior keeping qualities. Most furan compounds also are inoperative. As to the lignin, the types of papers containing sufficient lignin to give even relatively poor images, without need for lignin substitutes are generally lower grade, unsized papers. High grade papers are preferably used in my invention and for its reason only certain lignin substitutes in conjunction with the above-mentioned select group of nitrate compounds, are suitable for producing satisfactory heat-sensitive compositions and heat-sensitive recording elements or sheets. Suitable reactive organic compounds for practicing the invention are thus strictly limited to a select group including syringaldehyde, lignin sulfonic acid, vanillyl alcohol, vanillin, vanillil, guaiacol, resorcinol, gallic acid, Z-naphthol, 2,4- dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, 2- naphthyloxy acetic acid, 2-furanacrolein, 2-furanacry 1ic acid, bis(p-nitrophenyl) disulfide and furoin.
The concentration of the metal nitrate compounds in the heat-sensitive compositions of the invention can vary quite widely, but preferably from 5 to 30% while that of the reactive organic compound can vary about from 2 to 25%, based in each case on the total weight of the solution. The usual practice is to dissolve the metal nitrate salt in the aqueous medium and then add thereto the reactive organic compound dissolved in, for example, acetone or methanol. One hundred ml. of the solution sufiices to coat on the average of from 50 to 80, 9" x 12 sheets having satisfactory heat-sensitivity and good image recording. This latter result depends somewhat on the paper stock used. For example, on thin sheets of paper stock normally employed for bireflex exposures in thermographic systems, image intensity appears undesirably weak because of light transmitted through the paper. This disadvantage can be overcome, if desired, by employing paper stock having a layer of a brightening agent on at least one surface such as aluminum oxide, titanium dioxide, baryta, lead oxide, etc. Advantageously, an organic acid which is normally solid at room temperature can be added to increase the speed of the heat-sensitive compositions and heat-sensitive recording elements. For example, a typical heat-sensitive composition containing 20% by weight of Al(NO will produce coated papers giving relatively weak images at a setting of 2 on a Thermofax machine. However, on addition to the composition of 5 to 15% of citric acid, tartaric acid, mandelic acid or benzenephosphonic acid, the sensitivity of the coated paper is sufficiently increased to give dark strong images at a machine setting of 6. Acids such as 2,4-dinitrophenylacetic, m-nitrobenzoic, picolinic and 1,23,4- butanetetracarboxylic acids also produce speed increases but of somewhat lower order than that of the aforementioned acids. If desired, a thickening agent can also be incorporated into the composition to increase the viscosity and improve the coating ease. Suitable thickeners include hydrophilic colloids such as gelatin, albumin, agar-agar, gum arabic, alginic acid, etc., or a hydrophilic synthetic resin such as polyvinyl alcohol, polyvinyl pyrrolidone, a cellulose ether, etc. The concentration of the thickener can range from about 0.5 to 5% depending on'the particular thickening agent and the desired result. The heat-sensitive compositions can be also contain other materials that alter or improve the qualities of the heat-sensitive recording elements or sheets produced therewith for example, infrared absorbents to increase sensitivity, humectants or hydrated salts to control the moisture content, stabilizers to improve image permanence and to prevent increase of background color, or activity controlling compounds such as 2,2-(phenylimino)diethanol, aminodietha- 1101, etc. which function to maintain the heat-sensitive recording elements or sheet in a uniformly active condition for several weeks or more, and thereafter for some time still operable at a gradually reduced sensitivity level. The activity controlling compound is preferably present in an amount of about from 1-5 based on the total weight of the composition or solution.
4, The following examples illustrate more specifically the manner whereby I practice my invention.
Example I.Preparation of heat-sensitized sheet A thin sheet of acid resistant, heat-conducting paper was coated on one side by sprayingwith a brightening composition comprising titanium dioxide, and dried. This coatedsurface was then overcoated by spraying thereover a thin coating ofthe following heat-sensitive composition:
Aluminum 'nitrate 'g 10.0 a-Resorcyclic acid g 7.0 2,2-(phenylimino)diethanol g 3.0 Acetone ml 28.0 Water to bring total to ml The coating was then allowed to air dry.
In place of the titanium dioxide, there can be substituted in the above example any other of the mentioned brightening agents such as aluminum oxide, baryta, lead oxide, etc. Also, the application of the heat-sensitive coat can also be done by brushing, dipping, etc. or by using a coating knife, when the compositions contain a thickening agent such as the mentioned hydrophilic materials.
Example -II.Pr0duction of image by heat A printed page to be copied was covered with the sensitized sheet prepared as described in Example I, with the unsensitized side of the copy paper in contact with the original. The assembly was then passed through a Thermofax Secretary machine (trade name of a commercial thermographic machine) at a speed in the region of the buff setting. A legible dark brown image of good stability was obtained on a white background. This was repeated with other samples of heat-sensitive sheets prepared as in Example I, excellent images being obtained on freshly coated sheets as well as on sheets aged for one month before exposure.
By substituting either the aluminum nitrate or the mresorcylic acid, or both, in above Examples I and II with any other of the mentioned nitrates or reactive organic compounds, other species of heat-sensitive compositions and corresponding heat-sensitive recording elements or sheets can be readily prepared. Such sensitized sheets likewise have good keeping properties and produce legible and stable dark images on white backgrounds. Thus, in the procedures of Examples I and II, combinations of nickel nitrate and a-resorcylic acid; the combination of coppernitrate and guaiacol; the combination of aluminum nitrate and gallic acid; etc., likewise give satisfactory heat-sensitive compositions or solutions and corresponding excellent heat-sensitive recording sheets.
The chemistry involved in image formation in my invention is not definitely known. The evidence gathered to date indicates, however, that the color-forming reaction apparently involves oxidation of the reactive organic compounds with the metal nitrates on exposure to a heat source, possibly followed by chelation with the metal ion. Only the metal nitrates previously mentioned as suitable in the practice of the invention give this desirable color-forming reaction.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention as described hereinabove and as defined in the appended claims.
What I claim is:
1. A heat-sensitive composition comprising (1) a compound selected from the group consisting of copper nitrate, zinc nitrate, magnesium nitrate, mercury nitrate, aluminum nitrate, yttrium nitrate, thorium nitrate, bismuth nitrate, chromium nitrate, iron nitrate, cobalt nitrate and nickel nitrate, (2) an organic compound selected from the group consisting of syringaldehyde, lignin sulfonic acid, vanillyl alcohol, .vanillin, vanillil, guaiacol, resorcinol, gallic acid, Z-naphthol, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, Z-naphthyloxy acetic acid, Z-furanacrolein, Z-furanacrylic acid, bis(p-nitrophenyl) disulfide and furoin, (3) an aqueous solvent system comprising a mixture of water and a water-soluble organic solvent, and (4) an activity controlling compound selected from the group consisting of 2,2'-(phenylimino) diethanol and aminodiethanol.
2. A heat-sensitive composition of claim 1 composed of from 5 to 30% by weight of said (1), from 2 to 25% by weight of said (2), from 1 to 5% by weight of said (4), and the remainder to make a total of 100% of said (3).
3. A heat-sensitive composition of claim 1 wherein a hydrophilic colloid material is included.
4. A heat-sensitive composition of claim 1 wherein a normally solid, water-soluble carboxylic acid is included.
5. A heat-sensitive composition of claim 2 wherein said (1) is aluminum nitrate, said (2) is a-resorcylic acid, said (4) is 2,2'-(phenylimino)diethanol, and said (3) is a mixture consisting of from 40-90% by Weight of water and from 60-10% by Weight of acetone.
6. A heat-sensitive composition of claim 2 wherein said 1) is nickel nitrate, asid (2) is a-resorcyclic acid, said (4) is 2,2'-(phenylimino)diethanol, and said (3) is a mixture consisting of from 40-90% by weight of water and from 60-10% by weight of acetone.
7. A heat-sensitive composition of claim 2 wherein said (1) is zinc nitrate, said (2) is resorcinol, said (4) is 2,2'-(phenylimino)diethanol, and said (3) is a mixture consisting of from 40-90% by weight of water and 60- by weight of acetone.
8. A heat-sensitive composition of claim 2 wherein said (1) is copper nitrate, said (2) is guaiacol, said (4) is 2,2'-(phenylimino)diethanol, and said (3) is a mixture consisting of from 40-90% by weight of water and from 60-10% by weight of acetone.
9. A heat-sensitive composition of claim 2 wherein said (1) is aluminum nitrate, said (2) is gallic acid, said (4) is 2,2'-(phenylimino)diethanol, and said (3) is a mixture consisting of from 40-90% by weight of water and from 60-10% by weight of acetone.
10. A heat-sensitive recording element comprising a paper support coated with a heat-sensitive composition comprising (1) a compound selected from the group consisting of silver nitrate, copper nitrate, zinc nitrate, magnesium nitrate, thorium nitrate, bismuth nitrate, chromium nitrate, iron nitrate, cobalt nitrate and nickel nitrate, (2) an organic compound selected from the group consisting of syringaldehyde, lignin sulfonic acid, vanillyl alcohol, vanillin, vanillil, guaiacol, resorcinol, gallic acid,
Z-naphthol, 2,4-dihydroxybenzoic acid, 3,5-dihydroxybenzoic acid, Z-naphthyloxyacetic acid, 2-furanacrolein, 2- furanacrylic acid, bis(p-nitrophenyl)disulfide and furoin, (3) an aqueous solvent system comprising a mixture of water and a water-soluble organic solvent, and (4) an activity controlling compound selected from the group consisting of 2,2-(phenylimino)diethanol and aminodiethanol.
11. A heat-sensitive recording element comprising a paper support coated on one surface with at least one layer of heat-sensitive composition of claim 2.
12. A heat-sensitive recording element comprising a paper support coated on one surface with at least one layer of the heat-sensitive composition of claim 3.
13. A heat-sensitive recording element comprising a paper support coated on one surface with at least one layer of the heat-sensitive composition of claim 4.
14. A heat-sensitive recording element comprising a thin sheet of acid resistant, heat-conducting paper support coated on at least one surface with a brightening agent and having at least one surface thereof coated .with a layer of the heat-sensitive composition of claim 5.
15. A heat-sensitive recording element comprising a thin sheet of acid resistant, heat-conducting paper support coated on at least one surface with a brightening agent and having at least one surface thereof coated with a layer of the heat-sensitive composition of claim 6.
16. A heat-sensitive recording element comprising a thin sheet of acid resistant, heat-conducting paper support coated on at least one surface with a brightening agent and having at least one surface thereof coated with a layer of the heat-sensitive composition of claim 7.
17. A heat-sensitive recording element comprising a thin sheet of acid resistant, heat-conducting paper support coated on at least one surface with a brightening agent and having at least one surface thereof coated with a layer of the heat-sensitive composition of claim 8.
18. A heat-sensitive recording element comprising a thin sheet of acid resistant, heat-conducting paper support coated on at least one surface with a brightening agent and having at least one surface thereof coated with a layer of the heat-sensitive composition of claim 9.
No references cited.
MURRAY KATZ, Primary Examiner US. Cl. X.R.
1062l; ll7-36, 155, 156; 26041
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US41233264A | 1964-11-19 | 1964-11-19 |
Publications (1)
Publication Number | Publication Date |
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US3460964A true US3460964A (en) | 1969-08-12 |
Family
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Application Number | Title | Priority Date | Filing Date |
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US412332A Expired - Lifetime US3460964A (en) | 1964-11-19 | 1964-11-19 | Heat-sensitive recording element and composition |
Country Status (1)
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US (1) | US3460964A (en) |
Cited By (15)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3925088A (en) * | 1973-07-20 | 1975-12-09 | Us Navy | Thermally sensitive ink |
US4051283A (en) * | 1968-09-03 | 1977-09-27 | A. B. Dick Company | Printed sheets containing concealed images and method and materials for preparation and visual development of same |
US4082879A (en) * | 1975-08-04 | 1978-04-04 | Minnesota Mining And Manufacturing Company | Stabilized transparent receptor sheet |
US4128428A (en) * | 1974-04-10 | 1978-12-05 | Fuji Photo Film Co., Ltd. | Heat developable light-sensitive material |
US4239832A (en) * | 1978-11-30 | 1980-12-16 | Eaton Allen Corp. | Adhesively correctable transfer medium with delayed alteration resistance characteristics |
WO1981001756A1 (en) * | 1979-12-07 | 1981-06-25 | Minnesota Mining & Mfg | Diazonium imaging system |
EP0041540A1 (en) * | 1979-12-07 | 1981-12-16 | Minnesota Mining & Mfg | Color imaging system. |
US4333984A (en) * | 1979-12-18 | 1982-06-08 | Fuji Photo Film Co., Ltd. | Heat-sensitive recording sheets |
US4336323A (en) * | 1979-12-07 | 1982-06-22 | Minnesota Mining And Manufacturing Company | Decolorizable imaging system |
EP0055111A2 (en) * | 1980-12-22 | 1982-06-30 | Minnesota Mining And Manufacturing Company | Black image from a thermographic imaging system |
US4370401A (en) * | 1979-12-07 | 1983-01-25 | Minnesota Mining And Manufacturing Company | Light sensitive, thermally developable imaging system |
US4373020A (en) * | 1979-12-07 | 1983-02-08 | Minnesota Mining And Manufacturing Company | Decolorizable imaging system |
US4423139A (en) * | 1980-12-22 | 1983-12-27 | Minnesota Mining And Manufacturing Company | Stabilizer combination for dye oxidation |
EP0159874A2 (en) * | 1984-04-16 | 1985-10-30 | Minnesota Mining And Manufacturing Company | Prevention of spotting in thermal imaging compositions |
USRE34515E (en) * | 1979-06-11 | 1994-01-18 | Pymah Corporation | Steam sterilization indicator |
-
1964
- 1964-11-19 US US412332A patent/US3460964A/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
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None * |
Cited By (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4051283A (en) * | 1968-09-03 | 1977-09-27 | A. B. Dick Company | Printed sheets containing concealed images and method and materials for preparation and visual development of same |
US3925088A (en) * | 1973-07-20 | 1975-12-09 | Us Navy | Thermally sensitive ink |
US4128428A (en) * | 1974-04-10 | 1978-12-05 | Fuji Photo Film Co., Ltd. | Heat developable light-sensitive material |
US4082879A (en) * | 1975-08-04 | 1978-04-04 | Minnesota Mining And Manufacturing Company | Stabilized transparent receptor sheet |
US4239832A (en) * | 1978-11-30 | 1980-12-16 | Eaton Allen Corp. | Adhesively correctable transfer medium with delayed alteration resistance characteristics |
USRE34515E (en) * | 1979-06-11 | 1994-01-18 | Pymah Corporation | Steam sterilization indicator |
US4336323A (en) * | 1979-12-07 | 1982-06-22 | Minnesota Mining And Manufacturing Company | Decolorizable imaging system |
EP0041540A1 (en) * | 1979-12-07 | 1981-12-16 | Minnesota Mining & Mfg | Color imaging system. |
US4370401A (en) * | 1979-12-07 | 1983-01-25 | Minnesota Mining And Manufacturing Company | Light sensitive, thermally developable imaging system |
US4373020A (en) * | 1979-12-07 | 1983-02-08 | Minnesota Mining And Manufacturing Company | Decolorizable imaging system |
WO1981001756A1 (en) * | 1979-12-07 | 1981-06-25 | Minnesota Mining & Mfg | Diazonium imaging system |
US4333984A (en) * | 1979-12-18 | 1982-06-08 | Fuji Photo Film Co., Ltd. | Heat-sensitive recording sheets |
EP0055111A2 (en) * | 1980-12-22 | 1982-06-30 | Minnesota Mining And Manufacturing Company | Black image from a thermographic imaging system |
EP0055111A3 (en) * | 1980-12-22 | 1983-01-05 | Minnesota Mining And Manufacturing Company | Black image from a thermographic imaging system |
US4379835A (en) * | 1980-12-22 | 1983-04-12 | Minnesota Mining And Manufacturing Company | Black image from a thermographic imaging system |
US4423139A (en) * | 1980-12-22 | 1983-12-27 | Minnesota Mining And Manufacturing Company | Stabilizer combination for dye oxidation |
EP0159874A2 (en) * | 1984-04-16 | 1985-10-30 | Minnesota Mining And Manufacturing Company | Prevention of spotting in thermal imaging compositions |
EP0159874A3 (en) * | 1984-04-16 | 1986-06-04 | Minnesota Mining And Manufacturing Company | Prevention of spotting in thermal imaging compositions |
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