US3153592A - Complex salt diazotype photoprinting materials - Google Patents
Complex salt diazotype photoprinting materials Download PDFInfo
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- US3153592A US3153592A US194960A US19496062A US3153592A US 3153592 A US3153592 A US 3153592A US 194960 A US194960 A US 194960A US 19496062 A US19496062 A US 19496062A US 3153592 A US3153592 A US 3153592A
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- United States
- Prior art keywords
- original
- acid
- diazo
- complex
- sulfonic acid
- Prior art date
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- Expired - Lifetime
Links
- 150000003839 salts Chemical class 0.000 title claims description 21
- 239000000463 material Substances 0.000 title description 31
- 239000000203 mixture Substances 0.000 claims description 31
- 239000002253 acid Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 150000008049 diazo compounds Chemical class 0.000 claims description 23
- 230000008569 process Effects 0.000 claims description 23
- 239000003381 stabilizer Substances 0.000 claims description 21
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 18
- 238000010168 coupling process Methods 0.000 claims description 16
- 238000005859 coupling reaction Methods 0.000 claims description 16
- 230000008878 coupling Effects 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 230000008707 rearrangement Effects 0.000 claims description 7
- 239000012954 diazonium Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 150000001989 diazonium salts Chemical class 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 42
- 239000002585 base Substances 0.000 description 21
- 235000013877 carbamide Nutrition 0.000 description 20
- 239000004202 carbamide Substances 0.000 description 19
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 16
- 239000000123 paper Substances 0.000 description 15
- -1 diazonium ion Chemical class 0.000 description 13
- 230000033458 reproduction Effects 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 11
- 239000000306 component Substances 0.000 description 9
- SCETWWDGKCBPMK-UHFFFAOYSA-N 4-[(4e)-4-diazocyclohexa-1,5-dien-1-yl]morpholine Chemical compound C1=CC(=[N+]=[N-])CC=C1N1CCOCC1 SCETWWDGKCBPMK-UHFFFAOYSA-N 0.000 description 8
- 150000007513 acids Chemical class 0.000 description 8
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 8
- 238000006149 azo coupling reaction Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000975 dye Substances 0.000 description 6
- WQJBDEHULKUMKX-UHFFFAOYSA-N [5-(2-aminoethyl)-2-hydroxyphenyl] benzoate Chemical compound NCCC1=CC=C(O)C(OC(=O)C=2C=CC=CC=2)=C1 WQJBDEHULKUMKX-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 230000005855 radiation Effects 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- WRUAHXANJKHFIL-UHFFFAOYSA-N benzene-1,3-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC(S(O)(=O)=O)=C1 WRUAHXANJKHFIL-UHFFFAOYSA-N 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
- 238000013461 design Methods 0.000 description 3
- 239000003517 fume Substances 0.000 description 3
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 3
- 125000001477 organic nitrogen group Chemical group 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- DKJVSIITPZVTRO-UHFFFAOYSA-N 6,7-dihydroxynaphthalene-2-sulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C2C=C(O)C(O)=CC2=C1 DKJVSIITPZVTRO-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001414 amino alcohols Chemical class 0.000 description 2
- 150000008064 anhydrides Chemical class 0.000 description 2
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 2
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 150000002357 guanidines Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- JFXDYPLHFRYDJD-UHFFFAOYSA-M sodium;6,7-dihydroxynaphthalene-2-sulfonate Chemical compound [Na+].C1=C(S([O-])(=O)=O)C=C2C=C(O)C(O)=CC2=C1 JFXDYPLHFRYDJD-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- KYVBNYUBXIEUFW-UHFFFAOYSA-N 1,1,3,3-tetramethylguanidine Chemical compound CN(C)C(=N)N(C)C KYVBNYUBXIEUFW-UHFFFAOYSA-N 0.000 description 1
- CZKKIYPWLBINSU-UHFFFAOYSA-N 2-[3-[2-[2-[bis(carboxymethyl)amino]-5-methylphenoxy]ethoxy]-N-(carboxymethyl)-4-(2-diazoacetyl)anilino]acetic acid Chemical compound Cc1ccc(N(CC(O)=O)CC(O)=O)c(OCCOc2cc(ccc2C(=O)C=[N+]=[N-])N(CC(O)=O)CC(O)=O)c1 CZKKIYPWLBINSU-UHFFFAOYSA-N 0.000 description 1
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 1
- PYBSFPTVHNWRRC-UHFFFAOYSA-N 2-ethoxy-4-n,4-n-diethylbenzene-1,4-diamine Chemical compound CCOC1=CC(N(CC)CC)=CC=C1N PYBSFPTVHNWRRC-UHFFFAOYSA-N 0.000 description 1
- CLAHOZSYMRNIPY-UHFFFAOYSA-N 2-hydroxyethylurea Chemical compound NC(=O)NCCO CLAHOZSYMRNIPY-UHFFFAOYSA-N 0.000 description 1
- NDZMGWMCVQXHET-UHFFFAOYSA-N 3-diazo-4-phenylmorpholine Chemical compound [N+](=[N-])=C1N(CCOC1)C1=CC=CC=C1 NDZMGWMCVQXHET-UHFFFAOYSA-N 0.000 description 1
- IOHSKBKUMUBQRZ-UHFFFAOYSA-N 7,8-dihydroxynaphthalene-1,3-disulfonic acid Chemical compound C1=C(S(O)(=O)=O)C=C(S(O)(=O)=O)C2=C(O)C(O)=CC=C21 IOHSKBKUMUBQRZ-UHFFFAOYSA-N 0.000 description 1
- LRSYZHFYNDZXMU-UHFFFAOYSA-N 9h-carbazol-3-amine Chemical compound C1=CC=C2C3=CC(N)=CC=C3NC2=C1 LRSYZHFYNDZXMU-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 101100039010 Caenorhabditis elegans dis-3 gene Proteins 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- RYECOJGRJDOGPP-UHFFFAOYSA-N Ethylurea Chemical compound CCNC(N)=O RYECOJGRJDOGPP-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- VGGLHLAESQEWCR-UHFFFAOYSA-N N-(hydroxymethyl)urea Chemical compound NC(=O)NCO VGGLHLAESQEWCR-UHFFFAOYSA-N 0.000 description 1
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-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
- FVFJGQJXAWCHIE-UHFFFAOYSA-N [4-(bromomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CBr)C=C1 FVFJGQJXAWCHIE-UHFFFAOYSA-N 0.000 description 1
- DYRDKSSFIWVSNM-UHFFFAOYSA-N acetoacetanilide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1 DYRDKSSFIWVSNM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 229940059913 ammonium carbonate Drugs 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- XKGUZGHMWUIYDR-UHFFFAOYSA-N benzyl n-(3-fluoro-4-morpholin-4-ylphenyl)carbamate Chemical compound C=1C=C(N2CCOCC2)C(F)=CC=1NC(=O)OCC1=CC=CC=C1 XKGUZGHMWUIYDR-UHFFFAOYSA-N 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- CNWSQCLBDWYLAN-UHFFFAOYSA-N butylurea Chemical compound CCCCNC(N)=O CNWSQCLBDWYLAN-UHFFFAOYSA-N 0.000 description 1
- STIAPHVBRDNOAJ-UHFFFAOYSA-N carbamimidoylazanium;carbonate Chemical compound NC(N)=N.NC(N)=N.OC(O)=O STIAPHVBRDNOAJ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- MPSUKRPHWLTODZ-UHFFFAOYSA-N diazanium;2-(carboxylatomethoxy)acetate Chemical compound [NH4+].[NH4+].[O-]C(=O)COCC([O-])=O MPSUKRPHWLTODZ-UHFFFAOYSA-N 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 238000010017 direct printing Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 229940031575 hydroxyethyl urea Drugs 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011872 intimate mixture Substances 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- ATGUVEKSASEFFO-UHFFFAOYSA-N p-aminodiphenylamine Chemical compound C1=CC(N)=CC=C1NC1=CC=CC=C1 ATGUVEKSASEFFO-UHFFFAOYSA-N 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010424 printmaking Methods 0.000 description 1
- ZQZJKHIIQFPZCS-UHFFFAOYSA-N propylurea Chemical compound CCCNC(N)=O ZQZJKHIIQFPZCS-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 230000011514 reflex Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- JVNBYZLBVASWIM-UHFFFAOYSA-M sodium;2,3-dihydroxynaphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(O)C(O)=CC2=C1 JVNBYZLBVASWIM-UHFFFAOYSA-M 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000013022 venting Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 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
- G03C1/52—Compositions containing diazo compounds as photosensitive substances
Definitions
- the present invention relates to the production of diazotype photoprinting materials. More particularly, the subject invention is directed to improve diazotype photoprinting compositions which are developed under the influence of heat.
- Diazotype reproduction processes are classified as either moist processes or dry processes.
- a moist process the base is coated with a diazo compound which is exposed to light under a pattern. Thereafter, color development is brought about by contacting the latent diazo image with a solution of a coupling compound and aqueous alkali.
- the light sensitive layer contains both the diazo compound and a coupler together with acids and various other stabilizing substances.
- Stabilizing methods such as placing the coupler within a gelatin coating and dusting powdered coupler on the diazo coated paper prevented precoupling but also resulted in the development of faint and weak reproduc tions.
- Another object of the invention is to provide heat developable diazotype photoprinting materials; which have an excellent shelf life.
- a further object of the invention is to provide stable diazotype photoprinting materials which produce permanent prints of excellent quality.
- a still further object is to provide diazotype photoprinting materials and methods which produce prints having excellent color density.
- the present invention comprises the discovery that improved diazotype photoprinting compositions can be prepared by using a complex salt in place of a diazo compound and a coupler compound.
- a complex salt in place of a diazo compound and a coupler compound.
- Such compounds which will be described more fully below, underg0 molecular rearrangement to form an azoic dye.
- the physical attachment of the diazo compound and'the coupler in the present invention produces a greatly accelerated dye forming reaction when the copy paper is heat treated.
- astable salt of a diazo compound and a sulfonic acid coupler is formed in such a way that when a coating containing the complex and an alkaline generating material such as urea is'lieated, the complex need only undergo a molecular rearrangement to produce the azoic dye.
- an acid stabilizer also be present 7
- this stabiiizer is a 'noncoupling' sulfonic acid stabilizer.
- iazo sulfonic acid coupler complex can be formed and thenapplied to a base material in the coating solution, or the complex can be'formed in situ. In the latter case, a complex of diazo compound and a noncoupling sulfonic acid, such as m-benzene disulfonic acid, is formed. This complex is thenapplied in solution to a base material'along with a coupling sulfonic acid. When the complex and the coupler are dissolved in the solution, the
- diazo ionizes to form a diazonium ion.
- the less soluble complex of the diazo and the coupler is primarily formed.
- a suitable base is coated with a solution containing a diazo compound-sulfonic acid coupler complex, an acid stabilizer, and an alkaline generating compound such as urea.
- the coating solution contains a diazo compound-noncoupling sulfonic acid complex, a coupling sulfonic acid, and an alkaline generating agent. Thereafter, the volatile constituents of the solution are removed.
- the coating will consist of a diazo compound-coupling sulfonic acid complex, an acid stabilizer (preferably a noncoupling sulfonic acid), and an alkali generating material.
- the treated base is exposed to the action of ultraviolet rays through the master to be copied.
- the rays destroy or otherwise inactivate the print-forming components in all areas of the coated material which are not protected by the lines or designs of the original.
- the print is formed by heating the exposed base above the temperature required to decompose urea or another alkaline generating compound.
- the ammonia that is generated causes a sudden molecular rearrange ment of the complex to form an azoic dye.
- the print may be made by applying infrared radiation to the original while the original is in contact with the reproduction material. In this manner the design or letter areas of the original are heated above the temperature at which the urea decomposes.
- the heat thus generated is transmitted to the reproduction paper whereupon ammonia produces an alkaline reaction which causes an intramolecular rearrangement of to complex.
- the resulting print is a precise positive copy of the original. Subsequently, the nondeveloped portions of the coated base can be treated with ultraviolet rays to destroy the diazo compound.
- Metal sulfates such as cadmium sulfate, zinc sulfate, nickel sulfate, cobalt sulfate, aluminum sulfate, magnesium sulfate, and ceric ammonium sulfate can also be added to These agents include such the composition.
- sulfates in heat developaole processes is described in copending application Serial No. 156,260 which was filed on December 1, 1961. The disclosure or" this copending application is also incorporated in the present specification by reference.
- Example I discloses a method for preparing the complex of p-diazophenylmorpholine and 2,3-dihydroxynaphthalene-G-sulfonic acid.
- H 0 held at approximately 30 C.
- 2.5 ml. of 37% HCl 10 g. of citric acid
- 40 g. of p-diazophenylmorpholine zinc chloride salt The mixture is stirred until the diazo is completely dissolved.
- Twenty (20) g. of Nuchar is added to the solution and the solution is stirred for twenty minutes. After the Nuchar has been filtered out, the filtrate is poured into a clean beaker equipped with a stirrer.
- Example II This example disclose the preparation of the complex of m-benzenedisulfonic acid (a noncoupling sulfonic acid) and p-diazophenylmorpholine.
- the diazo and the acid are dissolved in a minimum amount of Water.
- a ratio of two equivalents of diazo to one equivalent of acid is maintained.
- the temperature is kept at about 35 C. and the solution is protected from light.
- Five (5) g. portions of diazo are added to the acid. The first portion should be dissolved before adding the second portion. When no more diazo will go into the solution, the solution is cooled to a temperature of about 5 C.
- the product is then filtered off with a coarse filter.
- the reaction is as follows:
- Example 111 Complex salt of N-p-diazophenylmorpholine and Saponin g naphthalene-6-sulfonic acid.
- 6 g. of tartaric acid, ml. of 37% HCl, and 11.4 g. of 4- diazo-2,5-dibutoxy-N-benzoylaniline zinc chloride salt are dissolved in 5 85 ml. H O at 35 C.
- 5 g. of charcoal is added and the solution is stirred for minutes and filtered.
- a solution containing 9 g. of 2,3-dihydroxynaphthalene-6- sodium sulfonate and 225 ml. of B 0 is added dropwise (approximately one drop per second) to the previously prepared solution. The resultant product is then filtered and dried.
- Example IV This example illustrates a suitable composition which can be. used in preparing the subject heat developable papers.
- the composition included the following materials:
- the complex consisted of the diazo and a noncoupling sulfonic acid.
- the diazo ionized into a diazonium ion and after being applied to sheet paper the less soluble complex of the diazo and 2,3-dihydroxynaphthalene-6-sulfonic acid was primarily formed.
- the composition was applied to standard commercial diazo process paper at the rate of about 30 g. of the complex per 1,000 square feet.
- An original and the reproduction paper were placed in face-to-back contact with each other and conducted through the focal Zone of an infrared beam. The materials travelled through the focal zone at a rate of about 1 to 2 inches per second and reached temperatures of about 205 to 220 C. By this process a black line reproduction was obtained having good color and shelf life.
- Example V In this test, the following formulations were applied to standard reproduction paper in the manner described above in connection with Example IV. Once again, the paper was developed by the use of an infrared beam. In each instance, a reproduction was obtained having good color and shelf life characteristics.
- urea derivatives would include methyl urea, ethyl urea, propyl urea, and butyl urea, and hydroxy ureas such as hydroxy methyl urea and hydroxy ethyl urea. It is often advantageous to use a plurality of such compounds, such as mixtures of urea and guanidine, and urea and tetramethyl guanidine.
- Organic nitrogen base salts which produce an alkaline reaction when heated may be employed, particularly salts of amines with volatile or decomposable acids such as acetic acid, malonic acid, gluconic acid, and other heat fugitive acids.
- Amino-parafiins and especially hydroxylated derivatives thereof or amino alcohols are preferred, particularly those having low volatility, substantial alkalinity, and no odor, and which are resistant to oxidation.
- Examples of such amines are tri-(hydroxymethyl)- aminomethane, 2-amino-2-methyl-1,3-propanediol, ethanolamine, diethanolamine, and ethyl diethanolamine.
- guanidines are also basic, and their basicity may provide or contribute to the necessary alkaline reaction, with or without decomposition thereof to produce ammonia.
- Other compounds which are contemplated include the ammonium salts of Weak acids, such as ammonium gluconate, ammonium acetate, ammonium carbonate, ammonium diglycolate, and ammonium oleate.
- the compounds containing the ammonium ion presently are not prefeired as the materials produced therewith tend to have a reduced shelf life.
- Various drafting and print-making papers are suitable, as are regenerated cellulose, synthetic plastic and other such sheet materials capable of transmitting the radiation without substantial absorption thereof.
- the coupling component is employed in a proportion preferably at least sufficient to constitute a stoichiometric amount with respect to the diazo compound, and preferably in substantial excess. Thus, about 2 to equivalents of coupler perequivalent of diazo compound is preferred in most cases.
- alkaline reacting material employed should be sufiicient to elevate the pH of the sensitized layer to that required for coupling, and this quantity will likewise depend upon the characteristics of the material and of the other substances in the sensitive layer. It has been found, for example, that compounds of the type of urea may be employed in a weight ratio to diazo compound of about 3-1021. The proportion of an amino alcohol while varying with its basicity and molecular weight, will frequently be in the range of about 0.5-l0 parts by weight to 1 part of diazo compound. Other compounds may be employed at rates corresponding thereto on the basis of the ammonia evolved or the resulting pH change.
- the primary source of the necessary heat may be a quartz lamp used in conjunction with an elliptical reflector so as to provide an intense zone of near infrared and infrared light.
- the lamp may produce a color temperature of about 2750 K. with about 1500 watts.
- the reflector ellipse dimensions may be 0.750 inch for the minor axis and 0.845 inch for the major axis.
- the tungsten element of the lamp is located at one focus of the ellipse, and the surface of the original or master at the other.
- Reproduction material which comprises: a supported layer of a visibly heat-sensitive composition, said composition comprising a mixture of the complex salt reaction product of a diazonium salt and a coupling aromatic sulfonic acid, an acid stabilizer, said stabilizer being free of azo coupling groups, and an organic nitrogen base producing an alkaline reaction when heated, said composi tion being free of any substantial precoupling.
- a process for graphically reproducing an original which comprises: placing the original to be reproduced in superimposed relationship with a supported layer of. a visibly heat-sensitive composition, said composition comprising the complex salt reaction product of a diazonium salt and a coupling aromatic sulfonic acid, an acid stabilizer, said stabilizer being free of azo coupling groups, and an or anic nitrogen base which produces an alkaline reaction when heated, irradiating said superimposed original to render the diazo compoundincapable of coupling in the areas not protected by the characters of said original, and thereafter heating said supported layer of said visibly heat-sensitive composition whereby said complex salt undergoes an intramolecular rearrangement to form an azo dye, and whereby said original is visibly reproduced.
- Reproduction material which comprises: a supported layer of a visibly heat-sensitive composition, said composition comprising a mixture of the complex salt of p diazophenylmorpholine and 2,3-dihydroxynaphthalene-6- sulfonic acid, an acid stabilizer, said stabilizer being free of azo coupling groups, and urea, said composition being free of any substantial precoupling.
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Description
United States Patent 3,153,592 COMPLEX SALT DIAZOTYPE PHOTOPRENTING MATERIALS Robert J. Kiirnkowshi, Chicago, and Richard E. Flory,
Bensenviile, ill, assiguors to Eugene Dietzgen (30., Chicago, illi., a corporation of Delaware N Drawing. Filed May 15, 1%2, Ser. No. 1%,960 6.Claims. (Cl. 96-49) The present invention relates to the production of diazotype photoprinting materials. More particularly, the subject invention is directed to improve diazotype photoprinting compositions which are developed under the influence of heat.
In diazotype photoprinting processes, a suitable base such as paper is treated with a solution of two dye components. One of the components is a diazo compound which is sensitive to light, and the other component is an azo coupling compound. The coupling compound is capable of reacting under proper conditions with the diazo component to form a dye. In making a print, the treated base is exposed to light under a translucent original or master. In those areas of the base which are reached by the light,the diazo compound is at least partially destroyed. In those areas that are beneath opaque lines or designs, on the other hand, the diazo compound is not afiected by the light. The print is developed by reacting the retained diazo compound with the coupler to form a highly colored azo dyestufr" in precise duplication of the original.
Diazotype reproduction processes are classified as either moist processes or dry processes. In a moist process the base is coated with a diazo compound which is exposed to light under a pattern. Thereafter, color development is brought about by contacting the latent diazo image with a solution of a coupling compound and aqueous alkali. In the dry process the light sensitive layer contains both the diazo compound and a coupler together with acids and various other stabilizing substances. After the treated base has been exposed to light the print is formed by the use of hot aqueous ammonia fumes.-
Each of the above systems has'serious disadvantages. The principal objection to the dry. process is that it requires the use of ammoniafumes. Because of the pungent and corrosive nature of the fumes it is necessary to pro vide special venting devices before the process can be used tov any great extent.
tion between the components at the desired time. In the first heat developable system s, satisfactory shelf lifewas Although the moist process does not require the use of ammonia fumes it has the dis-3 advantage that the developing solution must be mixed in the dye-formingcomposition.
3,1535% ?ater1ted Get. as, rea
only accomplished at the expense of print quality. Stabilizing methods such as placing the coupler within a gelatin coating and dusting powdered coupler on the diazo coated paper prevented precoupling but also resulted in the development of faint and weak reproduc tions.
More recently, a heat developable diazotype system has been developed which is feasible from a commercial standpoint. In this system a layer containing an intimate mixture of a diazo compound, an azo coupling compo nent, and an alkali generating compound is formed on a suitable base. A solution of the various materials is brushed or otherwise applied to the base. Following the removal of volatiles from the liquid coat, the paper, cloth plastic, etc., is ready for photoprinting. A description of a preferred heat developable process is disclosed in a copending application Serial No. 5,688, which was filed on February 1, 1960. The disclosure of application Serial No. 5,688 is incorporated in the present specification by reference.
Even though the most recent heat developable processes provide commercially acceptable results, there is still room for improvement both as to the shelf life of the coated materials and as to the color density of the resultant reproduction.
It is an object of the present invention to provide improved diazotype photoprinting materials and methods.
Another object of the invention is to provide heat developable diazotype photoprinting materials; which have an excellent shelf life.
A further object of the invention is to provide stable diazotype photoprinting materials which produce permanent prints of excellent quality.
A still further object is to provide diazotype photoprinting materials and methods which produce prints having excellent color density.
Other objects will become apparent to those skilled in the art from the following detailed description of the invention.
In general, the present invention comprises the discovery that improved diazotype photoprinting compositions can be prepared by using a complex salt in place of a diazo compound and a coupler compound. Such compounds, which will be described more fully below, underg0 molecular rearrangement to form an azoic dye. The physical attachment of the diazo compound and'the coupler in the present invention produces a greatly accelerated dye forming reaction when the copy paper is heat treated.
In our process, astable salt of a diazo compound and a sulfonic acid coupler is formed in such a way that when a coating containing the complex and an alkaline generating material such as urea is'lieated, the complex need only undergo a molecular rearrangement to produce the azoic dye. it is essential that an acid stabilizer also be present 7 Preferably, this stabiiizer is a 'noncoupling' sulfonic acid stabilizer. The
' iazo sulfonic acid coupler complex can be formed and thenapplied to a base material in the coating solution, or the complex can be'formed in situ. In the latter case, a complex of diazo compound and a noncoupling sulfonic acid, such as m-benzene disulfonic acid, is formed. This complex is thenapplied in solution to a base material'along with a coupling sulfonic acid. When the complex and the coupler are dissolved in the solution, the
diazo ionizes to form a diazonium ion. Upon drying of the coating on a sheet of paper or the like the less soluble complex of the diazo and the coupler is primarily formed.
In practicing the invention, a suitable base is coated with a solution containing a diazo compound-sulfonic acid coupler complex, an acid stabilizer, and an alkaline generating compound such as urea. As an alternative, the coating solution contains a diazo compound-noncoupling sulfonic acid complex, a coupling sulfonic acid, and an alkaline generating agent. Thereafter, the volatile constituents of the solution are removed. In either of the above alternatives the coating will consist of a diazo compound-coupling sulfonic acid complex, an acid stabilizer (preferably a noncoupling sulfonic acid), and an alkali generating material. The treated base is exposed to the action of ultraviolet rays through the master to be copied. The rays destroy or otherwise inactivate the print-forming components in all areas of the coated material which are not protected by the lines or designs of the original. The print is formed by heating the exposed base above the temperature required to decompose urea or another alkaline generating compound. The ammonia that is generated causes a sudden molecular rearrange ment of the complex to form an azoic dye. Alternatively, the print may be made by applying infrared radiation to the original while the original is in contact with the reproduction material. In this manner the design or letter areas of the original are heated above the temperature at which the urea decomposes. The heat thus generated is transmitted to the reproduction paper whereupon ammonia produces an alkaline reaction which causes an intramolecular rearrangement of to complex. The resulting print is a precise positive copy of the original. Subsequently, the nondeveloped portions of the coated base can be treated with ultraviolet rays to destroy the diazo compound.
. Examples of diazo compounds which can be used to produce the diazo-coupling sulfonic acid complex include the following:
p-Amino-N,N-dimethylaniline p-Amino-N,N-diethylaniline p-Amino-N,N-dipropylaniline p-Amino-N-ethyl-N-propylaniline p-Amino-N-ethylaniline-N-propyl p-Amino-N-ethyl-N-[3-hydroxyethylaniline p-Amino-N-methyl-N-fi-hydroxyethylaniline p-Amino-N,N-di-,8-hydroxyethylaniline p-Amino-m-ethoxy-N,N-diethylaniline p-AminoN ethylotoluidine p-Amino-N-ethyl-m-toluidine p-Amino-N,N-diethyl-m-toluidine p-Amino-N-ethyl-N-hydroxyethyl-m-toluidine p-Amino-N-ethyl-N-benzylaniline p-Amino-N-ethyl-N-fl-hydroxyethyl-m-toludine N-p-Amino-phenylmorpholine N-(2,5-diethoxy-4-aminophenyl)-morpholine p-Amino-diphenylamine 3-Aminocarbazole and the like As was indicated above, an acid stabilizing agent should be added to the composition. acids as malonic, gluconic, cyanoacetic, maleic, tartaric, citric, diglycolic, oxalic, acetic, and malic acids, and anhydrides of such acids, e.g., the lactones. Reference to such acids is intended to include the equivalent anhydrides. It is preferred that noncoupling aromatic sulionic acids such as rn-benzenedisulfonic acid be used as the stabilizing agent. The use of such aromatic sulfonic acids as stabilizers is described in copending application Serial No. 67,289 which was filed on November 4, 1960. The disclosure of said copending application is incorporated in the present specification'by reference. Metal sulfates such as cadmium sulfate, zinc sulfate, nickel sulfate, cobalt sulfate, aluminum sulfate, magnesium sulfate, and ceric ammonium sulfate can also be added to These agents include such the composition. The use of such sulfates in heat developaole processes is described in copending application Serial No. 156,260 which was filed on December 1, 1961. The disclosure or" this copending application is also incorporated in the present specification by reference.
The following examples illustrate suitable methods of preparing the diazo-sulfonic acid coupler complexes of the subject invention.
Example I This example discloses a method for preparing the complex of p-diazophenylmorpholine and 2,3-dihydroxynaphthalene-G-sulfonic acid. To 1 liter of H 0 held at approximately 30 C. is added 2.5 ml. of 37% HCl, 10 g. of citric acid, and 40 g. of p-diazophenylmorpholine zinc chloride salt. The mixture is stirred until the diazo is completely dissolved. Twenty (20) g. of Nuchar is added to the solution and the solution is stirred for twenty minutes. After the Nuchar has been filtered out, the filtrate is poured into a clean beaker equipped with a stirrer. Fifty (50) g. of 2,3-dihydroxynaphthalene-o-sulionic acid sodium salt is then added to the filtrate. After the sodium salt dissolves the solution is seeded with a pinch of complex which has previously been prepared. The mixture is allowed to stand overnight whereupon the product is filtered off with a coarse filter and dried at 45 C.
Example II This example disclose the preparation of the complex of m-benzenedisulfonic acid (a noncoupling sulfonic acid) and p-diazophenylmorpholine. The diazo and the acid are dissolved in a minimum amount of Water. A ratio of two equivalents of diazo to one equivalent of acid is maintained. The temperature is kept at about 35 C. and the solution is protected from light. Five (5) g. portions of diazo are added to the acid. The first portion should be dissolved before adding the second portion. When no more diazo will go into the solution, the solution is cooled to a temperature of about 5 C. The product is then filtered off with a coarse filter. The reaction is as follows:
Example 111 Complex salt of N-p-diazophenylmorpholine and Saponin g naphthalene-6-sulfonic acid. In the order given, 6 g. of tartaric acid, ml. of 37% HCl, and 11.4 g. of 4- diazo-2,5-dibutoxy-N-benzoylaniline zinc chloride salt are dissolved in 5 85 ml. H O at 35 C. After the chemicals have been dissolved, 5 g. of charcoal is added and the solution is stirred for minutes and filtered. A solution containing 9 g. of 2,3-dihydroxynaphthalene-6- sodium sulfonate and 225 ml. of B 0 is added dropwise (approximately one drop per second) to the previously prepared solution. The resultant product is then filtered and dried.
Example IV This example illustrates a suitable composition which can be. used in preparing the subject heat developable papers. The composition included the following materials:
Water ml 100 Urea g 27 Thiourea 1 MBDA g 2.032.89 2,3-dihydroxynaphthalene-6-sulfonic acid sodium salt 10 Complex salt of N-p-diazophenylmorpholine and mbenzenedisulfonic acid g 2.27-4.54
1 m-Benzenedisulfonic acid.
In this instance, the complex consisted of the diazo and a noncoupling sulfonic acid. In solution, however, the diazo ionized into a diazonium ion and after being applied to sheet paper the less soluble complex of the diazo and 2,3-dihydroxynaphthalene-6-sulfonic acid was primarily formed. The composition was applied to standard commercial diazo process paper at the rate of about 30 g. of the complex per 1,000 square feet. An original and the reproduction paper were placed in face-to-back contact with each other and conducted through the focal Zone of an infrared beam. The materials travelled through the focal zone at a rate of about 1 to 2 inches per second and reached temperatures of about 205 to 220 C. By this process a black line reproduction was obtained having good color and shelf life.
Example V In this test, the following formulations were applied to standard reproduction paper in the manner described above in connection with Example IV. Once again, the paper was developed by the use of an infrared beam. In each instance, a reproduction was obtained having good color and shelf life characteristics.
2,3-dihydroxynaphthalene-6,8-disulfonic acid g 12.3
MBDA g 4 Thiourea g l 0.3
Water g 14,000 Urea g 3,000 Thiourea g 400 Sulfamic acid g 1,000 Guanidine carbonate g 400 2,3-dihydroxynaphthalene-6,8-disulfonic acid g 6,000 Resorcinol g 1,000 X99 100 Complex salt of N-p-diazophenylmorpholine and MBDA g 1,000 Complex salt of N-p-diazophenylmorpholine and I 2,3-dihydroxynaphthalene sulfonic acid sodium salt g 400 Water ml 100 MBDA g 1.5 Urea g 5 0 Complex of N-p-diazophenylmorpholine and 2,3-
dihydroxynaphthalene-6,8-disulfonic acid g 2.8 Cadmium sulfate g 15 Water m1 100 100 Urea. .g 40 40 MB'DA a" 1 Malonic acid g 2. 3 2, B-dihydroxynaphthalcne-G,
8-disulf0nic acid sodium salt g 6 6 Complex of p-diazo-ml-diethylaniline and 2,
S-dihydroxynaphthalene-fi, s-disulfom'c acid g 2. 8 2. 8 Water a 100 100 Malonic acid s1 1 1 Urea. g 20 10 Complex of N-4'diazo-2, 5-diethoxy-phenylmorpholine and 2, 3-dihydroxynaphthalene-G-sulfonic acid g 5 5 Water- 100 100 100 100 100 Urea. 20 20 20 15 20 'lhioure 1 1 3 3 2 MBDA 3 4 3 3 3 2, 3-dihydroxynaphthalencfi-sulfonic acid g 5. 5 5. 5 2 4 3. 8 Complex salt of N-p-diazo-phenylmorpholine and 2, 3-dihydroxynaphthalene-S-sulfonic acid g 6. 86 6. 86 6 4 6. 4 Acetoacet anilide g. 3 5 5 4 Water .ml. 100 100 100 100 MTBDA", --g 2. 5 1. 5 Urea g 21. 5 21. 5 21. 5 21. 5 2, 3-dinydroxynaphtha c 6-sulfonic acid g 2 2 2 2 Complex salt of N-p-diazophenylmorpholine and 2, S-dihydroxynaphthalencfi-sulfomc acid g 3 3 3 3 Sulfamic acid g 2 3 Water 1 ml 100 100 100 100 100 2, B-dihydroxynaphthalcnc- 6 sulfonic acid sodium salt 2 2 2 2 Urea 25 21. 5 21.5 21. 5 Thiourea g 1 1 1 1 1 Complex salt of N-p-diazophenylmorpholine and 2, E-dihydroxynaphthalene- 6-sulfonic acid g 3 3 3 3 3 Sulfamic acid. .g. 5 5 3 3 3 Boric acid 2 Citric AcitL 2 Tartaric aci 2 stituted urea, and alkyl substituted guanidines, saidalkyl groups containing from 1 to 4; carbon atoms. Specific urea derivatives would include methyl urea, ethyl urea, propyl urea, and butyl urea, and hydroxy ureas such as hydroxy methyl urea and hydroxy ethyl urea. It is often advantageous to use a plurality of such compounds, such as mixtures of urea and guanidine, and urea and tetramethyl guanidine.
Organic nitrogen base salts which produce an alkaline reaction when heated may be employed, particularly salts of amines with volatile or decomposable acids such as acetic acid, malonic acid, gluconic acid, and other heat fugitive acids. Amino-parafiins and especially hydroxylated derivatives thereof or amino alcohols are preferred, particularly those having low volatility, substantial alkalinity, and no odor, and which are resistant to oxidation. Examples of such amines are tri-(hydroxymethyl)- aminomethane, 2-amino-2-methyl-1,3-propanediol, ethanolamine, diethanolamine, and ethyl diethanolamine. The aforementioned guanidines are also basic, and their basicity may provide or contribute to the necessary alkaline reaction, with or without decomposition thereof to produce ammonia. Other compounds which are contemplated include the ammonium salts of Weak acids, such as ammonium gluconate, ammonium acetate, ammonium carbonate, ammonium diglycolate, and ammonium oleate. The compounds containing the ammonium ion presently are not prefeired as the materials produced therewith tend to have a reduced shelf life.
Paper, cloth, plastic sheet materials, plastic impregnated materials, and metal bodies all may be employed as the base material in the direct printing process, provided that the material is not so heat-conductive as to interfere with the process. The reproduction material for use in the reflex process requires that the base be capable of transmitting the heat-producing radiations, and conducting the heat from the original to the sensitive layer.
Various drafting and print-making papers are suitable, as are regenerated cellulose, synthetic plastic and other such sheet materials capable of transmitting the radiation without substantial absorption thereof.
The diazo-sulfonic acid coupler complex, the acid stabilizer, the alkali generator, and the other constituents of the coating composition are applied to the base in solution by one of the conventional coating methods. The materials are preferably dissolved in water, and the one-phase liquid coat is dried by evaporation to a residual moisture content of preferably less than about A volatile organic solvent may also be employed, although such is not ordinarily necessary and therefore is not preferred due to the increased cost and normal disadvantages attendant upon such use. It is necessary that the solvent be one which can be removed substantially completely in the drying process, so as not to have an adverse effect on the shelf life.
The diazo compound is preferably employed in a proportion of about 1 to by weight on the basis of the Water or other solvent content of the sensitizer composition. The composition is applied to the base at standard rates of application, for example, application to diazo process paper is made at the rate of about 10 to 50 grams of diazo compound per one thousand square feet.
The coupling component is employed in a proportion preferably at least sufficient to constitute a stoichiometric amount with respect to the diazo compound, and preferably in substantial excess. Thus, about 2 to equivalents of coupler perequivalent of diazo compound is preferred in most cases.
The quantity of alkaline reacting material employed should be sufiicient to elevate the pH of the sensitized layer to that required for coupling, and this quantity will likewise depend upon the characteristics of the material and of the other substances in the sensitive layer. It has been found, for example, that compounds of the type of urea may be employed in a weight ratio to diazo compound of about 3-1021. The proportion of an amino alcohol while varying with its basicity and molecular weight, will frequently be in the range of about 0.5-l0 parts by weight to 1 part of diazo compound. Other compounds may be employed at rates corresponding thereto on the basis of the ammonia evolved or the resulting pH change.
The conditions of time and temperature for developing the image are selected for the system employed to produce the necessary alkaline reaction without undesirable decomposition of the diazo compound. The results are generally advantageous when the sensitive layer is subjected to a relatively high temperature of about C. to 220 C. for a short time, ranging from a few seconds to about a minute. While rapid development is preferred, the materials can be heated for a longer period of time at a lower temperature. As an example, the temperatures reached in the sensitive layers in the examples which follow were about 205 C. to 220 C. for a period of about six to fifteen seconds. These rates are very advantageous and enable a number of copies to be made in a short period of time. As was indicated above, the use of the diazo-sulfonic acid coupler complex substantially increases the development speed of the composition.
Satisfactory temperatures may be provided in the sensitive layer in a number of ways. Thus, the primary source of the necessary heat may be a quartz lamp used in conjunction with an elliptical reflector so as to provide an intense zone of near infrared and infrared light. The lamp may produce a color temperature of about 2750 K. with about 1500 watts. The reflector ellipse dimensions may be 0.750 inch for the minor axis and 0.845 inch for the major axis. The tungsten element of the lamp is located at one focus of the ellipse, and the surface of the original or master at the other.
The duplicating machine may be allowed to operate without cooling the parts, so that part of the heat increment is supplied by the parts such as the rollers or conveyor means, or the heat produced by absorption of the radiations may be supplemented in another manner. If the background diazo compound is first decomposed in the direct process the latent image produced thereby may be developed if desired by contact with a heated surface.
As has been indicated above, the essential components of the subject composition include (1) a diazo compound, (2) a coupling sulfonic acid, (3) an alkaline producing compound, and (4) an acid stabilizer. It is preferred that the acid stabilizer be an organic sulfonic acid stabilizer of the type decribed in application Serial No. 67,- 289 which was filed on November 4, 1960. Any aromatic compound which is capable of coupling and which contains at least one sulfonic acid group can be used as the coupler in preparing the subject complex. Coupling naphthol sulfonic acids are of particular interest. Amino naphthol sulfonic acids can also be used, although these materials tend to become discolored on storage.
Obviously many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof, and therefore only such limitations should be imposed as are indicated in the appended claims.
We claim:
1. Reproduction material which comprises: a supported layer of a visibly heat-sensitive composition, said composition comprising a mixture of the complex salt reaction product of a diazonium salt and a coupling aromatic sulfonic acid, an acid stabilizer, said stabilizer being free of azo coupling groups, and an organic nitrogen base producing an alkaline reaction when heated, said composi tion being free of any substantial precoupling.
2. A process for graphically reproducing an original which comprises: placing the original to be reproduced in superimposed relationship with a supported layer of. a visibly heat-sensitive composition, said composition comprising the complex salt reaction product of a diazonium salt and a coupling aromatic sulfonic acid, an acid stabilizer, said stabilizer being free of azo coupling groups, and an or anic nitrogen base which produces an alkaline reaction when heated, irradiating said superimposed original to render the diazo compoundincapable of coupling in the areas not protected by the characters of said original, and thereafter heating said supported layer of said visibly heat-sensitive composition whereby said complex salt undergoes an intramolecular rearrangement to form an azo dye, and whereby said original is visibly reproduced.
3. A process as in claim 2 wherein said compound which produces an alkaline reaction when heated is urea. 4. A process for graphically reproducing an original which comprises: placing an original having preferential radiation-absorbing areas in contact with a supported layer of a visibly heat-sensitive composition, said composition comprising the complex salt reaction product of a diazonium salt and a coupling aromatic sulfonic acid, an acid stabilizer, said stabilizer being free of azo coupling groups, and an organic nitrogen base which produces an alkaline reaction when heated, and irradiating said original with heat producing radiations to effect an intramolecular rearrangement of said complex salt in the areas of said supported layer registering with said radiation-absorbing areas of said original, whereby said original is visibly reproduced.
5. A process as in claim 4 wherein said compound which produces an alkaline reaction when heated is urea.
6. Reproduction material which comprises: a supported layer of a visibly heat-sensitive composition, said composition comprising a mixture of the complex salt of p diazophenylmorpholine and 2,3-dihydroxynaphthalene-6- sulfonic acid, an acid stabilizer, said stabilizer being free of azo coupling groups, and urea, said composition being free of any substantial precoupling.
References Eited in the tile of this patent UNITED STATES PATENTS 2,217,189 Sus Oct. 8, 1940 2,501,874 Peterson Mar. 28, 1950 2,597,306 Eaton et a1. May 20, 1952 2,680,062 Sus June 1, 1954 2,694,009 Sus Nov. 9, 1954 2,727,820 Botkin et a1. Dec. 20, 1955 FOREIGN PATENTS 1,249,913 France Nov. 28, 1960 OTHER REFERENCES Photographic Science and Engineering, vol. 5, No. 4, July-August, 1961, pages 243 (Copy in Sci. Libr.)
UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,153,592 October 20, 1964 Robert J. Klimkowski et alla It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below,
Column 3, line 44, for "pAmino-N-ethylaniline-N-propyl" read p-Amino-N-ethy,laniline line 49, for "pAmino- N ethylotoluidine" read p-AminoN-=ethylo-to1uidine column 4, lines 56 to 6 8, for that portion of the formula reading:
I IQ I IlI:N-o s@-SO -N=N read NEN Q3S i column 5, in the table, first column, line 10 thereof, for "Cyanamide (50%) --g" read Cyanamide (50%) -=--ml column 6, in the table, second column, line 4 thereof, for "2.3" read 2.5 "same table, first column line 7 thereof,
for read same column 6, same table, fir t column, line 9 thereof, for "Water g" read Water 1 Signed and sealed this 30th day of March l 965.
(SEAL) Attest:
ERNEST W. SWIDER ..,ED.WARD .J. BRENNER Attesting Officer Commissioner of Patents-
Claims (1)
- 2. A PROCESS FOR GRAPHICALLY REPRODUCING AN ORIGINAL WHICH COMPRISES: PLACING THE ORIGINAL TO BE REPRODUCED IN SUPERIMPOSED RELATIONSHIP WITH A SUPPORTED LAYER OF A VISIBLY HEAT-SENSITIVE COMPOSITION, SAID COMPOSITION COMPRISING THE COMPLES SALT REACTION PRODUCT OF A DIAZONIUM SALT AND A COUPLING ATOMATIC SULFONIC ACID, AN ACID STABILIZER, SAID STABILIZER BEING FREE OF AZO COUPLDING GROUPS, AND AN ORGANIC NITROGEN BASE WHICH PRODUCES AN ALKALINE REACTION WHEN HEATED, IRRADIATING SAID SUPERIMPOSED ORIGINAL TO RENDER THE DIAZO COMPOUND INCAPABLE OF COUPLING IN THE AREAS NOT PROTECTED BY THE CARACTERS OF SAID ORIGINAL, AND THEREAFTER HEATING SAID SUPPORTED LAYER OF SAID VISIBLY HEAT-SENSITVE COMPOSITION WHEREBY SAID COMPLEX SALT UNDERGOES AN INTRAMOLECULAR REARRANGEMENT TO FORM AN AZO DYE, AND WHEREBY SAID ORIGINAL IS VISIBLY REPRODUCED.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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US194960A US3153592A (en) | 1962-05-15 | 1962-05-15 | Complex salt diazotype photoprinting materials |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US194960A US3153592A (en) | 1962-05-15 | 1962-05-15 | Complex salt diazotype photoprinting materials |
Publications (1)
Publication Number | Publication Date |
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US3153592A true US3153592A (en) | 1964-10-20 |
Family
ID=22719526
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US194960A Expired - Lifetime US3153592A (en) | 1962-05-15 | 1962-05-15 | Complex salt diazotype photoprinting materials |
Country Status (1)
Country | Link |
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US (1) | US3153592A (en) |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3309200A (en) * | 1963-06-03 | 1967-03-14 | Itek Corp | Data reproduction process |
US3389995A (en) * | 1964-09-15 | 1968-06-25 | Gen Aniline & Film Corp | Two-component heat developable diazotypes containing amidine compounds |
US3458314A (en) * | 1963-09-25 | 1969-07-29 | Keuffel & Esser Co | Process and device for developing a two-component diazotype material |
US3479183A (en) * | 1965-06-16 | 1969-11-18 | Tecnifax Corp | Negative-working diazosulfonate reproduction process |
US3713825A (en) * | 1970-04-27 | 1973-01-30 | Plastic Coating Corp | Light-activated diazography |
US3770442A (en) * | 1971-10-15 | 1973-11-06 | Minnesota Mining & Mfg | Stabilized light-sensitive intermediate sheet |
US4230492A (en) * | 1978-01-17 | 1980-10-28 | The Richardson Company | Aryl sulfonic acid based stabilizers for presensitized planographic plates |
US4326020A (en) * | 1980-09-10 | 1982-04-20 | Polychrome Corporation | Method of making positive acting diazo lithographic printing plate |
EP0118846A2 (en) * | 1983-03-09 | 1984-09-19 | Hoechst Aktiengesellschaft | Two-component diazo type material |
US4478926A (en) * | 1981-12-28 | 1984-10-23 | Andrews Paper & Chemical Co., Inc. | Zinc sulfonates and their use in diazotypy |
US5188924A (en) * | 1984-05-14 | 1993-02-23 | Kabushiki Kaisha Toshiba | Pattern forming method utilizing material with photoresist film underlayer and contrast enhancement overlayer containing photosensitive diazonium salt |
WO2015166217A3 (en) * | 2014-04-30 | 2015-12-23 | De La Rue International Limited | Security device components and methods of manufacture thereof |
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US2217189A (en) * | 1938-12-05 | 1940-10-08 | Kalle & Co Ag | Process of preparing photographic prints |
US2501874A (en) * | 1946-06-12 | 1950-03-28 | Gen Aniline & Film Corp | Photographic diazo-sensitized glassine paper |
US2597306A (en) * | 1949-10-05 | 1952-05-20 | Little Inc A | Printing process wherein an alkaline substance passing through stencil openings effects coupling of an azo dye in situ |
US2680062A (en) * | 1949-07-23 | 1954-06-01 | Keuffel & Esser Co | Process for the production of azo dyestuff images |
US2694009A (en) * | 1948-10-01 | 1954-11-09 | Keuffel & Esser Co | Diazo-n-sulfonate light-sensitive material |
US2727820A (en) * | 1952-04-29 | 1955-12-20 | Gen Aniline & Film Corp | Light-sensitive diazotype layers containing carboxamides |
FR1249913A (en) * | 1959-11-23 | 1961-01-06 | Bauchet & Cie Ets | Heat-developable diazotype product |
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1962
- 1962-05-15 US US194960A patent/US3153592A/en not_active Expired - Lifetime
Patent Citations (7)
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US2217189A (en) * | 1938-12-05 | 1940-10-08 | Kalle & Co Ag | Process of preparing photographic prints |
US2501874A (en) * | 1946-06-12 | 1950-03-28 | Gen Aniline & Film Corp | Photographic diazo-sensitized glassine paper |
US2694009A (en) * | 1948-10-01 | 1954-11-09 | Keuffel & Esser Co | Diazo-n-sulfonate light-sensitive material |
US2680062A (en) * | 1949-07-23 | 1954-06-01 | Keuffel & Esser Co | Process for the production of azo dyestuff images |
US2597306A (en) * | 1949-10-05 | 1952-05-20 | Little Inc A | Printing process wherein an alkaline substance passing through stencil openings effects coupling of an azo dye in situ |
US2727820A (en) * | 1952-04-29 | 1955-12-20 | Gen Aniline & Film Corp | Light-sensitive diazotype layers containing carboxamides |
FR1249913A (en) * | 1959-11-23 | 1961-01-06 | Bauchet & Cie Ets | Heat-developable diazotype product |
Cited By (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3309200A (en) * | 1963-06-03 | 1967-03-14 | Itek Corp | Data reproduction process |
US3458314A (en) * | 1963-09-25 | 1969-07-29 | Keuffel & Esser Co | Process and device for developing a two-component diazotype material |
US3389995A (en) * | 1964-09-15 | 1968-06-25 | Gen Aniline & Film Corp | Two-component heat developable diazotypes containing amidine compounds |
US3479183A (en) * | 1965-06-16 | 1969-11-18 | Tecnifax Corp | Negative-working diazosulfonate reproduction process |
US3713825A (en) * | 1970-04-27 | 1973-01-30 | Plastic Coating Corp | Light-activated diazography |
US3770442A (en) * | 1971-10-15 | 1973-11-06 | Minnesota Mining & Mfg | Stabilized light-sensitive intermediate sheet |
US4230492A (en) * | 1978-01-17 | 1980-10-28 | The Richardson Company | Aryl sulfonic acid based stabilizers for presensitized planographic plates |
US4326020A (en) * | 1980-09-10 | 1982-04-20 | Polychrome Corporation | Method of making positive acting diazo lithographic printing plate |
US4478926A (en) * | 1981-12-28 | 1984-10-23 | Andrews Paper & Chemical Co., Inc. | Zinc sulfonates and their use in diazotypy |
EP0118846A2 (en) * | 1983-03-09 | 1984-09-19 | Hoechst Aktiengesellschaft | Two-component diazo type material |
US4590143A (en) * | 1983-03-09 | 1986-05-20 | Hoechst Aktiengesellschaft | Two-component diazotype material with diazonium salt with anion of benzene or toluene sulfonate |
EP0118846A3 (en) * | 1983-03-09 | 1987-05-27 | Hoechst Aktiengesellschaft | Two-component diazo type material |
US5188924A (en) * | 1984-05-14 | 1993-02-23 | Kabushiki Kaisha Toshiba | Pattern forming method utilizing material with photoresist film underlayer and contrast enhancement overlayer containing photosensitive diazonium salt |
WO2015166217A3 (en) * | 2014-04-30 | 2015-12-23 | De La Rue International Limited | Security device components and methods of manufacture thereof |
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