US3893860A - Photothermographic element and process - Google Patents
Photothermographic element and process Download PDFInfo
- Publication number
- US3893860A US3893860A US489029A US48902974A US3893860A US 3893860 A US3893860 A US 3893860A US 489029 A US489029 A US 489029A US 48902974 A US48902974 A US 48902974A US 3893860 A US3893860 A US 3893860A
- Authority
- US
- United States
- Prior art keywords
- acrylamide
- photothermographic
- photothermographic element
- layer
- poly
- 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
- 238000000034 method Methods 0.000 title claims description 24
- 230000008569 process Effects 0.000 title claims description 11
- -1 silver halide Chemical class 0.000 claims abstract description 60
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 55
- 229910052709 silver Inorganic materials 0.000 claims abstract description 55
- 239000004332 silver Substances 0.000 claims abstract description 55
- 241001061127 Thione Species 0.000 claims abstract description 40
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 33
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011230 binding agent Substances 0.000 claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims description 69
- 229920001577 copolymer Polymers 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 14
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 11
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 11
- 239000004848 polyfunctional curative Substances 0.000 claims description 11
- 229940045105 silver iodide Drugs 0.000 claims description 11
- 239000000178 monomer Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 9
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 9
- 150000003378 silver Chemical class 0.000 claims description 8
- QLAJNZSPVITUCQ-UHFFFAOYSA-N 1,3,2-dioxathietane 2,2-dioxide Chemical compound O=S1(=O)OCO1 QLAJNZSPVITUCQ-UHFFFAOYSA-N 0.000 claims description 6
- FVQQWSSTYVBNST-UHFFFAOYSA-N 2-(4-methyl-2-sulfanylidene-1,3-thiazol-3-yl)acetic acid Chemical class CC1=CSC(=S)N1CC(O)=O FVQQWSSTYVBNST-UHFFFAOYSA-N 0.000 claims description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 4
- ZEQIWKHCJWRNTH-UHFFFAOYSA-N 1h-pyrimidine-2,4-dithione Chemical compound S=C1C=CNC(=S)N1 ZEQIWKHCJWRNTH-UHFFFAOYSA-N 0.000 claims description 3
- AFBBKYQYNPNMAT-UHFFFAOYSA-N 1h-1,2,4-triazol-1-ium-3-thiolate Chemical compound SC=1N=CNN=1 AFBBKYQYNPNMAT-UHFFFAOYSA-N 0.000 claims description 2
- YRZCFCHJGYSSML-UHFFFAOYSA-N 3-(2-sulfanylidene-1,3-benzothiazol-3-yl)propanoic acid Chemical class C1=CC=C2SC(=S)N(CCC(=O)O)C2=C1 YRZCFCHJGYSSML-UHFFFAOYSA-N 0.000 claims 1
- KZFMGQGVVIBTIH-UHFFFAOYSA-N 3-(4-methyl-2-sulfanylidene-1,3-thiazol-3-yl)propanoic acid Chemical class CC1=CSC(=S)N1CCC(O)=O KZFMGQGVVIBTIH-UHFFFAOYSA-N 0.000 claims 1
- VSRSZPHFDAWIKX-UHFFFAOYSA-N 3-[4-(hydroxymethyl)-2-sulfanylidene-1,3-thiazol-3-yl]propanoic acid Chemical class OCC1=CSC(=S)N1CCC(O)=O VSRSZPHFDAWIKX-UHFFFAOYSA-N 0.000 claims 1
- 239000003638 chemical reducing agent Substances 0.000 abstract description 20
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 230000002411 adverse Effects 0.000 abstract description 10
- 239000010410 layer Substances 0.000 description 98
- 239000000463 material Substances 0.000 description 45
- 238000012545 processing Methods 0.000 description 21
- 125000004432 carbon atom Chemical group C* 0.000 description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 16
- 229920006322 acrylamide copolymer Polymers 0.000 description 14
- 239000000123 paper Substances 0.000 description 13
- 239000000203 mixture Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 125000002947 alkylene group Chemical group 0.000 description 7
- 239000004094 surface-active agent Substances 0.000 description 7
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 6
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- 238000011534 incubation Methods 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 5
- 229910052721 tungsten Inorganic materials 0.000 description 5
- 239000010937 tungsten Substances 0.000 description 5
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 4
- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000004181 carboxyalkyl group Chemical group 0.000 description 4
- 229920002678 cellulose Polymers 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002301 cellulose acetate Polymers 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002391 heterocyclic compounds Chemical class 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 description 3
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 2
- SGWZVZZVXOJRAQ-UHFFFAOYSA-N 2,6-Dimethyl-1,4-benzenediol Chemical compound CC1=CC(O)=CC(C)=C1O SGWZVZZVXOJRAQ-UHFFFAOYSA-N 0.000 description 2
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical group SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 150000000996 L-ascorbic acids Chemical class 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 229960005070 ascorbic acid Drugs 0.000 description 2
- 239000011668 ascorbic acid Substances 0.000 description 2
- 125000005605 benzo group Chemical group 0.000 description 2
- 230000005587 bubbling Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052729 chemical element Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 125000005528 methosulfate group Chemical group 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 2
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- OSSNTDFYBPYIEC-UHFFFAOYSA-O 1-ethenylimidazole;hydron Chemical compound C=CN1C=C[NH+]=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-O 0.000 description 1
- DBCKMJVEAUXWJJ-UHFFFAOYSA-N 2,3-dichlorobenzene-1,4-diol Chemical compound OC1=CC=C(O)C(Cl)=C1Cl DBCKMJVEAUXWJJ-UHFFFAOYSA-N 0.000 description 1
- ZKEGGSPWBGCPNF-UHFFFAOYSA-N 2,5-dihydroxy-5-methyl-3-(piperidin-1-ylamino)cyclopent-2-en-1-one Chemical compound O=C1C(C)(O)CC(NN2CCCCC2)=C1O ZKEGGSPWBGCPNF-UHFFFAOYSA-N 0.000 description 1
- GPASWZHHWPVSRG-UHFFFAOYSA-N 2,5-dimethylbenzene-1,4-diol Chemical compound CC1=CC(O)=C(C)C=C1O GPASWZHHWPVSRG-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- HIGSPBFIOSHWQG-UHFFFAOYSA-N 2-Isopropyl-1,4-benzenediol Chemical compound CC(C)C1=CC(O)=CC=C1O HIGSPBFIOSHWQG-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical class NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
- 125000000143 2-carboxyethyl group Chemical group [H]OC(=O)C([H])([H])C([H])([H])* 0.000 description 1
- PHNGKIFUTBFGAG-UHFFFAOYSA-N 2-ethoxybenzene-1,4-diol Chemical compound CCOC1=CC(O)=CC=C1O PHNGKIFUTBFGAG-UHFFFAOYSA-N 0.000 description 1
- VJOWMORERYNYON-UHFFFAOYSA-N 5-ethenyl-2-methylpyridine Chemical compound CC1=CC=C(C=C)C=N1 VJOWMORERYNYON-UHFFFAOYSA-N 0.000 description 1
- YPXQSGWOGQPLQO-UHFFFAOYSA-N 5-nitro-1,3-dihydrobenzimidazole-2-thione Chemical compound [O-][N+](=O)C1=CC=C2N=C(S)NC2=C1 YPXQSGWOGQPLQO-UHFFFAOYSA-N 0.000 description 1
- GIQKIFWTIQDQMM-UHFFFAOYSA-N 5h-1,3-oxazole-2-thione Chemical class S=C1OCC=N1 GIQKIFWTIQDQMM-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000001856 Ethyl cellulose Substances 0.000 description 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000003863 ammonium salts Chemical group 0.000 description 1
- 239000013011 aqueous formulation Substances 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- CBEQRNSPHCCXSH-UHFFFAOYSA-N iodine monobromide Chemical compound IBr CBEQRNSPHCCXSH-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000004986 phenylenediamines Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical class O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 125000004076 pyridyl group Chemical group 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 125000004929 pyrrolidonyl group Chemical group N1(C(CCC1)=O)* 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 150000003839 salts Chemical group 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- G03C1/49872—Aspects relating to non-photosensitive layers, e.g. intermediate protective layers
-
- 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
- Y10S430/162—Protective or antiabrasion layer
Definitions
- ABSTRACT Certain acrylamide polymers in a layer contiguous to a photothermographic layer comprising (a) photographic silver halide in association with (b) a silver salt of certain heterocyclic thione compounds, (c) an organic reducing agent, and (d) a polymeric, synthetic binder for the photothermographic layer of a photothermographic element provide, for example, increased stability prior to imagewise exposure without significantly adversely affecting sensitometric properties of the photothermographic element.
- the acrylamide polymers can comprise an overcoat layer or a layer between the photothermographic layer and a support for the photothermographic element or can be in both such layers.
- This invention relates to certain acrylamide polymers in certain photothermographic materials comprising photographic silver halide in association with a silver salt of certain heterocyclic thione compounds.
- a photothermographic element comprising a support having thereon (I) a layer comprising the described silver salts of a heterocyclic thione and a contiguous layer (II) comprising certain acrylamide copolymers.
- a method of developing a latent image in a photothermographic element comprising the described acrylamide polymers In another of its aspects, it relates to a method of developing a latent image in a photothermographic element comprising the described acrylamide polymers.
- Phototherrnographic materials comprising photographic silver halide in association with a silver salt of certain heterocyclic thione compounds and an organic reducing agent are known in the art. These photothermographic materials are described, for example, in US. Pat. No. 3,785,830 issued Jan. I5, I974.
- One problem which has been encountered with these photothermographic materials is the need for increased preprocessing stability of the photothermographic element. This problem is illustrated in the following comparative Example 2. This problem is illustrated by failure of the photothermographic material to provide a desired developed image after storage at elevated temperatures such as storage at 38 C. at 50% relative hu midity.
- a commonly employed overcoat layer for photothermographic ele ments comprises cellulose acetate.
- Such an overcoat layer is described, for example, in Belgian Pat. No. 729,043 and US. Pat. No. 2,732,304 issued Jan. 24, I956.
- Such an overcoat comprising cellulose acetate does not provide a useful solution to problems encountered with photothermographic materials comprising photographic silver halide in association with silver salts of certain heterocyclic thiones as described in US. Pat. No. 3,785,830 issued Jan. 15, I974.
- Polymer overcoat layers have been proposed for photothermographic elements to reduce susceptibility to abrasion marks, especially in machine processing wherein the photothermographic layer side of the element is contacted with a metal roller or the like.
- the processing of photothermographic elements by contacting the photothermographic element with a heating means can cause undesired physical properties such as surface cracking, reticulation and bubbling which can detract from the overall image quality desired in the photothermographic element.
- An ethyl cellulose overcoat layer and other overcoat layers have not satisfactorily overcome these problems in a photothermographic element as described.
- Polymers in order to be satisfactory with the photothermographic materials as described, must satisfy each of the following characteristics in addition to those described: (1) they provide sufficient resistance to abrasion and fingerprint marking to enable machine processing, (2) they provide sufficient resistance to reticulation and surface cracking upon processing with heat in a photothermographic element, (3) they provide sufficient resistance to surface bubbling in a photothermographic material upon processing with heat, (4) they do not significantly adversely afiect sen sitometric properties of the photothermographic materials, and (5) they are sufficiently transparent for desired viewing of an image.
- a photothermographic element comprising a support having thereon a layer comprising (a) photographic silver halide in association with (b) a silver salt of a heterocyclic thione as described herein, (c) an organic reducing agent for the silver salt of the heterocyclic thione, and (d) a polymeric, synthetic binder for layer (I) and a polymer layer (II), contiguous to layer (I), wherein the polymer layer (II) comprises at least 50% by weight of a polymer (A) comprising the repeating units represented by the formulas:
- R is hydrogen or alkyl containing l to 4 carbon atoms
- azonia nitrogen-containing ring such as an imidazoliurn salt group, such as a l-aza- 3-methyl-3-azoniacyclopenta-2,4-diene-l-yl methosulfate salt group, or a pyridinium salt group, such as l,2-dimethyl-l-azonia-S-phenyl methosulfate salt group, and
- the weight ratio of starting monomers for the units B and C is, respectively, about 60:40 to 100:0.
- the described polymers are acrylamide polymers.
- the acrylamide polymers are preferably copolymers which exhibit reduced or no adverse physical or chemical properties resulting from the thermal processing described herein. This is intended to mean that the described polymers are preferably copolymers which do not adversely discolor, decompose, crystallize, flow or the like as a result of the heating described herein.
- a process for developing an image in the described photo thermographic element by uniformly heating the element, such as from about 80 to about 200 C., for a sufficient time to provide the desired developed image.
- This process can be carried out by contacting the photothermographic element with a suitable heating means to provide the described temperature.
- Useful acrylamide polymers do not adversely flow, smear or distort at the processing temperatures for a described photothermographic material.
- the acrylamide polymers also do not cause adverse opacification of the photothermographic material.
- Useful acrylamide polymers have an average molecular weight of at least about 50,000, and preferably from about 100,000 to about 2,000,000. The molecular weight can be determined by methods known in the polymer art.
- Useful acrylamide polymers have inherent viscosities, measured at a concentration of 0.25 g. per deciliter in 1 normal sodium chloride solution at 25 C., ranging from 0.2 to 2.0, and preferably from 0.6 to 17.
- Useful acrylamide polymers are typically transparent and colorless. It is necessary, if the polymer is not completely transparent, that it be at least transparent to the wavelength of radiation employed to provide a latent image in the photothermographic element of the invention when exposure is through a layer comprising the acrylamide polymer.
- acrylamide polymers especially acrylamide copolymers, useful in photothermographic elements according to the invention are described in, for example, U.S. Pat. No. 3,658,878 of Smith issued Apr. 25, 1972.
- U.S. Pat. No. 3,591,386 of Abbott et al. issued July 6, 1971 U.S. Pat. No. 3,488,708 of Smith issued Jan, 6, 1970, U.S. Pat. No. 3,459,790 of Smith issued Aug. 5, 1969, and U.S. Pat. No. 3,554,987 of of Smith issued Jan. 12, 1971.
- Useful acrylamide polymers can be prepared empolying procedures known in the polymer art, such as described in the above U.S. patents. Generally, any of the known poly merization procedures, particularly copolymerization procedures used in the polymer art, are useful for making the described acrylamide polymers.
- Typical reactants employed when preparing the polymers within the described structure (A) are acrylamide and acrylamide copolymerized with one of the following monomers:
- Examples of useful acrylamide polymers according to the invention include:
- the concentration of acrylamide polymer which is useful in a layer of a photothermographic element according to this invention can vary, depending upon such factors as the particular photothermographic ele ment, processing conditions, components in the photothermographic element, particular acrylamide polymer and the like.
- a useful concentration range or coating coverage is about 0.1 g. to about 1.08 g. of acrylamide polymer/m. of support of the photothermographic element.
- a useful concentration of acrylamide polymer, when the acrylamide polymer is used as an overcoat layer is about 0.3 g. to about 7.5 g., such as about 0.40 g. to about 2.15 g., of acrylamide polymer/m. of support of the photothermographic element.
- a useful concentration of acrylamide polymer is about 0.3 g. to about 5.0 g., such as about 2.15 g. of acrylamide polymer/m. of support of the photothermographic element.
- the described acrylamide polymer comprises at least 50% by weight of the layer contiguous the photothermographic layer (1) as described.
- Other polymers can be useful with the acrylamide copolymers. However, typically, the acrylamide polymer comprises about 100% of the contiguous layer.
- Other polymers which can be useful with the acrylamide polymers include, for example, poly(vinyl alcohol) and polymers having properties similar to poly(vinyl alcohol) such as other acrylamide and N-substituted acrylamide copolymers including. for instance, poly-(acrylamide-co-acrylic acid), and cellulosic materials such as sulfoethyl cellulose and sodium cellulose sulfate.
- Photothermographic elements according to this invention can comprise, if desired, multiple polymer-containing layers.
- the photothermographic element can comprise an overcoat layer containing an acrylamide polymer as described and an additional overcoat layer comprising another polymer such as poly(vinyl alcohol).
- One embodiment of the invention is in a photother mographic element comprising a support having thereon (l):
- R represents the atoms completing a 5- member heterocyclic nucleus and Z is alkylene containing l to 30 carbon atoms, typically 1 to carbon atoms,
- polymer layer (ll) contiguous to (I), at least one polymer layer (ll), the improvement being one wherein said polymer layer (ll) comprises at least 50% by weight of a polymer (A) comprising the repeating units represented by the formulas:
- R is hydrogen or alkyl containing l to 4 carbon atoms, R is as described, and the weight ratio of starting monomers for the units B and C are respectively about 60:40 to l00:0.
- concentration of photographic silver halide which is useful in a photothermographic element of the invention can be very low compared with photographic materials which contain photographic silver halide in the absence of the other components of the photothermographic element of the invention.
- concentration of photographic silver halide which is suitable in a photothermographic element of the inven tion can be about 0.0025 to about 0.3 mole of photographic silver halide per mole of silver as the silver salt of the described heterocyclic thione.
- the concentration of photographic silver halide is typically about 0. l0 times 10' to about 1.29 times 10' moles of photographic silver halide/m of support.
- Useful photographic silver halides include, for example, silver chloride, silver bromide, silver iodide, silver bromoiodide, silver chloro bromoiodide, silver iodide, or mixtures thereof.
- the photographic silver halide can be coarseor fine-grain, very fine-grain silver halide being especially useful.
- the photographic silver halide can be prepared by any of the known procedures employed in the photographic art.
- the silver halide can be prepared, for example, employing single-jet preparation techniques or double-jet preparation techniques such as techniques employed in preparing Lippmann emulsions and the like.
- Surfaceimage silver halide can be useful. If desired, mixtures of surfaceand internal-image silver halide can be used. Negative-type silver halide is typically employed.
- the silver halide can be regulargrain silver halide such as described in Klein and Moisar, Journal of Photographic Science, Vol. 12, No. 5, Sept-Oct, l964. pp. 242-251. Photographic silver iodide is especially useful as the photographic silver halide.
- the photographic silver halide according to this invention can be unwashed or washed, and can be chemically sensitized employing techniques empolyed in the photographic art.
- the latent image formed in the photographic silver halide upon imagewise exposure of the photothermographic material increases the reaction rate between the components of the photothermographic material upon heating of the photothermo graphic material. It is believed this enables a lower processing temperature to be employed for developing an image which otherwise would not be possible.
- photographic silver halide in association with is intended to mean the photographic silver halide is in a location with respect to the other described components of the photothermographic material which enables this desired lower processing temperature and provides a more useful developed image.
- a useful silver salt of a heterocyclic thione is a silver salt of a heterocyclic thione represented by the formula (XX) as described. Selection of an optimum heterocyclic thione silver salt will depend upon such factors as the particular photothermographic material, particular toning agent, processing temperature, desired image and the like.
- Examples of useful 5- member heterocyclic nuclei containing the described carboxyalkyl group are thiazoline-Z-thione, benzothiazoline-Z-thione, imida2oline-2-thione, oxazoline-Z- thione, or similar heterocyclic thione nuclei.
- the heter ocyclic thione nucleus can be substituted with groups which do not adversely affect the photothermographic properties of the photothermographic element of the invention, such as alkyl containing l to 3 carbon atoms, or phenyl.
- thiazoline-Z-thiones represented by the formula:
- Z is alkylene containing 1 to 4 carbon atoms; and R and R are each, independently, hydrogen, alkyl containing l to 4 carbon atoms, such as methyl, ethyl, propyl or butyl, or aryl containing 6 to 10 carbon atoms, such as phenyl or tolyl, or taken together are the atoms necessary to complete a benzo group represented by the broken line between R and R
- Other useful heterocyclic thiones within formula (XX) are imidazoline-Z-thiones represented by the formula:
- Z is alkylene containing 1 to 4 carbon atoms
- R and R are each, independently, hydrogen, alkyl containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl, or aryl containing 6 to 10 carbon atoms, such as phenyl or tolyl, or taken together are the atoms necessary to complete a benzo group represented by the broken line between R and R"; and R is alkyl, typically alkyl containing 1 to 3 carbon atoms, such as methyl, ethyl or propyl, aryl containing 6 to carbon atoms, such as phenyl, or carboxyalkyl such as carboxyalkyl containin l to 3 carbon atoms, for example, carboxymethyl and carboxyethyl.
- Other useful heterocyclic thiones within structure (XX) are oxazoline- 2-thiones represented by the formula:
- alkylene includes straight-chain alkylene and branched-chain alkylene, such as:
- Preparation of the thione compounds can be carried out employing procedures described, for example, in an article of R. W. Lamon and W. J. Humphlett, Journal of Heleroc'yclic Chemistry, Vol. 4, pp. 605609, 1967, or as described in Belgian Pat. No. 739,705.
- Preparation of 4-thiazoline-2-thiones bearing a carboxyalkyl group in the 3 position can, for instance, be effected by treating a dithiocarbamic acid derived from an amino acid and carbon disulfide with an a-halogenated ketone. In this process the use of methyl alcohol as a solvent can improve the solubility of the reactants.
- the preparation of the silver salt of 3-carboxymethyl- 4-methyl-4-thiazoline-2-thione is typical.
- This silver complex is prepared by mixing the described thiazoline-2-thione with silver trifluoroacetate in water and thoroughly dispersing the reactants. Concentrations of the reactants can be varied to provide the desired ratio of silver to heterocyclic compound. Typically, the ratio of the thione compound to silver ion is less than about 2: l
- the resulting silver salt can be purified and stored for later mixture with other components of the described photothermographic materials. Dispersing of the silver trifluoroacetate with the heterocyclic compound is typically carried out at about 38 to about 71 Various reducing agents can be employed in the photothermographic materials of the invention.
- polyhydroxybenzenes such as hydroquinones including, for instance, hydroquinone; alkyl-substituted hydroquinones such as tertiarybutylhydroquinone, methylhydroquinone, 2,5-dimethylhy droquinone and 2,6
- silver halide developing agents which can be employed as reducing agents include reductones such as anhydro dihydro piperidino hexose reductone; hydroxytetronic acids and hydroxytetronimides; 3-pyrazolidones such as l-phenyl- 3-pyrazolidone 4-methyl-4- hydroxymethyl l -phenyl-3-pyrazolidone, and those described in British Pat. No. 930,572 published July 3, 1963; hydroxylamines; ascorbic acids such as ascorbic acid, ascorbic acid ketals, and other ascorbic acid derivatives; phenylenediamines; aminophenols; and the like. Combinations of reducing agents can also be employed.
- a suitable reducing agent typically is one which in the photothermographic compositions of the invention provides a developed image within about sec. at a temperature of about l00 to 250 C.
- a photothermographic element according to the invention can comprise a support having thereon in the photothermographic layer (A) about 0.10 times l0 to about 1.29 times l0 moles of photographic silver halide in association with (B) about 2.69 times ID to about 21.5 times 10 moles of reducing agent and (C) about 2.69 times 10 to about 2l .5 times 10 moles of silver as the described complex per m of support.
- A about 0.10 times l0 to about 1.29 times l0 moles of photographic silver halide in association with
- B about 2.69 times ID to about 21.5 times 10 moles of reducing agent and
- C about 2.69 times 10 to about 2l .5 times 10 moles of silver as the described complex per m of support.
- An optimum concentration of each component will depend upon such factors as the particular components, the desired image, processing temperature and the like.
- one or more components of the photothermographic element can be present in one or more lay ers of the element.
- the reducing agent, silver salt of the described heterocyclic thione and/or photographic silver halide in the described layer (ll) comprising an acrylamide polymer. This can reduce, for example, migration of certain addenda throughout the layers of the photothermographic element.
- Suitable binders for photothermographic layer (1) can be hydrophilic or hydrophobic, transparent or translucent, and include synthetic polymeric materials useful in the described photothermographic materials. It is desirable in many cases to use an acrylamide polymer both as a component of polymer layer (11) and as a binder for layer (1). Useful acrylamide polymers for this purpose are within the described formulae.
- Typical supports include those film supports which can withstand processing temperatu res employed for developing an image in a photothermographic element of the invention.
- film supports include, for example, cellulose ester film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthaL ate) film, polycarbonate film, film supports as described in U.S. Pat. No. 3,634,089 of Hamb issued Jan. ll, 1972, and U.S. Pat. No. 3,725,070 of Hamb et al. issued Apr. 3, 1973, and related films or resinous materials.
- Other useful supports include glass, paper, metal and the like. Typically, a flexible support is employed.
- the photothermographic elements according to the invention can contain addenda commonly employed in photothermographic elements, such as antistatic and- /or conducting layers, plasticizers, lubricants, surfactants, matting agents, sensitizing dyes, brightening agents, light-absorbing materials, filter dyes, antihalation dyes, absorbing dyes and the like.
- addenda commonly employed in photothermographic elements such as antistatic and- /or conducting layers, plasticizers, lubricants, surfactants, matting agents, sensitizing dyes, brightening agents, light-absorbing materials, filter dyes, antihalation dyes, absorbing dyes and the like.
- a toning agent can be employed in the photothermographic element of the invention to provide a desired image.
- useful toning agents include, for example, certain heterocyclic compounds which can provide a more neutral tone image.
- useful toning agents include 3-mercapto-1,2,4-triazole and 2,4dimercaptopyrimidine, described in copending U.S. application Ser. No. 466,331, of White, filed May 2, 1974.
- the various components of the photothermographic materials of the invention can be added from water solutions, or suitable organic solvents can be useful to aid in addition.
- the components can be mixed using various procedures known in the photographic art.
- a hardener especially an aldehyde hardener like formaldehyde
- This can provide improved incubation stability.
- a range of concentration of the aldehyde hardener can be employed depending upon such factors as the particular acrylamide polymer, particular components of the photothermographic element, desired image, desired stability and the like.
- a concentration of about 0.l to about such as about 0.1 to about 5%, by weight of aldehyde hardener, particularly formaldehyde, is incorporated in the acrylamide polymer before coating on the photothermographic element.
- the aldehyde hardener in the acrylamide polymer when the acrylamide polymer is coated directly on the support before coating of the photothermographic layer.
- the aldehyde hardener can be employed in any one or more of the layers of the photothermographic element.
- improved incubation stability is observed when the photothermographic element containing the aldehyde hardener is stored for a period of time, such as about at least 2 days, before imagewise exposure and processing as described. It is believed that this storage time permits a crosslinking of the polymer in the photothermographic element. However, the exact mechanism which results in the improved incubation stability is not fully understood.
- An especially useful embodiment of the invention comprises a photothermographic element comprising a support having thereon, respectively, (A) a layer comprising about 1.08 g./m. of support of poly(acrylamide-co-l-vinylimidazole) (weight ratio :10) containing 1% by weight of formaldehyde, (B) a photothermographic layer containing photographic silver iodide in association with a silver salt of a heterocyclic thione as described, a hydroquinone reducing agent for the silver salt of the heterocyclic thione, and a synthetic polymeric binder comprising poly(acrylamide-co-Z- acetoacetoxyethyl mmethacrylate) (weight ratio 98:2) or poly(acrylamide-co-l-vinylimidazole) (weight ratio 90:10), and (C) an overcoat layer comprising about L08 g./m. of support of poly(acrylamide-co-lvinylimidazole (weight ratio 90:10).
- a range of concentration of the described acrylamide polymer can be useful in an overcoat on the described photothermographic element according to the invention. While such factors as the particular photothermographic materials, the particular acrylamide copolymer, processing temperature and the like will influence the optimum concentration range of acrylamide copolymer in the overcoat layer, typically a concentration of about 0.3 to about 7.5 g., such as about 0.4 to about 2.l5 g., of acrylamide copolymer in the overcoat layer per m. of support is useful.
- a useful reducing agent concentration range in the acrylamide copolymer when the acrylamide copolymer is used as an overcoat is typically about 0.25 to about 0.55 g. of reducing agent per m. of support.
- concentration of about 2.15 to about 4.30 g. of reducing agent is used per m? of support.
- Photothermographic materials according to the invention are typically sensitive to the ultraviolet and blue regions of the spectrum and exposure means which provide this radiation are preferred.
- a photothermographic element according to the invention is exposed imagewise with a visible light source such as a tungsten lamp.
- a visible image can be developed in a photothermographic element as described, after imagewise exposure, within a short time by overall heating of the photothermographic element.
- the photothermographic element can be overall heated for about 1 to about 90 sec. at a temperature of about 100 to about 200 C., preferably about l40 to about l70 C.
- the time of heating is less than about 20 sec., such as about l to about 4 sec., at a temperature of about l5O to about 170 C.
- Increasing or decreasing the length of time of heating can enable use of a lower or higher temperature within the described range.
- the heating means can be, for example, a simple hot plate, iron or roller; or hot-air convection heating means; or dielectric heating means.
- the described acrylamide polymers can be useful in various layers of photothermographic materials known in the art, such as materials described in U.S. Pat. No. 3,589,903 of Birkeland issued June 29, l97l, U.S. Pat. No. Reissue 26,719 of Sorenson et al. issued Nov. 18, 1969, U.S. Pat. No. 3,429.706 of Shepard et al. issued Feb. 25, I969, U.S. Pat. No. 3,645,739 of Ohkubo et al. issued Feb. 29, 1972, U.S. Pat. No. 3,515,559 of Druker et al. issued June 2, l970, and U.S. Pat. No.
- the described acrylamide polymers can be useful in thermographic materials also.
- Thermographic materials in which the acrylamide polymers can be useful are described, for example, in U.S. Pat. Nos. 2,910,377 and 3,094,417 ofworkman issued June l8, 1963. Selection of an optimum acrylamide polymer as described for use in one or more layers of the photothermographic materials or thermographic materials described in the above art will depend upon such factors as the compatability of the acrylamide polymer with the other components of the photothermographic or thermographic material, the desired image, processing temperature and the like.
- the acrylamide polymers described are used with hydrophilic materials such as photothermographic materials coated from aqueous formulations.
- EXAMPLE l poly(vinyl alcohol) as a binder 2.15 gJm. hydroquinone l.
- the resulting layer was designated layer (1).
- poly(vinyl alcohol) as a binder surfactant (Surfactant 106 which is a nonylphenoxypolyglycidol sold by Rohm and Haas Co., USA.
- Poly(acrylamide-co-2-acetoacetoxyethyl methacrylate) (weight ratio 98:2) (inherent viscosity l.40) measured in L0 N NaCl solution at a concentration of 0.25 g./dl. at a temperature of 25 C. was then coated on layer (2) at the concentration of 7.26 g. of the acrylamide copolymer per m? of support.
- the acrylamide copolymer layer was designated layer (3).
- the resulting photothermographic element was packaged in a so-called double paper envelope, that is, a black paper envelope inside a yellow paper envelope.
- the double paper envelope was stored in a controlled temperature-relative humidity chamber at 38 C. and 50% relative humidity.
- samples of the photothermographic element were removed from the double paper envelope and imagewiseexposed for 10 sec. to xenon light in a sensitometer.
- the samples of exposed photothermographic element were uniformly heated after exposure by passing them over a metal roller for 4 sec. at C. A developed image was observed in each of the samples.
- the Dmax, Dmin and photographic speed for each of the images in the samples were the same as those of an image developed in an equivalent photothermographic element with the exception that the imagewise exposure and image development were carried out without storing the photothermographic element for a period of time.
- EXAMPLE 2 This is a comparative example.
- a control photothermographic element (B) was prepared as in Example 1 without the described acrylamide copolymer overcoat (layer 3), and then imagewiseexposed and developed in the same manner as in Example 1. This control photothermographic element provided no acceptable developed image after storage for 14 days under the described incubation conditions in a double paper envelope.
- the resulting layer was designated as layer (2).
- the resulting photothermographic element was imagewise-exposed to tungsten light as described in Examples 4-10 and then overall heated by contacting the element with a metal block at 160 CV for 4 see. A de veloped image is observed.
- the image had the sensitometric properties given in following Table 2.
- EXAMPLE 12 The procedure in Example 1 l was repeated with the exception that an overcoat containing 1.08 g./m. of poly(acrylamide-co-2-acetoacetoxyethyl methacrylate) (weight ratio 98:2) was applied to layer (2) prior to imagewise exposure.
- the resulting sensitometric properties are reported in following Table 2.
- the overcoated photothermographic element was T bl 2 imagewise-exposed to tungsten light in a sensitometer l b L E R l for sec.
- the exposed photothermographic element gg was overall heated by contacting it with a metal block
- Similar samples of the photothermographic element were incubated in a double paper H f h 1'3 rcfuence poi, envelope at 38 C and 50% relative humidity for up to i )2 3 WEE S 15 days.
- the resulting samples were then lm agewlse- 12 fresh 08 reference pom exposed and overall heated as above.
- the Dmin. Dmax 25 1 week 108 .06 and relative photographic speed values for each photo- 2 098 3weeks 1.16 .14 thermographic element are given in following Table 1.
- a resin-coated paper support was coated with 1.08 g./m. of polymer Vll containing 1% by weight of formaldehyde based on the weight of the polymer. This was designated as layer (1 On layer 1) was coated a photothermographic composition containing:
- 3-mercapto-l .2.4 triazole 0.022 g./rn. isopropylhydroquinone 1.62 g./m.
- Surfactant 100 0.008 g./m. total silver as silver iodide and 0.81 g./m.
- a resin-coated paper support was coated with a layer comprising a mixture of the following:
- the sensitometric results of the photothermographic element are given in following Table 3, including the results from incubation.
- silver iodide gelatino emulsion 0.075 g. Ag/m. silver complex of 3-carboxy 0.68 g. Ag/m? methy1-4-methyl-4-thiazo1ine Z-thione tertiary-hutylhydroquinorie 1.88 g./m. 3-mcrcapto1.2,4triazo1e 0.0094 gjm. 2.4-dimercuptopyrimidine 0.0024 g./m. Surfactant 106 0.008 g./m.
- R represents atoms completing a 5 member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms,
- an organic reducing agent for said silver salt of a heterocyclic thione and d. a polymeric, synthetic binder and contiguous to (l), at least one polymer layer (H), the improvement wherein said polymer layer (II) comprises at least 50% by weight of a polymer (A) compris ing the repeating units represented by the formulas:
- R is hydrogen or alkyl containing 1 to 4 carbon atoms
- R is an imidazolyl, N-substituted carbamoyl, 2-
- pyrrolidonyl acetoacetoxyethoxycarbonyl, acetoacetonylmethylphenyl, ethoxycarbonylaceto, pyridyl, hydroxy, hydroxyalkyl containing 1 to 4 carbon atoms, carboxy, carboxyethoxycarbonyl, a heterocyclic ammonium salt group having a S- or 6-membered azonia nitrogen-containing ring, or a pyridinium salt group, and
- the weight ratio of starting monomers for said units B and C is, respectively. about 60:40 to lz0.
- a photothermographic element as in claim 1 also comprising in said layer (II) at least one polymer other than said copolymer (A),
- a photothermographic element as in claim 1 comprising a support having thereon, in sequence:
- a photothermographic layer comprising:
- a photothermographic element as in claim 1 wherein said polymeric synthetic binder comprises a polymer selected from the group consisting of poly(acrylamide), poly(acrylamide-co-Z-acetoacetoxyethyl methacrylate), poly(acrylamide-co-a-chloroacrylic acid), poly(acrylamide-co-l-vinylimidazole), poly- (vinyl alcohol), and combinations thereof.
- a photothermographic element as in claim 1 also comprising a hardener in said layer ([1).
- a photothermographic element as in claim 1 also comprising a aldehyde hardener in said layer (ll).
- a photothermographic element as in claim 1 also comprising a 3-mercapto-l,2,4-triazole toner.
- a photothermographic element as in claim 1 also comprising a 2,4-dimercaptopyrimidine toner.
- a process of developing a latent image in a photothermographic element as defined in claim 1 comprising heating said element to a temperature of about to about 200 C.
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Abstract
Certain acrylamide polymers in a layer contiguous to a photothermographic layer comprising (a) photographic silver halide in association with (b) a silver salt of certain heterocyclic thione compounds, (c) an organic reducing agent, and (d) a polymeric, synthetic binder for the photothermographic layer of a photothermographic element provide, for example, increased stability prior to imagewise exposure without significantly adversely affecting sensitometric properties of the photothermographic element. The acrylamide polymers can comprise an overcoat layer or a layer between the photothermographic layer and a support for the photothermographic element or can be in both such layers.
Description
United States Patent n91 Sutton et al.
[ PHOTOTHERMOGRAPHIC ELEMENT AND PROCESS [75] Inventors: Richard C. Sutton; Heinz E.
Stapelfeldt, both of Rochester, NY.
[73] Assignee: Eastman Kodak Company,
Rochester, NY.
[22] Filed: July 16, 1974 [21] Appl. No.: 489,029
[52] U.S. Cl. 96/66 T; 96/48 HD; 96/76 R;
96/1 14.1 [51] Int. Cl. G030 5/30; G03c l/04; G03c H72 [58] Field of Search 96/48 HD, 66 T, 76 R, 95,
[451 July 8,1975
[/1974 Sullivan et al. 96/1 14.! 12/1974 Hamb et al. 96]! 14.1
[57] ABSTRACT Certain acrylamide polymers in a layer contiguous to a photothermographic layer comprising (a) photographic silver halide in association with (b) a silver salt of certain heterocyclic thione compounds, (c) an organic reducing agent, and (d) a polymeric, synthetic binder for the photothermographic layer of a photothermographic element provide, for example, increased stability prior to imagewise exposure without significantly adversely affecting sensitometric properties of the photothermographic element. The acrylamide polymers can comprise an overcoat layer or a layer between the photothermographic layer and a support for the photothermographic element or can be in both such layers.
17 Claims, No Drawings PHOTOTHERMOGRAPHIC ELEMENT AND PROCESS BACKGROUND OF THE INVENTION Field of the Invention This invention relates to certain acrylamide polymers in certain photothermographic materials comprising photographic silver halide in association with a silver salt of certain heterocyclic thione compounds. In one of its aspects, it relates to a photothermographic element comprising a support having thereon (I) a layer comprising the described silver salts of a heterocyclic thione and a contiguous layer (II) comprising certain acrylamide copolymers. In another of its aspects, it relates to a method of developing a latent image in a photothermographic element comprising the described acrylamide polymers.
Description of the State of the Art Phototherrnographic materials comprising photographic silver halide in association with a silver salt of certain heterocyclic thione compounds and an organic reducing agent are known in the art. These photothermographic materials are described, for example, in US. Pat. No. 3,785,830 issued Jan. I5, I974. One problem which has been encountered with these photothermographic materials is the need for increased preprocessing stability of the photothermographic element. This problem is illustrated in the following comparative Example 2. This problem is illustrated by failure of the photothermographic material to provide a desired developed image after storage at elevated temperatures such as storage at 38 C. at 50% relative hu midity.
It has been proposed in some cases to provide the photothermographic material with a protective layer, such as a protective overcoat layer. A commonly employed overcoat layer for photothermographic ele ments comprises cellulose acetate. Such an overcoat layer is described, for example, in Belgian Pat. No. 729,043 and US. Pat. No. 2,732,304 issued Jan. 24, I956. Such an overcoat comprising cellulose acetate does not provide a useful solution to problems encountered with photothermographic materials comprising photographic silver halide in association with silver salts of certain heterocyclic thiones as described in US. Pat. No. 3,785,830 issued Jan. 15, I974.
Polymer overcoat layers have been proposed for photothermographic elements to reduce susceptibility to abrasion marks, especially in machine processing wherein the photothermographic layer side of the element is contacted with a metal roller or the like. In ad dition, the processing of photothermographic elements by contacting the photothermographic element with a heating means can cause undesired physical properties such as surface cracking, reticulation and bubbling which can detract from the overall image quality desired in the photothermographic element. An ethyl cellulose overcoat layer and other overcoat layers have not satisfactorily overcome these problems in a photothermographic element as described.
In the application of polymeric layers, i.e., either overcoat layers or layers between the support and the photothermographic layer, it is necessary to employ polymers which are resistant to decomposition or other undesired effects at the processing temperatures employed, such as temperatures above about 100 C,
Polymers, in order to be satisfactory with the photothermographic materials as described, must satisfy each of the following characteristics in addition to those described: (1) they provide sufficient resistance to abrasion and fingerprint marking to enable machine processing, (2) they provide sufficient resistance to reticulation and surface cracking upon processing with heat in a photothermographic element, (3) they provide sufficient resistance to surface bubbling in a photothermographic material upon processing with heat, (4) they do not significantly adversely afiect sen sitometric properties of the photothermographic materials, and (5) they are sufficiently transparent for desired viewing of an image. Although there are many polymers that are resistant to high-temperature decomposition, these polymers, as a class, are not satisfactory for use with the described photothermographic materials because properties are required other than the property of resistance to decomposition at high temperatures. This is illustrated by appended comparative examples.
There has, accordingly, been a continuing need to provide improved photothermographic materials comprising photographic silver halide in association with silver salts of certain heterocyclic thione compounds, as described, to provide the desired described properties such as improved stability prior to imagewise exposure, resistance to abrasion marks, fingerprint marks and undesired surface properties, without significantly adversely affecting sensitometric properties of the photothermographic material.
Summary of the Invention It has been found, according to this invention, that the described properties are provided in a photothermographic element comprising a support having thereon a layer comprising (a) photographic silver halide in association with (b) a silver salt of a heterocyclic thione as described herein, (c) an organic reducing agent for the silver salt of the heterocyclic thione, and (d) a polymeric, synthetic binder for layer (I) and a polymer layer (II), contiguous to layer (I), wherein the polymer layer (II) comprises at least 50% by weight of a polymer (A) comprising the repeating units represented by the formulas:
l +CH C|H+ and +cn, c+
CI'=O R2 NH2 wherein:
R is hydrogen or alkyl containing l to 4 carbon atoms;
or 6-membered azonia nitrogen-containing ring such as an imidazoliurn salt group, such as a l-aza- 3-methyl-3-azoniacyclopenta-2,4-diene-l-yl methosulfate salt group, or a pyridinium salt group, such as l,2-dimethyl-l-azonia-S-phenyl methosulfate salt group, and
the weight ratio of starting monomers for the units B and C is, respectively, about 60:40 to 100:0.
The described polymers are acrylamide polymers. The acrylamide polymers are preferably copolymers which exhibit reduced or no adverse physical or chemical properties resulting from the thermal processing described herein. This is intended to mean that the described polymers are preferably copolymers which do not adversely discolor, decompose, crystallize, flow or the like as a result of the heating described herein.
Also, according to the invention, a process is provided for developing an image in the described photo thermographic element by uniformly heating the element, such as from about 80 to about 200 C., for a sufficient time to provide the desired developed image. This process can be carried out by contacting the photothermographic element with a suitable heating means to provide the described temperature.
Detailed Description of the Invention Various acrylamide polymers within the designated formula are useful in photothermographic materials according to the invention.
Useful acrylamide polymers do not adversely flow, smear or distort at the processing temperatures for a described photothermographic material. The acrylamide polymers also do not cause adverse opacification of the photothermographic material. Useful acrylamide polymers have an average molecular weight of at least about 50,000, and preferably from about 100,000 to about 2,000,000. The molecular weight can be determined by methods known in the polymer art. Useful acrylamide polymers have inherent viscosities, measured at a concentration of 0.25 g. per deciliter in 1 normal sodium chloride solution at 25 C., ranging from 0.2 to 2.0, and preferably from 0.6 to 17.
Useful acrylamide polymers are typically transparent and colorless. It is necessary, if the polymer is not completely transparent, that it be at least transparent to the wavelength of radiation employed to provide a latent image in the photothermographic element of the invention when exposure is through a layer comprising the acrylamide polymer.
Some acrylamide polymers, especially acrylamide copolymers, useful in photothermographic elements according to the invention are described in, for example, U.S. Pat. No. 3,658,878 of Smith issued Apr. 25, 1972. U.S. Pat. No. 3,591,386 of Abbott et al. issued July 6, 1971, U.S. Pat. No. 3,488,708 of Smith issued Jan, 6, 1970, U.S. Pat. No. 3,459,790 of Smith issued Aug. 5, 1969, and U.S. Pat. No. 3,554,987 of of Smith issued Jan. 12, 1971.
Useful acrylamide polymers, especially acrylamide copolymers, can be prepared empolying procedures known in the polymer art, such as described in the above U.S. patents. Generally, any of the known poly merization procedures, particularly copolymerization procedures used in the polymer art, are useful for making the described acrylamide polymers.
Typical reactants employed when preparing the polymers within the described structure (A) are acrylamide and acrylamide copolymerized with one of the following monomers:
1 -vinylimidazole 2-methy1- l -vinylimidazole B-methyl- 1 vinylimidazo1ium methosulfate N-methylolacrylamide 2-acetoacetoxyethyl methacrylate acrylic acid l-vinyl-2-pyrrolidone 2-methyl-5-vinylpyridine 1,Z-dimethyl-S-vinylpyridinium methosulfate The described acrylamide polymers do not, in the absence of interfering components, significantly adversely affect the sensitometric properties of the described photothermographic materials, such as minimum density, maximum density, photographic speed and the like, whereas cellulose acetate, a commonly employed overcoat, causes significant undesired changes in sensitometric behavior. The described acrylamide polymers also provide desired increased sta bility prior to imagewise exposure of a described photothermographic element. This is illustrated in the following examples.
Examples of useful acrylamide polymers according to the invention include:
Polymer No, Polymer l poly(acrylamide-co'1-vinylimidazole)( weight ratio :10) 11 poly( acrylamideco-Z-methyll -vinylimidazole weight ratio 90:10) poly( acrylamide-co-S-methyll -vinylimidazolium methosulfate weight ratio 90: 10) gglygascrylarnideco-N-methylo1acrylamide weight ratio Vlll IX poly( acrylamide-col ,Z-dimethyl-S-vinyl-pyridinium methosulfate)(weight ratio 88: 1 2) X1 poly(acrylamide-co-2-vinylpyridine)(weight ratio 89:1 l)
The concentration of acrylamide polymer which is useful in a layer of a photothermographic element according to this invention can vary, depending upon such factors as the particular photothermographic ele ment, processing conditions, components in the photothermographic element, particular acrylamide polymer and the like. A useful concentration range or coating coverage, is about 0.1 g. to about 1.08 g. of acrylamide polymer/m. of support of the photothermographic element. A useful concentration of acrylamide polymer, when the acrylamide polymer is used as an overcoat layer, is about 0.3 g. to about 7.5 g., such as about 0.40 g. to about 2.15 g., of acrylamide polymer/m. of support of the photothermographic element. When the acrylamide polymer is used as a so-called undercoat, that is, a coating on the support between the support and the photothermographic layer, a useful concentration of acrylamide polymer is about 0.3 g. to about 5.0 g., such as about 2.15 g. of acrylamide polymer/m. of support of the photothermographic element.
The described acrylamide polymer comprises at least 50% by weight of the layer contiguous the photothermographic layer (1) as described. Other polymers can be useful with the acrylamide copolymers. However, typically, the acrylamide polymer comprises about 100% of the contiguous layer. Other polymers which can be useful with the acrylamide polymers include, for example, poly(vinyl alcohol) and polymers having properties similar to poly(vinyl alcohol) such as other acrylamide and N-substituted acrylamide copolymers including. for instance, poly-(acrylamide-co-acrylic acid), and cellulosic materials such as sulfoethyl cellulose and sodium cellulose sulfate. Photothermographic elements according to this invention can comprise, if desired, multiple polymer-containing layers. For example, the photothermographic element can comprise an overcoat layer containing an acrylamide polymer as described and an additional overcoat layer comprising another polymer such as poly(vinyl alcohol).
One embodiment of the invention is in a photother mographic element comprising a support having thereon (l):
a. photographic silver halide in association with b. a silver salt of a heterocyclic thione, said heterocy clic thione being represented by the formula:
Z-COOH wherein R represents the atoms completing a 5- member heterocyclic nucleus and Z is alkylene containing l to 30 carbon atoms, typically 1 to carbon atoms,
0. an organic reducing agent for said silver salt ofa heterocyclic thione, and
d. a polymeric, synthetic binder and,
contiguous to (I), at least one polymer layer (ll), the improvement being one wherein said polymer layer (ll) comprises at least 50% by weight of a polymer (A) comprising the repeating units represented by the formulas:
wherein R is hydrogen or alkyl containing l to 4 carbon atoms, R is as described, and the weight ratio of starting monomers for the units B and C are respectively about 60:40 to l00:0.
Various photographic silver halides can be employed in the described photothermographic element. The concentration of photographic silver halide which is useful in a photothermographic element of the invention can be very low compared with photographic materials which contain photographic silver halide in the absence of the other components of the photothermographic element of the invention. For example, the concentration of photographic silver halide which is suitable in a photothermographic element of the inven tion, can be about 0.0025 to about 0.3 mole of photographic silver halide per mole of silver as the silver salt of the described heterocyclic thione. In a photothermo' graphic element of the invention, the concentration of photographic silver halide is typically about 0. l0 times 10' to about 1.29 times 10' moles of photographic silver halide/m of support. Useful photographic silver halides include, for example, silver chloride, silver bromide, silver iodide, silver bromoiodide, silver chloro bromoiodide, silver iodide, or mixtures thereof. The photographic silver halide can be coarseor fine-grain, very fine-grain silver halide being especially useful. The photographic silver halide can be prepared by any of the known procedures employed in the photographic art. The silver halide can be prepared, for example, employing single-jet preparation techniques or double-jet preparation techniques such as techniques employed in preparing Lippmann emulsions and the like. Surfaceimage silver halide can be useful. If desired, mixtures of surfaceand internal-image silver halide can be used. Negative-type silver halide is typically employed. The silver halide can be regulargrain silver halide such as described in Klein and Moisar, Journal of Photographic Science, Vol. 12, No. 5, Sept-Oct, l964. pp. 242-251. Photographic silver iodide is especially useful as the photographic silver halide.
The photographic silver halide according to this invention can be unwashed or washed, and can be chemically sensitized employing techniques empolyed in the photographic art.
it is believed that the latent image formed in the photographic silver halide upon imagewise exposure of the photothermographic material increases the reaction rate between the components of the photothermographic material upon heating of the photothermo graphic material. It is believed this enables a lower processing temperature to be employed for developing an image which otherwise would not be possible.
The term photographic silver halide in association with is intended to mean the photographic silver halide is in a location with respect to the other described components of the photothermographic material which enables this desired lower processing temperature and provides a more useful developed image.
Various silver salts of a heterocyclic thione are useful in the described photothermographic materials of the invention. A useful silver salt of a heterocyclic thione is a silver salt of a heterocyclic thione represented by the formula (XX) as described. Selection of an optimum heterocyclic thione silver salt will depend upon such factors as the particular photothermographic material, particular toning agent, processing temperature, desired image and the like. Examples of useful 5- member heterocyclic nuclei containing the described carboxyalkyl group are thiazoline-Z-thione, benzothiazoline-Z-thione, imida2oline-2-thione, oxazoline-Z- thione, or similar heterocyclic thione nuclei. The heter ocyclic thione nucleus can be substituted with groups which do not adversely affect the photothermographic properties of the photothermographic element of the invention, such as alkyl containing l to 3 carbon atoms, or phenyl.
especially useful thione compounds within formula (XX) are thiazoline-Z-thiones represented by the formula:
wherein Z is alkylene containing 1 to 4 carbon atoms; and R and R are each, independently, hydrogen, alkyl containing l to 4 carbon atoms, such as methyl, ethyl, propyl or butyl, or aryl containing 6 to 10 carbon atoms, such as phenyl or tolyl, or taken together are the atoms necessary to complete a benzo group represented by the broken line between R and R Other useful heterocyclic thiones within formula (XX) are imidazoline-Z-thiones represented by the formula:
wherein Z is alkylene containing 1 to 4 carbon atoms; R and R are each, independently, hydrogen, alkyl containing 1 to 4 carbon atoms, such as methyl, ethyl, propyl or butyl, or aryl containing 6 to 10 carbon atoms, such as phenyl or tolyl, or taken together are the atoms necessary to complete a benzo group represented by the broken line between R and R"; and R is alkyl, typically alkyl containing 1 to 3 carbon atoms, such as methyl, ethyl or propyl, aryl containing 6 to carbon atoms, such as phenyl, or carboxyalkyl such as carboxyalkyl containin l to 3 carbon atoms, for example, carboxymethyl and carboxyethyl. Other useful heterocyclic thiones within structure (XX) are oxazoline- 2-thiones represented by the formula:
xxm I\RJ N/ t Z'COOH wherein Z, R and R are as defined.
In the definition of Z, as well as Z, Z and Z", as employed herein, alkylene includes straight-chain alkylene and branched-chain alkylene, such as:
CH CH CH Examples of useful thione compounds within the described formulae include:
3-( 2-carboxyethyl 4-methyl-4-thiazoline-2-thione 3-( Z-carboxyethyl )benzothiazoline-2-thione 3-( 2-carboxyethyl )-5-phenyll ,3,4-oxadiazoline-2- thione 3-( 2-carboxyethyl )-5-phenyll ,3,4-thiadiazoline-2- thione 3-carboxymethyl-4-methyl-4 thiazoline-2-thione 3-( 2-carboxyethyl) l -phenyl-1 ,3,4-triazoline-2- thione l,3-bis( 2-carboxyethyl)imidazoline-Z-thione l,3-bis( Z-carboxyethyl)benzimidazoline-Z-thione 3-( 2-carboxyethyl l -methylimidazoline-2-thione 3-( 2-carboxyethyl )benzoxazoline-Z-thione 3-( l-carboxyethyl )-4-methyl-4-thia2oline-2-thione The silver salt of the described thione can be prepared directly in the photothermographic composition by combining a source of silver, such as silver trifluoroacetate, with the thione compound in the composi tion. or the silver salts can be preformed and isolated before addition to the photothermographic composition. The described thione compounds can be prepared employing processes known in the art. It is desirable to avoid preparation of the silver salt in the presence of compounds which could cause reduction.
Preparation of the thione compounds can be carried out employing procedures described, for example, in an article of R. W. Lamon and W. J. Humphlett, Journal of Heleroc'yclic Chemistry, Vol. 4, pp. 605609, 1967, or as described in Belgian Pat. No. 739,705. Preparation of 4-thiazoline-2-thiones bearing a carboxyalkyl group in the 3 position can, for instance, be effected by treating a dithiocarbamic acid derived from an amino acid and carbon disulfide with an a-halogenated ketone. In this process the use of methyl alcohol as a solvent can improve the solubility of the reactants.
The preparation of the silver salt of 3-carboxymethyl- 4-methyl-4-thiazoline-2-thione is typical. This silver complex is prepared by mixing the described thiazoline-2-thione with silver trifluoroacetate in water and thoroughly dispersing the reactants. Concentrations of the reactants can be varied to provide the desired ratio of silver to heterocyclic compound. Typically, the ratio of the thione compound to silver ion is less than about 2: l The resulting silver salt can be purified and stored for later mixture with other components of the described photothermographic materials. Dispersing of the silver trifluoroacetate with the heterocyclic compound is typically carried out at about 38 to about 71 Various reducing agents can be employed in the photothermographic materials of the invention. These are typically silver halide developing agents and include, for example, polyhydroxybenzenes such as hydroquinones including, for instance, hydroquinone; alkyl-substituted hydroquinones such as tertiarybutylhydroquinone, methylhydroquinone, 2,5-dimethylhy droquinone and 2,6-dimethylhydroquinone; catechols and pyrogallol; halo-substituted hydroquinones such as chlorohydroquinone or dichlorohydroquinone; alkoxysubstituted hydroquinones such as methoxyhydroquinone or ethoxyhydroquinone; and the like. Other silver halide developing agents which can be employed as reducing agents include reductones such as anhydro dihydro piperidino hexose reductone; hydroxytetronic acids and hydroxytetronimides; 3-pyrazolidones such as l-phenyl- 3-pyrazolidone 4-methyl-4- hydroxymethyl l -phenyl-3-pyrazolidone, and those described in British Pat. No. 930,572 published July 3, 1963; hydroxylamines; ascorbic acids such as ascorbic acid, ascorbic acid ketals, and other ascorbic acid derivatives; phenylenediamines; aminophenols; and the like. Combinations of reducing agents can also be employed. A suitable reducing agent typically is one which in the photothermographic compositions of the invention provides a developed image within about sec. at a temperature of about l00 to 250 C.
A range of concentrations of each component is useful in the described photothermographic material. Typically, a photothermographic element according to the invention can comprise a support having thereon in the photothermographic layer (A) about 0.10 times l0 to about 1.29 times l0 moles of photographic silver halide in association with (B) about 2.69 times ID to about 21.5 times 10 moles of reducing agent and (C) about 2.69 times 10 to about 2l .5 times 10 moles of silver as the described complex per m of support. An optimum concentration of each component will depend upon such factors as the particular components, the desired image, processing temperature and the like.
If desired, one or more components of the photothermographic element can be present in one or more lay ers of the element. For example. in some cases it can be desirable to include certain percentages of the reducing agent, silver salt of the described heterocyclic thione and/or photographic silver halide in the described layer (ll) comprising an acrylamide polymer. This can reduce, for example, migration of certain addenda throughout the layers of the photothermographic element.
Suitable binders for photothermographic layer (1) can be hydrophilic or hydrophobic, transparent or translucent, and include synthetic polymeric materials useful in the described photothermographic materials. It is desirable in many cases to use an acrylamide polymer both as a component of polymer layer (11) and as a binder for layer (1). Useful acrylamide polymers for this purpose are within the described formulae.
Various supports are useful for the described photothermographic element. Typical supports include those film supports which can withstand processing temperatu res employed for developing an image in a photothermographic element of the invention. Such film supports include, for example, cellulose ester film, poly(vinyl acetal) film, polystyrene film, poly(ethylene terephthaL ate) film, polycarbonate film, film supports as described in U.S. Pat. No. 3,634,089 of Hamb issued Jan. ll, 1972, and U.S. Pat. No. 3,725,070 of Hamb et al. issued Apr. 3, 1973, and related films or resinous materials. Other useful supports include glass, paper, metal and the like. Typically, a flexible support is employed.
The photothermographic elements according to the invention can contain addenda commonly employed in photothermographic elements, such as antistatic and- /or conducting layers, plasticizers, lubricants, surfactants, matting agents, sensitizing dyes, brightening agents, light-absorbing materials, filter dyes, antihalation dyes, absorbing dyes and the like.
If desired, a toning agent can be employed in the photothermographic element of the invention to provide a desired image. Useful toning agents include, for example, certain heterocyclic compounds which can provide a more neutral tone image. Examples of useful toning agents include 3-mercapto-1,2,4-triazole and 2,4dimercaptopyrimidine, described in copending U.S. application Ser. No. 466,331, of White, filed May 2, 1974.
The various components of the photothermographic materials of the invention can be added from water solutions, or suitable organic solvents can be useful to aid in addition. The components can be mixed using various procedures known in the photographic art.
It is desirable in some cases to incorporate a hardener, especially an aldehyde hardener like formaldehyde, into the described acrylamide polymer materials. This can provide improved incubation stability. A range of concentration of the aldehyde hardener can be employed depending upon such factors as the particular acrylamide polymer, particular components of the photothermographic element, desired image, desired stability and the like. Typically, a concentration of about 0.l to about such as about 0.1 to about 5%, by weight of aldehyde hardener, particularly formaldehyde, is incorporated in the acrylamide polymer before coating on the photothermographic element. In some cases, it is desirable to incorporate the aldehyde hardener in the acrylamide polymer when the acrylamide polymer is coated directly on the support before coating of the photothermographic layer. The aldehyde hardener, however, can be employed in any one or more of the layers of the photothermographic element.
In some cases, improved incubation stability is observed when the photothermographic element containing the aldehyde hardener is stored for a period of time, such as about at least 2 days, before imagewise exposure and processing as described. It is believed that this storage time permits a crosslinking of the polymer in the photothermographic element. However, the exact mechanism which results in the improved incubation stability is not fully understood.
An especially useful embodiment of the invention comprises a photothermographic element comprising a support having thereon, respectively, (A) a layer comprising about 1.08 g./m. of support of poly(acrylamide-co-l-vinylimidazole) (weight ratio :10) containing 1% by weight of formaldehyde, (B) a photothermographic layer containing photographic silver iodide in association with a silver salt of a heterocyclic thione as described, a hydroquinone reducing agent for the silver salt of the heterocyclic thione, and a synthetic polymeric binder comprising poly(acrylamide-co-Z- acetoacetoxyethyl mmethacrylate) (weight ratio 98:2) or poly(acrylamide-co-l-vinylimidazole) (weight ratio 90:10), and (C) an overcoat layer comprising about L08 g./m. of support of poly(acrylamide-co-lvinylimidazole (weight ratio 90:10).
A range of concentration of the described acrylamide polymer can be useful in an overcoat on the described photothermographic element according to the invention. While such factors as the particular photothermographic materials, the particular acrylamide copolymer, processing temperature and the like will influence the optimum concentration range of acrylamide copolymer in the overcoat layer, typically a concentration of about 0.3 to about 7.5 g., such as about 0.4 to about 2.l5 g., of acrylamide copolymer in the overcoat layer per m. of support is useful.
In some cases, it is desirable to incorporate a portion of the described reducing agent in the acrylamide copolymer layers as described. While the concentration which is most useful of the described reducing agent will depend upon the described factors, such as particular reducing agent, desired image, processing temperature, particular acrylamide polymer and the like, a useful reducing agent concentration range in the acrylamide copolymer when the acrylamide copolymer is used as an overcoat is typically about 0.25 to about 0.55 g. of reducing agent per m. of support. When the reducing agent is employed in an acrylamide polymer layer between the support and the photothermographic layer, typically a concentration of about 2.15 to about 4.30 g. of reducing agent is used per m? of support.
Various imagewise-exposure means are useful with the photothermographic materials according to the invention. Photothermographic materials according to the invention are typically sensitive to the ultraviolet and blue regions of the spectrum and exposure means which provide this radiation are preferred. Typically, a photothermographic element according to the invention is exposed imagewise with a visible light source such as a tungsten lamp.
A visible image can be developed in a photothermographic element as described, after imagewise exposure, within a short time by overall heating of the photothermographic element. For example, the photothermographic element can be overall heated for about 1 to about 90 sec. at a temperature of about 100 to about 200 C., preferably about l40 to about l70 C. Usually, the time of heating is less than about 20 sec., such as about l to about 4 sec., at a temperature of about l5O to about 170 C. Increasing or decreasing the length of time of heating can enable use of a lower or higher temperature within the described range.
Any suitable means can be useful for providing the desired processing temperature range. The heating means can be, for example, a simple hot plate, iron or roller; or hot-air convection heating means; or dielectric heating means.
The described acrylamide polymers can be useful in various layers of photothermographic materials known in the art, such as materials described in U.S. Pat. No. 3,589,903 of Birkeland issued June 29, l97l, U.S. Pat. No. Reissue 26,719 of Sorenson et al. issued Nov. 18, 1969, U.S. Pat. No. 3,429.706 of Shepard et al. issued Feb. 25, I969, U.S. Pat. No. 3,645,739 of Ohkubo et al. issued Feb. 29, 1972, U.S. Pat. No. 3,515,559 of Druker et al. issued June 2, l970, and U.S. Pat. No. 3,672,904 of DeMauriac issued June 27, l972. The described acrylamide polymers can be useful in thermographic materials also. Thermographic materials in which the acrylamide polymers can be useful are described, for example, in U.S. Pat. Nos. 2,910,377 and 3,094,417 ofworkman issued June l8, 1963. Selection of an optimum acrylamide polymer as described for use in one or more layers of the photothermographic materials or thermographic materials described in the above art will depend upon such factors as the compatability of the acrylamide polymer with the other components of the photothermographic or thermographic material, the desired image, processing temperature and the like. Preferably, the acrylamide polymers described are used with hydrophilic materials such as photothermographic materials coated from aqueous formulations.
The following examples are included for a further understanding of the invention.
EXAMPLE l poly(vinyl alcohol) as a binder 2.15 gJm. hydroquinone l.
The resulting layer was designated layer (1).
The following components were mixed and then coated on layer (1):
poly(vinyl alcohol) as a binder surfactant (Surfactant 106 which is a nonylphenoxypolyglycidol sold by Rohm and Haas Co., USA.
total silver as silver iodide and silver complex of 3-carboxymethyl-t-methyl-4-thia -Continued ZoIine-Z'thione i) l0% by weight of silver as silver iodide in a gelatino emulsion ii) by weight of silver as a l.6:l (molar ratio) of silver to 3-carboxymethyl-4-methyl-4-thiazoline-Z-thione The resulting layer was designated as layer (2).
Poly(acrylamide-co-2-acetoacetoxyethyl methacrylate) (weight ratio 98:2) (inherent viscosity l.40) measured in L0 N NaCl solution at a concentration of 0.25 g./dl. at a temperature of 25 C. was then coated on layer (2) at the concentration of 7.26 g. of the acrylamide copolymer per m? of support. The acrylamide copolymer layer was designated layer (3).
The resulting photothermographic element was packaged in a so-called double paper envelope, that is, a black paper envelope inside a yellow paper envelope. The double paper envelope was stored in a controlled temperature-relative humidity chamber at 38 C. and 50% relative humidity. After 7 days and after 14 days, samples of the photothermographic element were removed from the double paper envelope and imagewiseexposed for 10 sec. to xenon light in a sensitometer. The samples of exposed photothermographic element were uniformly heated after exposure by passing them over a metal roller for 4 sec. at C. A developed image was observed in each of the samples. The Dmax, Dmin and photographic speed for each of the images in the samples were the same as those of an image developed in an equivalent photothermographic element with the exception that the imagewise exposure and image development were carried out without storing the photothermographic element for a period of time.
EXAMPLE 2 This is a comparative example.
A control photothermographic element (B) was prepared as in Example 1 without the described acrylamide copolymer overcoat (layer 3), and then imagewiseexposed and developed in the same manner as in Example 1. This control photothermographic element provided no acceptable developed image after storage for 14 days under the described incubation conditions in a double paper envelope.
EXAMPLE 3 EXAMPLES 4-10 A photothermographic element was prepared as follows.
The following components were mixed and then coated on a resin-coated paper support:
pol (vinyl alcohol) as a binder g./m. su actant (Surfactant IOG) The resulting photothermmographic layer was overcoated with the polymers designated in the polymer column of following Table l.
The resulting layer was designated as layer (2).
The resulting photothermographic element was imagewise-exposed to tungsten light as described in Examples 4-10 and then overall heated by contacting the element with a metal block at 160 CV for 4 see. A de veloped image is observed. The image had the sensitometric properties given in following Table 2.
EXAMPLE 12 The procedure in Example 1 l was repeated with the exception that an overcoat containing 1.08 g./m. of poly(acrylamide-co-2-acetoacetoxyethyl methacrylate) (weight ratio 98:2) was applied to layer (2) prior to imagewise exposure. The resulting sensitometric properties are reported in following Table 2.
The overcoated photothermographic element was T bl 2 imagewise-exposed to tungsten light in a sensitometer l b L E R l for sec. The exposed photothermographic element gg was overall heated by contacting it with a metal block Example Relative Density Above at 160 C. for 4 sec. Similar samples of the photothermographic element were incubated in a double paper H f h 1'3 rcfuence poi, envelope at 38 C and 50% relative humidity for up to i )2 3 WEE S 15 days. The resulting samples were then lm agewlse- 12 fresh 08 reference pom exposed and overall heated as above. The Dmin. Dmax 25 1 week 108 .06 and relative photographic speed values for each photo- 2 098 3weeks 1.16 .14 thermographic element are given in following Table 1.
Table 1 Example Log E Relative Speed at No. incubation Dmin Dmax 0.6 Density Above Dmin Polymer Overcoat 4 fresh 0.08 1.36 reference point no overcoat 7 days 0.07 1.20 0.90 14 days 0.06 1.02 l.07 5 f h L08 L08 M WMnr-rulnmMv-ro-2-mvwnrwt- 7 days 0.05 1.1 1 -0.30 oxyethyl methylacrylate)(weight ratio 98:2) 15 days 0.07 1.28 0.31 (polymer V 6 fresh 0.06 1.13 +0.04 2.15 g./rn." of equal parts by weight of poly- 7 days 0.10 1.12 +0.04 mer VII and poly(vinyl alcohol) 15 days 0.07 1128 +0.04 7 fresh 0.06 1.32 -0.08 double overcoat; first overcoat consisting of 7 days 0.08 1.24 0.04 1.08 g./m. of polymer VII and a top overcoat 14 days 0.08 1.30 -0. 12 consisting of 1.08 glm. of poly(vinyl alcohol) 8* fresh 0.09 0.94 same as ref 0.54 g./m. of sulfoethylcellulose 4 days 0.13 1.21 +006 13 days 0.05 1118 -0.48 9* fresh 0.16 0.96 +0.02 1.08 g./m.'- of sodium cellulose sulfate 4 days 0.08 1.17 +0.11 13 days 0.14 1.28 -0.04 10 fresh 0.09 1.16 +0.06 2.15 g./m. of equal parts by weight of poly- 4 days 0.09 1.16 +0.06 (acrylamide-co-acrylic acid) and poly(vinyl 13 days 0.09 1.29 0.18 alcohol) 'CDlTlpill'iillVC example EXAMPLE 1 1 EXAMPLE 13 This is a comparative example.
A resin-coated paper support was coated with 1.08 g./m. of polymer Vll containing 1% by weight of formaldehyde based on the weight of the polymer. This was designated as layer (1 On layer 1) was coated a photothermographic composition containing:
3-mercapto-l .2.4 triazole 0.022 g./rn. isopropylhydroquinone 1.62 g./m. Surfactant 100 0.008 g./m. total silver as silver iodide and 0.81 g./m.
silver complex of 3-carhoxymethyl-4-methyl-4-thiazoline-2- thione i) 10% by weight of silver as silver iodide in a gelatino emulsion ii) 90% by weight of silver as a 1.611 (molar ratio) of silver to 3-carboxymethyl- 4-methyl-4thia2oline'2- thione A photothermographic element was prepared as follows:
A resin-coated paper support was coated with a layer comprising a mixture of the following:
po1y(acrylamide-co-2acetoacetoxy- 2.42 g./m. ethyl)methacrylate (weight ratio tertiary-butylhydroquinone 1 .61 gJm. Surfactant 106 0.008 g./m.
agewise-exposed and then overall heated to develop an image as described in Example 1.
The sensitometric results of the photothermographic element are given in following Table 3, including the results from incubation.
Table 3 lncubation Log E Relative (38 C. at 50% Speed at 0.6 Relative Humidity Dmax Density Above Dmin fresh 1.2 reference point l week 1.2 +06 2 weeks 1.15 .2 3 weeks 1 1 .2
EXAMPLES l425 In each of the following examples, a photothermographic element was prepared by coating the following composition on a resin-coated paper support at the designated concentrations:
silver iodide gelatino emulsion 0.075 g. Ag/m. silver complex of 3-carboxy 0.68 g. Ag/m? methy1-4-methyl-4-thiazo1ine Z-thione tertiary-hutylhydroquinorie 1.88 g./m. 3-mcrcapto1.2,4triazo1e 0.0094 gjm. 2.4-dimercuptopyrimidine 0.0024 g./m. Surfactant 106 0.008 g./m.
lmagewise exposure was to tungsten light for 4 seconds and processing of the photothermographic elem ment was carried out by overall heating the exposed element for 4 seconds at 155C. The sensitometric results, polymer location and particular polymers employed for Examples 14-25 are described in following Table 4.
15 EXAMPLES 26-37 Table 4 Fresh l Wk./37.8 C./50% RH Polymer Location' Relative Relative Example Uct T-ct Polymer Speed* Contrast Dmin Dmax Speed* Contrast Dmin Dmax 14 X V 100 1.41 0.03 1.05 25 1.04 0.03 1.03 15 X X V 82 1.21 0.05 0.97 16.5 0.77 0.05 0.80 16 X V1 62 1.07 0.02 1.16 9.1 0.42 0.02 0.45 17 X X V1 31 0.67 0.05 0.90 3.2 0.34 0.05 0.40 18 X V11 89 1.26 0.02 1.06 18.5 0.48 0.02 0.78 19 X X V11 50 1.00 0.05 0.95 11.8 0.62 0.07 0.74 20 X V111 94 1.29 0.03 1.12 28 0.65 0.03 0.93 21 X X V111 73 1.09 0.05 1.00 15.5 0.50 0.05 0.66 22 X 1X 69 1.09 0.02 1 16 0.59 0.02 0.90 23 X X 1X 19.5 0.60 0.05 0.82 6.5 0.42 0.05 0.54 24 X 1 83 1.08 0.02 1.18 32.5 0.65 0.02 0.93 25 X X 1 63 0.97 0.03 1.06 22.5 0.57 0.03 0.64
relative speed measured at 0.30 above Dmin. 4 sec. imagcwise exposure to tungsten light; processed 4 sec./155C. all polymers coated at 1.08 gjm. "U-ct means a coating directly on the support and under the photothermographic layer; Tct means a coating directly on the photothcrmugraphic layer Table 5 Fresh 1 Wk./37.8 (750% RH Polymer Location Relative Relative Example U-ct T-ct Speed Contrast Dmin Dmax Speed Contrast Dmin Dmax Polymer 26 X 100 1.25 0.01 1.10 28 0.65 0.01 0.94 V 27 X X 107 1.26 0.07 0.78 57 1.14 0.08 1.02 V 28 X 53 0.91 0.01 1.06 25 0.70 0.01 0.82 V1 29 X X 29 0.85 0.06 0.93 8.5 0.51 0.07 0.48 V1 30 X 1.22 0.01 1,05 43 0.86 0.01 1.05 V11 31 X X 89 1.07 0.08 0.76 57 1.21 0.10 0.90 V11 32 X 95 1.25 0.01 1.06 41 0.75 0.01 1.06 V111 33 X X 107 1.15 0.06 0.72 105 1.28 0.09 0.86 V111 34 X 69 1.06 0.01 1.19 27 0.63 0.01 0.90 1X 35 X X 32.5 1.12 0.06 1.03 20 0.97 0.08 1.08 1X 36 X 1.40 0.01 l. 10 54 1.06 0.01 1.20 1 37 X X 107 1.22 0.01 0.84 87 1.40 0.03 1.10 1
all polymers at 1.011 gjm. "relative speed measured at 0.30 above Dmin 1 7 EXAMPLE 38 Results similar to Examples 14-25 were observed when 0.43 g./m. of polymer Vll was employed as a binder in the photothermographic layer and the described overcoat layer comprised polymer 1 having the weight ratios of 60:40, 80:20. 90: or 95:5. The sensitometric results provided with these materials are given in following Table 6.
orthosilicate was employed in both the undercoat layer and the overcoat layer for the photothermographic element according to Example 43. Each of the photothermographic elements contained 0.43 g. polymer Vll per m? as a binder in the photothermographic layer. Imagewise exposure and processing were carried out as described in Example 1 l. The sensitometric results are given in following Table 8.
Table 8 Fresh l Wk./37.8 C./50% RH Relative Relative Example Speed Contrast Dmin Dmax Speed* Contrast Dmin Dmax Polymar relative speed measured at 0.30 above Dmin "poly( 1-vinyl-2-pyrrolidonel (comparative example) Table 6 Fresh l Wk./37.8 C./50% RH Relative Relative Weight Ratio of Monomers Example Speed" Contrast Dmin Dmax Speed Contrast Dmin Dmax Used to Prepare Polymer 38C 132 1.16 0.0! 1.22 59 1.00 0.01 l.l l (901W) (polymer I) 38D 87 l.ll 0.01 1.12 45 1.22 0.01 0.92 (:5)
all polymers at 1.011 gjm. in overcoat layer; polymer is poly(acrylamide co-l-vinylimidazoie) "relative speed measured at 0.30 above Dmin EXAMPLES 39-42 The photothermographic element as described in Example 38 was used, with the exception that an overcoat layer was used comprising 1.08 g./m. of polymer l and a layer was used between the resin-coated paper support and the photothermographic layer also comprising 40 polymer l. The resulting photothermographic element was imagewise-exposed and processed as described in Example 14. The developed image resulting and the sensitometric properties of the developed image are 35 The described polymer (A) useful in photothermographic materials are most conveniently prepared as solution polymers and then used as such without isolation. Some of the resulting polymer solutions have rather high pH and should be adjusted to the desired coating pH, usually about pH 4, prior to coating.
The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifica tions can be effected within the spirit and scope of the given in following Table 7. 5 invention.
Table 7 Fresh 1 Wk./37.8 C./50% RH Relative Relative Weight Ratio of Monomers Example Speed" Contrast Dmin Dmax Speed** Contrast Dmin Dmax Used to Prepare Polymer 4] 339 1.07 0.02 1.]0 289 L48 0.02 1.26 (901K)) (polymer I) 42 316 0.95 0.02 1.00 276 1.60 0.02 1.20 (95.5)
all polymers at 1.08 g./m.'-' in undercoat layer and overcoat layer; formaldehyde is present only in the undercoat layer; the polymer is used in each of the overcoat and undercoat layers; the polymer is polytacrylamide-co-l-vinylimidazole] "rclatiu: speed measured at 0.30 above Dmin EXAMPLES 43-47 What is claimed is: l. [n a photothermographic element comprising a support having thereon (l):
a. photographic silver halide in association with b. a silver salt of a heterocyclic thione, said heterocyclic thione being represented by the formula:
wherein R represents atoms completing a 5 member heterocyclic nucleus and Z is alkylene containing 1 to 30 carbon atoms,
c. an organic reducing agent for said silver salt of a heterocyclic thione, and d. a polymeric, synthetic binder and contiguous to (l), at least one polymer layer (H), the improvement wherein said polymer layer (II) comprises at least 50% by weight of a polymer (A) compris ing the repeating units represented by the formulas:
RI -(-CH2CH+ and +CH C+ l C=O R wherein:
R is hydrogen or alkyl containing 1 to 4 carbon atoms,
R is an imidazolyl, N-substituted carbamoyl, 2-
pyrrolidonyl, acetoacetoxyethoxycarbonyl, acetoacetonylmethylphenyl, ethoxycarbonylaceto, pyridyl, hydroxy, hydroxyalkyl containing 1 to 4 carbon atoms, carboxy, carboxyethoxycarbonyl, a heterocyclic ammonium salt group having a S- or 6-membered azonia nitrogen-containing ring, or a pyridinium salt group, and
the weight ratio of starting monomers for said units B and C is, respectively. about 60:40 to lz0.
2. A photothermographic element as in claim 1 also comprising in said layer (II) at least one polymer other than said copolymer (A),
3. A photothermographic element as in claim 1 wherein said copolymer (A) comprises at least 50% by weight of poly-( acrylamide-co-3-methyll vinylimidazolium methosulfate).
4. A photothermographic element as in claim I wherein said copolymer (A) comprises at least 50% by weight of poly-(acrylamide).
5. A photothermographic element as in claim 1 wherein said copolymer (A) comprises at least 50% by weight of poly-(acrylamide-col -vinylimidazole).
6. A photothermographic element as in claim 1 wherein said copolymer (A) comprises at least 50% by weight of poly-( acrylamide-co-Z-methyll vinylimidazole).
7. A photothermographic element as in claim 1 wherein said copolymer (A) comprises at least 50% by weight of poly-(acrylarnide-co-lvinyl-2-pyrrolidone).
8. A photothermographic element as in claim 1 comprising a support having thereon, in sequence:
l. a layer of poly(acrylamide-co-l-vinylimidazole), wherein the weight ratio of starting monomers for said copolymer is, respectively, about 60:40 to about 98:2.
II. a photothermographic layer comprising:
a. photographic silver iodide in association with b. a silver salt of a heterocyclic thione selected from the group consisting of silver salts of 3 carboxymethyl-4-methyl-4-thiazoline-2-thione, 3-( Z-carboxyethyl )-4-hydroxymethyl-4- thiazoline-2-thione, 3-(2-carboxyethyl)benzothiazoline-Z-thione, 3 2-carboxyethyl )-4- methyl-4-thiazoline-2-thione, and combinations thereof,
c. t-butylhydroquinone, and
d. a poly(acrylamide-co-Z-acetoacetoxyethyl methacrylate or poly(acrylamide-col vinylimidazole) binder, and
Ill. an overcoat layer of poly(acrylamide-co-lvinylimidazole) wherein the weight ratio of starting monomers for said copolymer is, respectively, about 60:40 to about 98:2.
9. A photothermographic element as in claim 1 wherein said layer ([1) also comprises a silver halide developing agent.
10. A photothermographic element as in claim I wherein said layer (ll) comprises about 0.40 to about 2.15 g. of said copolymer (A) per in. of said support.
11. A photothermographic element as in claim 1 wherein said polymeric synthetic binder comprises a polymer selected from the group consisting of poly(acrylamide), poly(acrylamide-co-Z-acetoacetoxyethyl methacrylate), poly(acrylamide-co-a-chloroacrylic acid), poly(acrylamide-co-l-vinylimidazole), poly- (vinyl alcohol), and combinations thereof.
12. A photothermographic element as in claim 1 also comprising a hardener in said layer ([1).
13. A photothermographic element as in claim 1 also comprising a aldehyde hardener in said layer (ll).
14. A photothermographic element as in claim 1 also comprising a 3-mercapto-l,2,4-triazole toner.
15. A photothermographic element as in claim 1 also comprising a 2,4-dimercaptopyrimidine toner.
16. A process of developing a latent image in a photothermographic element as defined in claim 1 comprising heating said element to a temperature of about to about 200 C.
17. A process as in claim 16 wherein said photothermographic element is heated for about 0.5 to about 60 sec.
UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT NO. 3,893,860 Page 1 of 5 DATED 1 July 8, 1975 Richard C. Sutton and Heinz E. Stapelfeldt it is certified that error appears in the ab0ve-identified patent and that said Letters Patent are hereby corrected as shown below:
INVENTOR(S) 2 Column 3, line 20, "80" should read ---80C.--.
Column 5, line 25, the formula should read as follows:
Z-COOH Column 6, line 60, "especially" should read s (XXI) T I UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3,893, p 2 f 5 a e O DATED July 8, 1975 g lNvENTOkt 1 Richard C. Sutton and Heinz E. Stapelf It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:
Column 7, line 15, the formula should read as follows:
6 1 /R -N r 7 =s (XXII) 1 z coorr Column 7, line 35, the formula should read as follows:
3 ,R O\ r u t /-=s (XXIII) Y Z COOH Column 8, line 30, "38" should read -38C-- Column 10, line 30, mmethacrylate" should read -methacrylate--.
UNITED STATES PATENT AND TRADEMARK OFFICE CERTIFICATE OF CORRECTION PATENT N0. 3,893,860 DATED 1 July 8 Page 5 Of 5 INVENTORW 1 Richard c. Sutton and Heinz E. Stapelfeldt It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown betow:
Column ll, line 8, "100" should read ---lOOC.--- Line 9, "1 ro" should read ---1 roc.---. Line 12, "150" should read ---l50C.--.
Column l3, line 13, "photothermmographic" should read -photothermographic--.
Column 16, lines 22-23, "particular polymer location" should read ---particular polymer and polymer location---.
Column 20, line #0, "a aldehyde" should read --an aldehyde---.
Signed and Sealed this A ties r:
RUTH C. MASON C. MARSHALL DANN Arresting Ofi'r'cer Commissioner of Parents and Trademarks
Claims (17)
1. IN A PHOTOTHERMOGRAPHIC ELEMENT COMPRISING A SUPPORT HAVING THEREON (1): A. PHOTOGRAPHIC SILVER HALIDE IN ASSOCIATION WITH B. A SILVER SALT OF A HETEROCYCLIC THIONE, SAID HETEROCYCLIC THIONE BEING REPRESENTED BY THE FORMULA:
2. A photothermographic element as in claim 1 also comprising in said layer (II) at least one polymer other than said copolymer (A).
3. A photothermographic element as in claim 1 wherein said copolymer (A) comprises at least 50% by weight of poly-(acrylamide-co-3-methyl-1-vinylimidazolium methosulfate).
4. A photothermographic element as in claim 1 wherein said copolymer (A) comprises at least 50% by weight of poly-(acrylamide).
5. A photothermographic element as in claim 1 wherein said copolymer (A) comprises at least 50% by weight of poly-(acrylamide-co-1-vinylimidazole).
6. A photothermographic element as in claim 1 wherein said copolymer (A) comprises at least 50% by weight of poly-(acrylamide-co-2-methyl-1-vinylimidazole).
7. A photothermoGraphic element as in claim 1 wherein said copolymer (A) comprises at least 50% by weight of poly-(acrylamide-co-1-vinyl-2-pyrrolidone).
8. A photothermographic element as in claim 1 comprising a support having thereon, in sequence: I. a layer of poly(acrylamide-co-1-vinylimidazole), wherein the weight ratio of starting monomers for said copolymer is, respectively, about 60:40 to about 98:2. II. a photothermographic layer comprising: a. photographic silver iodide in association with b. a silver salt of a heterocyclic thione selected from the group consisting of silver salts of 3-carboxymethyl-4-methyl-4-thiazoline-2-thione, 3-(2-carboxyethyl)-4-hydroxymethyl-4-thiazoline-2-thione, 3-(2-carboxyethyl)benzothiazoline-2-thione, 3-(2-carboxyethyl)-4-methyl-4-thiazoline-2-thione, and combinations thereof, c. t-butylhydroquinone, and d. a poly(acrylamide-co-2-acetoacetoxyethyl methacrylate or poly(acrylamide-co-1-vinylimidazole) binder, and III. an overcoat layer of poly(acrylamide-co-1-vinylimidazole) wherein the weight ratio of starting monomers for said copolymer is, respectively, about 60:40 to about 98:2.
9. A photothermographic element as in claim 1 wherein said layer (II) also comprises a silver halide developing agent.
10. A photothermographic element as in claim 1 wherein said layer (II) comprises about 0.40 to about 2.15 g. of said copolymer (A) per m.2 of said support.
11. A photothermographic element as in claim 1 wherein said polymeric synthetic binder comprises a polymer selected from the group consisting of poly(acrylamide), poly(acrylamide-co-2-acetoacetoxyethyl methacrylate), poly(acrylamide-co- Alpha -chloroacrylic acid), poly(acrylamide-co-1-vinylimidazole), poly-(vinyl alcohol), and combinations thereof.
12. A photothermographic element as in claim 1 also comprising a hardener in said layer (II).
13. A photothermographic element as in claim 1 also comprising a aldehyde hardener in said layer (II).
14. A photothermographic element as in claim 1 also comprising a 3-mercapto-1,2,4-triazole toner.
15. A photothermographic element as in claim 1 also comprising a 2,4-dimercaptopyrimidine toner.
16. A process of developing a latent image in a photothermographic element as defined in claim 1 comprising heating said element to a temperature of about 80* to about 200* C.
17. A process as in claim 16 wherein said photothermographic element is heated for about 0.5 to about 60 sec.
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US489029A US3893860A (en) | 1974-07-16 | 1974-07-16 | Photothermographic element and process |
CA208,883A CA1027409A (en) | 1974-07-16 | 1974-09-10 | Photothermographic element, composition and process |
DE19752531563 DE2531563A1 (en) | 1974-07-16 | 1975-07-15 | PHOTOTHERMOGRAPHIC RECORDING MATERIAL |
FR7522062A FR2279131A1 (en) | 1974-07-16 | 1975-07-15 | PHOTOTHERMOGRAPHIC PRODUCT AND PROCESS FOR ITS IMPLEMENTATION |
BE158365A BE831443A (en) | 1974-07-16 | 1975-07-16 | PHOTOTHERMOGRAPHIC PRODUCT AND PROCESS FOR ITS IMPLEMENTATION |
JP50086257A JPS5135320A (en) | 1974-07-16 | 1975-07-16 | |
GB29848/75A GB1510539A (en) | 1974-07-16 | 1975-07-16 | Sensitive photothermographic material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US489029A US3893860A (en) | 1974-07-16 | 1974-07-16 | Photothermographic element and process |
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Publication Number | Publication Date |
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US3893860A true US3893860A (en) | 1975-07-08 |
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US489029A Expired - Lifetime US3893860A (en) | 1974-07-16 | 1974-07-16 | Photothermographic element and process |
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US (1) | US3893860A (en) |
JP (1) | JPS5135320A (en) |
BE (1) | BE831443A (en) |
CA (1) | CA1027409A (en) |
DE (1) | DE2531563A1 (en) |
FR (1) | FR2279131A1 (en) |
GB (1) | GB1510539A (en) |
Cited By (19)
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US3278295A (en) * | 1960-07-07 | 1966-10-11 | Ostberg Jan-Erik | Method of stirring dispersing or homogenizing metal or slag charges having a temperature of at least 800deg. c. |
US4105451A (en) * | 1976-12-22 | 1978-08-08 | Eastman Kodak Company | Photothermographic material, composition and process |
US4170480A (en) * | 1976-09-07 | 1979-10-09 | Fuji Photo Film Co., Ltd. | Thermally developable light-sensitive material |
US4186009A (en) * | 1978-05-30 | 1980-01-29 | Eastman Kodak Company | Covering power photothermographic material and process |
US4211839A (en) * | 1975-09-17 | 1980-07-08 | Fuji Photo Film Co., Ltd. | Method of producing light-sensitive composition for use in thermally developable light-sensitive elements and elements so produced |
EP0012855A1 (en) * | 1978-12-20 | 1980-07-09 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Overcoated photothermographic element having a dye-precursor retaining layer |
US4237213A (en) * | 1976-01-30 | 1980-12-02 | Canon Kabushiki Kaisha | Image forming method |
US4283477A (en) * | 1978-11-02 | 1981-08-11 | Eastman Kodak Company | Photothermographic material and process |
US4288531A (en) * | 1978-12-20 | 1981-09-08 | Eastman Kodak Company | Imaging elements |
US4704344A (en) * | 1983-12-05 | 1987-11-03 | Fuji Photo Film Co., Ltd. | Heat developable light-sensitive material with protective layer |
US4728600A (en) * | 1985-04-17 | 1988-03-01 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive material |
US4732846A (en) * | 1985-04-30 | 1988-03-22 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive material |
EP0849624A2 (en) * | 1996-12-18 | 1998-06-24 | Eastman Kodak Company | Silver halide photographic material containing a polymer with a phographically useful group which is rendered non-diffusive by cross-linking |
US5965347A (en) * | 1997-11-26 | 1999-10-12 | Eastman Kodak Company | Thermally processable imaging element having improved physical properties |
US6468725B2 (en) * | 2000-01-12 | 2002-10-22 | Konica Corporation | Photothermographic material |
US20040131982A1 (en) * | 2002-12-19 | 2004-07-08 | Agfa-Gevaert | Toning agents for use in substantially light-insensitive recording materials |
US20040152027A1 (en) * | 2002-12-19 | 2004-08-05 | Agfa-Gevaert | Toning agents for use in thermographic recording materials |
US20060142477A1 (en) * | 2004-12-29 | 2006-06-29 | Glasser Wolfgang G | Method for making sulfoalkylated cellulose polymer network |
US20060142484A1 (en) * | 2004-12-29 | 2006-06-29 | Glasser Wolfgang G | Sulfoalkylated cellulose polymer network |
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JPS54179700U (en) * | 1978-06-07 | 1979-12-19 |
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- 1975-07-15 DE DE19752531563 patent/DE2531563A1/en active Pending
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US3278295A (en) * | 1960-07-07 | 1966-10-11 | Ostberg Jan-Erik | Method of stirring dispersing or homogenizing metal or slag charges having a temperature of at least 800deg. c. |
US4211839A (en) * | 1975-09-17 | 1980-07-08 | Fuji Photo Film Co., Ltd. | Method of producing light-sensitive composition for use in thermally developable light-sensitive elements and elements so produced |
US4237213A (en) * | 1976-01-30 | 1980-12-02 | Canon Kabushiki Kaisha | Image forming method |
US4170480A (en) * | 1976-09-07 | 1979-10-09 | Fuji Photo Film Co., Ltd. | Thermally developable light-sensitive material |
US4105451A (en) * | 1976-12-22 | 1978-08-08 | Eastman Kodak Company | Photothermographic material, composition and process |
US4186009A (en) * | 1978-05-30 | 1980-01-29 | Eastman Kodak Company | Covering power photothermographic material and process |
US4283477A (en) * | 1978-11-02 | 1981-08-11 | Eastman Kodak Company | Photothermographic material and process |
EP0012855A1 (en) * | 1978-12-20 | 1980-07-09 | EASTMAN KODAK COMPANY (a New Jersey corporation) | Overcoated photothermographic element having a dye-precursor retaining layer |
US4288531A (en) * | 1978-12-20 | 1981-09-08 | Eastman Kodak Company | Imaging elements |
US4704344A (en) * | 1983-12-05 | 1987-11-03 | Fuji Photo Film Co., Ltd. | Heat developable light-sensitive material with protective layer |
US4728600A (en) * | 1985-04-17 | 1988-03-01 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive material |
US4732846A (en) * | 1985-04-30 | 1988-03-22 | Fuji Photo Film Co., Ltd. | Heat-developable light-sensitive material |
EP0849624A2 (en) * | 1996-12-18 | 1998-06-24 | Eastman Kodak Company | Silver halide photographic material containing a polymer with a phographically useful group which is rendered non-diffusive by cross-linking |
EP0849624A3 (en) * | 1996-12-18 | 1998-09-16 | Eastman Kodak Company | Silver halide photographic material containing a polymer with a phographically useful group which is rendered non-diffusive by cross-linking |
US5932404A (en) * | 1996-12-18 | 1999-08-03 | Eastman Kodak Company | Silver halide photographic material containing a polymer with a photographically useful group which is rendered non-diffusible by cross-linking |
US5965347A (en) * | 1997-11-26 | 1999-10-12 | Eastman Kodak Company | Thermally processable imaging element having improved physical properties |
US6468725B2 (en) * | 2000-01-12 | 2002-10-22 | Konica Corporation | Photothermographic material |
US20040131982A1 (en) * | 2002-12-19 | 2004-07-08 | Agfa-Gevaert | Toning agents for use in substantially light-insensitive recording materials |
US20040152027A1 (en) * | 2002-12-19 | 2004-08-05 | Agfa-Gevaert | Toning agents for use in thermographic recording materials |
US7018786B2 (en) | 2002-12-19 | 2006-03-28 | Agfa Gevaert | Toning agents for use in thermographic recording materials |
US7045487B2 (en) | 2002-12-19 | 2006-05-16 | Agfa Gevaert | Toning agents for use in substantially light-insensitive recording materials |
US20060142477A1 (en) * | 2004-12-29 | 2006-06-29 | Glasser Wolfgang G | Method for making sulfoalkylated cellulose polymer network |
US20060142484A1 (en) * | 2004-12-29 | 2006-06-29 | Glasser Wolfgang G | Sulfoalkylated cellulose polymer network |
Also Published As
Publication number | Publication date |
---|---|
FR2279131B1 (en) | 1977-12-09 |
FR2279131A1 (en) | 1976-02-13 |
GB1510539A (en) | 1978-05-10 |
CA1027409A (en) | 1978-03-07 |
JPS5135320A (en) | 1976-03-25 |
BE831443A (en) | 1976-01-16 |
DE2531563A1 (en) | 1976-02-05 |
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