US3679422A - Photothermic composition containing onium halide sensitizer and the use thereof - Google Patents
Photothermic composition containing onium halide sensitizer and the use thereof Download PDFInfo
- Publication number
- US3679422A US3679422A US43172A US3679422DA US3679422A US 3679422 A US3679422 A US 3679422A US 43172 A US43172 A US 43172A US 3679422D A US3679422D A US 3679422DA US 3679422 A US3679422 A US 3679422A
- Authority
- US
- United States
- Prior art keywords
- silver
- photosensitive
- bromide
- halide
- pat
- 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
- 150000004820 halides Chemical class 0.000 title description 29
- 239000000203 mixture Substances 0.000 title description 22
- -1 HALIDE COMPOUND Chemical class 0.000 abstract description 91
- 229910052709 silver Inorganic materials 0.000 abstract description 58
- 239000004332 silver Substances 0.000 abstract description 58
- 239000003795 chemical substances by application Substances 0.000 abstract description 36
- 239000003638 chemical reducing agent Substances 0.000 abstract description 30
- 239000007800 oxidant agent Substances 0.000 abstract description 24
- 150000003839 salts Chemical class 0.000 abstract description 21
- 238000012545 processing Methods 0.000 abstract description 16
- AQRYNYUOKMNDDV-UHFFFAOYSA-M silver behenate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCCCCCC([O-])=O AQRYNYUOKMNDDV-UHFFFAOYSA-M 0.000 abstract description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 abstract description 13
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 230000001235 sensitizing effect Effects 0.000 abstract description 9
- GNMJFQWRASXXMS-UHFFFAOYSA-M trimethyl(phenyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)C1=CC=CC=C1 GNMJFQWRASXXMS-UHFFFAOYSA-M 0.000 abstract description 8
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 7
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract description 6
- QRWZCJXEAOZAAW-UHFFFAOYSA-N n,n,2-trimethylprop-2-enamide Chemical compound CN(C)C(=O)C(C)=C QRWZCJXEAOZAAW-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 230000036211 photosensitivity Effects 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 4
- 239000000975 dye Substances 0.000 description 30
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 24
- 239000000839 emulsion Substances 0.000 description 21
- 238000000034 method Methods 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 14
- 150000004010 onium ions Chemical class 0.000 description 14
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 description 14
- 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 description 14
- 230000033116 oxidation-reduction process Effects 0.000 description 13
- KZNICNPSHKQLFF-UHFFFAOYSA-N succinimide Chemical class O=C1CCC(=O)N1 KZNICNPSHKQLFF-UHFFFAOYSA-N 0.000 description 13
- 125000000217 alkyl group Chemical group 0.000 description 12
- 239000011230 binding agent Substances 0.000 description 12
- 125000000623 heterocyclic group Chemical group 0.000 description 12
- 239000006185 dispersion Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000123 paper Substances 0.000 description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 6
- 229960002317 succinimide Drugs 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 229910052736 halogen Inorganic materials 0.000 description 5
- 150000002367 halogens Chemical class 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003378 silver Chemical class 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000035945 sensitivity Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- 150000005208 1,4-dihydroxybenzenes Chemical class 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 229960005070 ascorbic acid Drugs 0.000 description 3
- 235000010323 ascorbic acid Nutrition 0.000 description 3
- 239000011668 ascorbic acid Substances 0.000 description 3
- 238000005282 brightening Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- IJAPPYDYQCXOEF-UHFFFAOYSA-N phthalazin-1(2H)-one Chemical compound C1=CC=C2C(=O)NN=CC2=C1 IJAPPYDYQCXOEF-UHFFFAOYSA-N 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- LIXPXSXEKKHIRR-UHFFFAOYSA-M tetraethylphosphanium;bromide Chemical compound [Br-].CC[P+](CC)(CC)CC LIXPXSXEKKHIRR-UHFFFAOYSA-M 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- VFJYIHQDILEQNR-UHFFFAOYSA-M trimethylsulfanium;iodide Chemical compound [I-].C[S+](C)C VFJYIHQDILEQNR-UHFFFAOYSA-M 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- LAQYHRQFABOIFD-UHFFFAOYSA-N 2-methoxyhydroquinone Chemical compound COC1=CC(O)=CC=C1O LAQYHRQFABOIFD-UHFFFAOYSA-N 0.000 description 2
- NVXLIZQNSVLKPO-UHFFFAOYSA-N Glucosereductone Chemical compound O=CC(O)C=O NVXLIZQNSVLKPO-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-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
- 150000000996 L-ascorbic acids Chemical class 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 125000003282 alkyl amino group Chemical group 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-M behenate Chemical compound CCCCCCCCCCCCCCCCCCCCCC([O-])=O UKMSUNONTOPOIO-UHFFFAOYSA-M 0.000 description 2
- 229940116224 behenate Drugs 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 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
- 125000004181 carboxyalkyl group Chemical group 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- UKMSUNONTOPOIO-UHFFFAOYSA-N docosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCC(O)=O UKMSUNONTOPOIO-UHFFFAOYSA-N 0.000 description 2
- 150000002081 enamines Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000314 lubricant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 229910021645 metal ion Chemical group 0.000 description 2
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000002916 oxazoles Chemical class 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000004848 polyfunctional curative Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- XYKIUTSFQGXHOW-UHFFFAOYSA-N propan-2-one;toluene Chemical compound CC(C)=O.CC1=CC=CC=C1 XYKIUTSFQGXHOW-UHFFFAOYSA-N 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000008313 sensitization Effects 0.000 description 2
- ORYURPRSXLUCSS-UHFFFAOYSA-M silver;octadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCCCC([O-])=O ORYURPRSXLUCSS-UHFFFAOYSA-M 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000004964 sulfoalkyl group Chemical group 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- MUUHXGOJWVMBDY-UHFFFAOYSA-L tetrazolium blue Chemical compound [Cl-].[Cl-].COC1=CC(C=2C=C(OC)C(=CC=2)[N+]=2N(N=C(N=2)C=2C=CC=CC=2)C=2C=CC=CC=2)=CC=C1[N+]1=NC(C=2C=CC=CC=2)=NN1C1=CC=CC=C1 MUUHXGOJWVMBDY-UHFFFAOYSA-L 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CWGBFIRHYJNILV-UHFFFAOYSA-N (1,4-diphenyl-1,2,4-triazol-4-ium-3-yl)-phenylazanide Chemical compound C=1C=CC=CC=1[N-]C1=NN(C=2C=CC=CC=2)C=[N+]1C1=CC=CC=C1 CWGBFIRHYJNILV-UHFFFAOYSA-N 0.000 description 1
- PSBDWGZCVUAZQS-UHFFFAOYSA-N (dimethylsulfonio)acetate Chemical group C[S+](C)CC([O-])=O PSBDWGZCVUAZQS-UHFFFAOYSA-N 0.000 description 1
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- QZRSCKZNWLDYOR-UHFFFAOYSA-M 1-(1-phenylethyl)-4-propylpyridin-1-ium bromide Chemical compound [Br-].C1(=CC=CC=C1)C(C)[N+]1=CC=C(C=C1)CCC QZRSCKZNWLDYOR-UHFFFAOYSA-M 0.000 description 1
- LDHRTRUQNGWIEF-UHFFFAOYSA-M 1-(3-methyl-1-phenylbutyl)pyridin-1-ium bromide Chemical compound [Br-].C(C)(C)CC(C1=CC=CC=C1)[N+]1=CC=CC=C1 LDHRTRUQNGWIEF-UHFFFAOYSA-M 0.000 description 1
- ZPANWZBSGMDWON-UHFFFAOYSA-N 1-[(2-hydroxynaphthalen-1-yl)methyl]naphthalen-2-ol Chemical compound C1=CC=C2C(CC3=C4C=CC=CC4=CC=C3O)=C(O)C=CC2=C1 ZPANWZBSGMDWON-UHFFFAOYSA-N 0.000 description 1
- LKGFNNSOZPTLSS-UHFFFAOYSA-M 1-benzyl-2-methylpyridin-1-ium;bromide Chemical compound [Br-].CC1=CC=CC=[N+]1CC1=CC=CC=C1 LKGFNNSOZPTLSS-UHFFFAOYSA-M 0.000 description 1
- GKQHIYSTBXDYNQ-UHFFFAOYSA-M 1-dodecylpyridin-1-ium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+]1=CC=CC=C1 GKQHIYSTBXDYNQ-UHFFFAOYSA-M 0.000 description 1
- WOMOKTIBZHLCLG-UHFFFAOYSA-M 1-ethyl-2-methylquinolin-1-ium bromide Chemical compound [Br-].C(C)[N+]1=C(C)C=CC2=CC=CC=C12 WOMOKTIBZHLCLG-UHFFFAOYSA-M 0.000 description 1
- ABFDKXBSQCTIKH-UHFFFAOYSA-M 1-ethylpyridin-1-ium;bromide Chemical compound [Br-].CC[N+]1=CC=CC=C1 ABFDKXBSQCTIKH-UHFFFAOYSA-M 0.000 description 1
- RYGGXWHCWARUBH-UHFFFAOYSA-N 1-naphthalen-1-yl-3h-naphthalene-2,2-diol Chemical group C1=CC=C2C(C3=C4C=CC=CC4=CCC3(O)O)=CC=CC2=C1 RYGGXWHCWARUBH-UHFFFAOYSA-N 0.000 description 1
- XNVYXHPPYWIPKX-UHFFFAOYSA-N 2,2,5,7-tetramethyl-1-oxo-3h-indene-4-carbonyl chloride Chemical compound CC1=CC(C)=C(C(Cl)=O)C2=C1C(=O)C(C)(C)C2 XNVYXHPPYWIPKX-UHFFFAOYSA-N 0.000 description 1
- PKDBCJSWQUOKDO-UHFFFAOYSA-M 2,3,5-triphenyltetrazolium chloride Chemical compound [Cl-].C1=CC=CC=C1C(N=[N+]1C=2C=CC=CC=2)=NN1C1=CC=CC=C1 PKDBCJSWQUOKDO-UHFFFAOYSA-M 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
- VZYDKJOUEPFKMW-UHFFFAOYSA-N 2,3-dihydroxybenzenesulfonic acid Chemical class OC1=CC=CC(S(O)(=O)=O)=C1O VZYDKJOUEPFKMW-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- JHKKTXXMAQLGJB-UHFFFAOYSA-N 2-(methylamino)phenol Chemical class CNC1=CC=CC=C1O JHKKTXXMAQLGJB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PZTWFIMBPRYBOD-UHFFFAOYSA-N 2-acetylphthalazin-1-one Chemical compound C1=CC=C2C(=O)N(C(=O)C)N=CC2=C1 PZTWFIMBPRYBOD-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 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
- JJIBFFQMTFEYBS-UHFFFAOYSA-M 2-ethyl-3-methylisoquinolin-2-ium;bromide Chemical compound [Br-].C1=CC=C2C=C(C)[N+](CC)=CC2=C1 JJIBFFQMTFEYBS-UHFFFAOYSA-M 0.000 description 1
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 description 1
- DFZVZKUDBIJAHK-UHFFFAOYSA-N 2-hydroxyoctadecanoic acid silver Chemical compound [Ag].OC(C(=O)O)CCCCCCCCCCCCCCCC DFZVZKUDBIJAHK-UHFFFAOYSA-N 0.000 description 1
- SRJCJJKWVSSELL-UHFFFAOYSA-N 2-methylnaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(C)=CC=C21 SRJCJJKWVSSELL-UHFFFAOYSA-N 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- UIQPERPLCCTBGX-UHFFFAOYSA-N 2-phenylacetic acid;silver Chemical compound [Ag].OC(=O)CC1=CC=CC=C1 UIQPERPLCCTBGX-UHFFFAOYSA-N 0.000 description 1
- 125000000094 2-phenylethyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])C([H])([H])* 0.000 description 1
- UGWULZWUXSCWPX-UHFFFAOYSA-N 2-sulfanylideneimidazolidin-4-one Chemical compound O=C1CNC(=S)N1 UGWULZWUXSCWPX-UHFFFAOYSA-N 0.000 description 1
- IBWXIFXUDGADCV-UHFFFAOYSA-N 2h-benzotriazole;silver Chemical compound [Ag].C1=CC=C2NN=NC2=C1 IBWXIFXUDGADCV-UHFFFAOYSA-N 0.000 description 1
- XOHUESSDMRKYEV-UHFFFAOYSA-N 2h-phthalazin-1-one;silver Chemical compound [Ag].C1=CC=C2C(=O)NN=CC2=C1 XOHUESSDMRKYEV-UHFFFAOYSA-N 0.000 description 1
- MMINFSMURORWKH-UHFFFAOYSA-N 3,6-dioxabicyclo[6.2.2]dodeca-1(10),8,11-triene-2,7-dione Chemical compound O=C1OCCOC(=O)C2=CC=C1C=C2 MMINFSMURORWKH-UHFFFAOYSA-N 0.000 description 1
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 1
- OWIRCRREDNEXTA-UHFFFAOYSA-N 3-nitro-1h-indazole Chemical class C1=CC=C2C([N+](=O)[O-])=NNC2=C1 OWIRCRREDNEXTA-UHFFFAOYSA-N 0.000 description 1
- DSVIHYOAKPVFEH-UHFFFAOYSA-N 4-(hydroxymethyl)-4-methyl-1-phenylpyrazolidin-3-one Chemical compound N1C(=O)C(C)(CO)CN1C1=CC=CC=C1 DSVIHYOAKPVFEH-UHFFFAOYSA-N 0.000 description 1
- SGAREKHBOFWQBL-UHFFFAOYSA-N 4-methylquinolin-1-ium perchlorate Chemical compound OCl(=O)(=O)=O.C1=CC=C2C(C)=CC=NC2=C1 SGAREKHBOFWQBL-UHFFFAOYSA-N 0.000 description 1
- YWLXLRUDGLRYDR-ZHPRIASZSA-N 5beta,20-epoxy-1,7beta,10beta,13alpha-tetrahydroxy-9-oxotax-11-ene-2alpha,4alpha-diyl 4-acetate 2-benzoate Chemical compound O([C@H]1[C@H]2[C@@](C([C@H](O)C3=C(C)[C@@H](O)C[C@]1(O)C3(C)C)=O)(C)[C@@H](O)C[C@H]1OC[C@]12OC(=O)C)C(=O)C1=CC=CC=C1 YWLXLRUDGLRYDR-ZHPRIASZSA-N 0.000 description 1
- OYEVNZOZBVEAOL-UHFFFAOYSA-N 6-bromo-1-(6-bromonaphthalen-1-yl)-3h-naphthalene-2,2-diol Chemical group BrC1=CC=C2C(C3=C4C=CC(Br)=CC4=CCC3(O)O)=CC=CC2=C1 OYEVNZOZBVEAOL-UHFFFAOYSA-N 0.000 description 1
- 235000021357 Behenic acid Nutrition 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- BKGOEKOJWMSNRX-UHFFFAOYSA-L C(C1(C)C(C)(C)C(C(=O)[O-])CC1)(=O)[O-].[Ag+2] Chemical compound C(C1(C)C(C)(C)C(C(=O)[O-])CC1)(=O)[O-].[Ag+2] BKGOEKOJWMSNRX-UHFFFAOYSA-L 0.000 description 1
- SOPOWMHJZSPMBC-UHFFFAOYSA-L C(C1=CC=C(C(=O)[O-])C=C1)(=O)[O-].[Ag+2] Chemical compound C(C1=CC=C(C(=O)[O-])C=C1)(=O)[O-].[Ag+2] SOPOWMHJZSPMBC-UHFFFAOYSA-L 0.000 description 1
- AXVCDCGTJGNMKM-UHFFFAOYSA-L C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Ag+2] Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Ag+2] AXVCDCGTJGNMKM-UHFFFAOYSA-L 0.000 description 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 1
- 229920002085 Dialdehyde starch Polymers 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-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
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- NQTADLQHYWFPDB-UHFFFAOYSA-N N-Hydroxysuccinimide Chemical compound ON1C(=O)CCC1=O NQTADLQHYWFPDB-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920002367 Polyisobutene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 description 1
- 241000009298 Trigla lyra Species 0.000 description 1
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- GHKJXEICAPOWQS-UHFFFAOYSA-K [Au+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O Chemical compound [Au+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O GHKJXEICAPOWQS-UHFFFAOYSA-K 0.000 description 1
- XJAKVTUWCOGXNJ-UHFFFAOYSA-M [Br-].C(C)CC(C1=CC=CC=C1)[N+]1=CC=CC=C1 Chemical compound [Br-].C(C)CC(C1=CC=CC=C1)[N+]1=CC=CC=C1 XJAKVTUWCOGXNJ-UHFFFAOYSA-M 0.000 description 1
- DEBAJJOWBOLVCM-UHFFFAOYSA-M [Br-].C1(=CC=CC=C1)C(C)[N+]1=CC(=CC=C1)C Chemical compound [Br-].C1(=CC=CC=C1)C(C)[N+]1=CC(=CC=C1)C DEBAJJOWBOLVCM-UHFFFAOYSA-M 0.000 description 1
- GESJRZFDVPOJHJ-UHFFFAOYSA-M [Br-].CCC(C1=CC=CC=C1)[N+]1=CC=C(C=C1)C Chemical compound [Br-].CCC(C1=CC=CC=C1)[N+]1=CC=C(C=C1)C GESJRZFDVPOJHJ-UHFFFAOYSA-M 0.000 description 1
- UONKJIMCBFTUOW-UHFFFAOYSA-N [Br-].CC[S+](CC)CC(O)=O Chemical compound [Br-].CC[S+](CC)CC(O)=O UONKJIMCBFTUOW-UHFFFAOYSA-N 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000007754 air knife coating Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005250 alkyl acrylate group Chemical group 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 125000001204 arachidyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 150000001541 aziridines Chemical class 0.000 description 1
- 150000007656 barbituric acids Chemical class 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 229910001864 baryta Inorganic materials 0.000 description 1
- 229940116226 behenic acid Drugs 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 1
- AFWARTLPQGAFMN-UHFFFAOYSA-M butyl(dimethyl)sulfanium;bromide Chemical compound [Br-].CCCC[S+](C)C AFWARTLPQGAFMN-UHFFFAOYSA-M 0.000 description 1
- 150000001661 cadmium Chemical class 0.000 description 1
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- UMPZROCPMSJJNQ-UHFFFAOYSA-N carboxymethyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CC(=O)O)C1=CC=CC=C1 UMPZROCPMSJJNQ-UHFFFAOYSA-N 0.000 description 1
- 229920006217 cellulose acetate butyrate Polymers 0.000 description 1
- NEUSVAOJNUQRTM-UHFFFAOYSA-N cetylpyridinium Chemical compound CCCCCCCCCCCCCCCC[N+]1=CC=CC=C1 NEUSVAOJNUQRTM-UHFFFAOYSA-N 0.000 description 1
- 229960004830 cetylpyridinium Drugs 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- HGAZMNJKRQFZKS-UHFFFAOYSA-N chloroethene;ethenyl acetate Chemical compound ClC=C.CC(=O)OC=C HGAZMNJKRQFZKS-UHFFFAOYSA-N 0.000 description 1
- AJPXTSMULZANCB-UHFFFAOYSA-N chlorohydroquinone Chemical compound OC1=CC=C(O)C(Cl)=C1 AJPXTSMULZANCB-UHFFFAOYSA-N 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007766 curtain coating Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- ZGSBKNYSPZRUIW-UHFFFAOYSA-M dimethyl(phenyl)sulfanium;bromide Chemical compound [Br-].C[S+](C)C1=CC=CC=C1 ZGSBKNYSPZRUIW-UHFFFAOYSA-M 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 125000001240 enamine group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229920001249 ethyl cellulose Polymers 0.000 description 1
- 235000019325 ethyl cellulose Nutrition 0.000 description 1
- 238000007765 extrusion coating Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002343 gold Chemical class 0.000 description 1
- 229940093915 gynecological organic acid Drugs 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 150000004668 long chain fatty acids Chemical class 0.000 description 1
- CUONGYYJJVDODC-UHFFFAOYSA-N malononitrile Chemical compound N#CCC#N CUONGYYJJVDODC-UHFFFAOYSA-N 0.000 description 1
- 239000006224 matting agent Substances 0.000 description 1
- 150000002730 mercury Chemical class 0.000 description 1
- BRMYZIKAHFEUFJ-UHFFFAOYSA-L mercury diacetate Chemical compound CC(=O)O[Hg]OC(C)=O BRMYZIKAHFEUFJ-UHFFFAOYSA-L 0.000 description 1
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 1
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 description 1
- 229960001490 methapyrilene hydrochloride Drugs 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 description 1
- WTMBHEPQQKNQAC-UHFFFAOYSA-N methyl(phenyl)azanium;bromide Chemical compound [Br-].C[NH2+]C1=CC=CC=C1 WTMBHEPQQKNQAC-UHFFFAOYSA-N 0.000 description 1
- JNMIXMFEVJHFNY-UHFFFAOYSA-M methyl(triphenyl)phosphanium;iodide Chemical compound [I-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(C)C1=CC=CC=C1 JNMIXMFEVJHFNY-UHFFFAOYSA-M 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- VMGAPWLDMVPYIA-HIDZBRGKSA-N n'-amino-n-iminomethanimidamide Chemical compound N\N=C\N=N VMGAPWLDMVPYIA-HIDZBRGKSA-N 0.000 description 1
- 150000004780 naphthols Chemical class 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 150000002918 oxazolines Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000004344 phenylpropyl group Chemical group 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920006289 polycarbonate film Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- FYRHIOVKTDQVFC-UHFFFAOYSA-M potassium phthalimide Chemical compound [K+].C1=CC=C2C(=O)[N-]C(=O)C2=C1 FYRHIOVKTDQVFC-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013014 purified material Substances 0.000 description 1
- NDGRWYRVNANFNB-UHFFFAOYSA-N pyrazolidin-3-one Chemical compound O=C1CCNN1 NDGRWYRVNANFNB-UHFFFAOYSA-N 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 1
- 150000003236 pyrrolines Chemical class 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000004023 quaternary phosphonium compounds Chemical class 0.000 description 1
- 239000001397 quillaja saponaria molina bark Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- BOLDJAUMGUJJKM-LSDHHAIUSA-N renifolin D Natural products CC(=C)[C@@H]1Cc2c(O)c(O)ccc2[C@H]1CC(=O)c3ccc(O)cc3O BOLDJAUMGUJJKM-LSDHHAIUSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 229930182490 saponin Natural products 0.000 description 1
- 150000007949 saponins Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- NBYLLBXLDOPANK-UHFFFAOYSA-M silver 2-carboxyphenolate hydrate Chemical compound C1=CC=C(C(=C1)C(=O)O)[O-].O.[Ag+] NBYLLBXLDOPANK-UHFFFAOYSA-M 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- YRSQDSCQMOUOKO-KVVVOXFISA-M silver;(z)-octadec-9-enoate Chemical compound [Ag+].CCCCCCCC\C=C/CCCCCCCC([O-])=O YRSQDSCQMOUOKO-KVVVOXFISA-M 0.000 description 1
- OEVSPXPUUSCCIH-UHFFFAOYSA-M silver;2-acetamidobenzoate Chemical compound [Ag+].CC(=O)NC1=CC=CC=C1C([O-])=O OEVSPXPUUSCCIH-UHFFFAOYSA-M 0.000 description 1
- QRVRRRYTKFPCEL-UHFFFAOYSA-M silver;2-aminobenzoate Chemical compound [Ag+].NC1=CC=CC=C1C([O-])=O QRVRRRYTKFPCEL-UHFFFAOYSA-M 0.000 description 1
- CLDWGXZGFUNWKB-UHFFFAOYSA-M silver;benzoate Chemical compound [Ag+].[O-]C(=O)C1=CC=CC=C1 CLDWGXZGFUNWKB-UHFFFAOYSA-M 0.000 description 1
- JKOCEVIXVMBKJA-UHFFFAOYSA-M silver;butanoate Chemical compound [Ag+].CCCC([O-])=O JKOCEVIXVMBKJA-UHFFFAOYSA-M 0.000 description 1
- OIZSSBDNMBMYFL-UHFFFAOYSA-M silver;decanoate Chemical compound [Ag+].CCCCCCCCCC([O-])=O OIZSSBDNMBMYFL-UHFFFAOYSA-M 0.000 description 1
- MNMYRUHURLPFQW-UHFFFAOYSA-M silver;dodecanoate Chemical compound [Ag+].CCCCCCCCCCCC([O-])=O MNMYRUHURLPFQW-UHFFFAOYSA-M 0.000 description 1
- GXBIBRDOPVAJRX-UHFFFAOYSA-M silver;furan-2-carboxylate Chemical compound [Ag+].[O-]C(=O)C1=CC=CO1 GXBIBRDOPVAJRX-UHFFFAOYSA-M 0.000 description 1
- LTYHQUJGIQUHMS-UHFFFAOYSA-M silver;hexadecanoate Chemical compound [Ag+].CCCCCCCCCCCCCCCC([O-])=O LTYHQUJGIQUHMS-UHFFFAOYSA-M 0.000 description 1
- OHGHHPYRRURLHR-UHFFFAOYSA-M silver;tetradecanoate Chemical compound [Ag+].CCCCCCCCCCCCCC([O-])=O OHGHHPYRRURLHR-UHFFFAOYSA-M 0.000 description 1
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Inorganic materials [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001629 stilbenes Chemical class 0.000 description 1
- 235000021286 stilbenes Nutrition 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003461 sulfonyl halides Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003498 tellurium compounds Chemical class 0.000 description 1
- 239000004250 tert-Butylhydroquinone Substances 0.000 description 1
- 235000019281 tert-butylhydroquinone Nutrition 0.000 description 1
- 150000004026 tertiary sulfonium compounds Chemical class 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- VJFXTJZJJIZRKP-UHFFFAOYSA-M tetraphenylazanium;bromide Chemical compound [Br-].C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 VJFXTJZJJIZRKP-UHFFFAOYSA-M 0.000 description 1
- BRKFQVAOMSWFDU-UHFFFAOYSA-M tetraphenylphosphanium;bromide Chemical compound [Br-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 BRKFQVAOMSWFDU-UHFFFAOYSA-M 0.000 description 1
- GKXDJYKZFZVASJ-UHFFFAOYSA-M tetrapropylazanium;iodide Chemical compound [I-].CCC[N+](CCC)(CCC)CCC GKXDJYKZFZVASJ-UHFFFAOYSA-M 0.000 description 1
- 125000003831 tetrazolyl group Chemical group 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 150000003549 thiazolines Chemical class 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical compound [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229960005196 titanium dioxide Drugs 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- ANUSMYJRISPAKG-UHFFFAOYSA-M triethylsulfanium;bromide Chemical compound [Br-].CC[S+](CC)CC ANUSMYJRISPAKG-UHFFFAOYSA-M 0.000 description 1
- YRUWHUWWXSWGJV-UHFFFAOYSA-M trimethyl(phenyl)phosphanium;bromide Chemical compound [Br-].C[P+](C)(C)C1=CC=CC=C1 YRUWHUWWXSWGJV-UHFFFAOYSA-M 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
- 125000005023 xylyl group Chemical group 0.000 description 1
- 235000014692 zinc oxide Nutrition 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/494—Silver salt compositions other than silver halide emulsions; Photothermographic systems ; Thermographic systems using noble metal compounds
- G03C1/498—Photothermographic systems, e.g. dry silver
- G03C1/49836—Additives
- G03C1/49845—Active additives, e.g. toners, stabilisers, sensitisers
Definitions
- a combination of a bis-fl-naphthol reducing agent and a colorless, speed-increasing, onium halide compound in conjunction with a stable source of silver for physical development is useful in photosensitive elements for dry processing.
- the element can contain a sensitizing dye and an activator-toning agent.
- a stable, developed image can be provided by heating the element after exposure.
- the photosensitive component can be photographic silver halide or other suitable photosensitive metal salts.
- This invention relates to photosensitive elements, compositions and processes for developing a latent image using so-called dry processing with heat.
- it relates to photosensitive elements suitable for dry processing with heat containing a reducing agent, especially a bis-naphtol reducing agent, an oxidizing agent, especially a heavy metal salt oxidizing agent, and a substantially colorless speed-increasing onium halide compound, especially one containing a quaternary ammonium halide salt which increases the photosensitivity of the element as described.
- Still another of its aspects involves a method of increasing the photographic speed of a photosensitive and thermosensitive composition comprising an oxidation-reduction imageforming combination, especially one containing a colorless speed-increasing onium halide compound.
- a further aspect relates to a dry process of developing and increasing the speed with a reduction of minimum density in some cases in a photosensitive and thermosensitive element containing a reducing agent, an oxidizing agent and a colorless onium halide speed-increasing compound as described.
- Some examples are trimethylsulfonium iodide, methyltriphenylphosphonium iodide and methyl-tri-(3- 3,679,422 Patented July 25, 1972 "ice active cycloammonium salts in photographic silver halideemulsions, such as silver bromide or silver chlorobromide,
- the sensitivity of these emulsions is increased measurably and is generally independent of spectral sensitization.
- Some examples are N-p-phenylethyl-u-picolinium bromide, N-ethylquinaldinium bromide and N-phydroxyethyl lepidinium perchlorate.
- Quaternary ammonium salts have also been included in an aqueous post-fixation bath for silver halide gelatinpeptized elements as protection against sulfiding, staining, inadequate washing after fixing and image fading as shown in US. Pat. 3,093,479 of OlivaIes et al. published June 11, 1963.
- Some examples are laurylpyridinium chloride, lauryltrimethylammonium chloride and cetylpyridinium fluoride.
- Some examples are 1-(fl-phenethyl)-2-methylpyridinium bromide, lbenzyl-Z-methylpyridinium bromide, diethylcarboxymethyl sulfonium bromide and carboxymethyltriphenylphosphonium bromide.
- Alkaline solutions of onium compounds are known to expedite the diffusion of dye developers from unexposed areas to the surface of a photographic element and the transfer of the resulting diffused positive image to a dye developer receiving sheet superimposed on the photographic element as described in US. Pat. 3,253,915 of Weyerts and Salminen issued May 31, 1966.
- Some examples of the onium compounds are 1-benzyl-2-pico-. linium bromide, 1-phenethyl-2-picolinium bromide, anhydro-l-(4-sulfobutyl)-2-picolinium hydroxide, lauryldimethtylsulfonium p-toluene sulfonate and tetraethylphosphonium bromide.
- tetrazolium salts such as blue tetrazolium or red tetrazolium can be employed as imageforrning compounds and as organic oxidizing agents in the top layer of a photosensitive non-silver halide element comprising zinc oxide as a photocatalyst and sodium oxalate as a reducing agent.
- a photosensitive non-silver halide element comprising zinc oxide as a photocatalyst and sodium oxalate as a reducing agent.
- a photosensitive and thermosensitive element comprising a support, an oxidation-reduction image-forming combination comprising an oxidizing agent with a reducing agent, photographic silver halide, a binder and a substantially oolor1ess,.photographic speed-increasing onium halide.
- creasing onium halide compound is a quaternary onium halide salt or atertiary sulfonium halide salt of the Ilia 9 [Re-S ]X 10 wherein X is halide such as chloride, bromide or iodide; R to R are each alkyl such as alkyl containing 1 to 20 carbon atoms, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and eicosyl, aryl such as phenyl and naphthyl,
- arylalkyl such as benzyl, phenethyl and phenylpropyl
- heterocyclic nucleus or groups I .can contain substituents which do not adversely atfect the de-' sired properties of the compound, such as halogen, lower alkyl'aiid halo lower alkyl.
- An especially suitable speed-increasing quaternary ammonium compound is 1-phenethyl-2-picolinium bromide of the formula:
- Methapyrilene hydrochloride Trimethylphenylammonium bromide Tetra-n-propylammonium bromide. Tetra-n-propylammonium. iodide. waHydroxydecylpyridinium-chloride.. 1-benzyl-2-picolinium bromide. 1-'y-phenylpropyl-2-picolinium bromide. 2,4-dimethyl-l-phenethylpyridinium bromide. 2,G-dimethyl-l-phenethylpyridinium bromide. S-ethyI-Z-methyl-l-phenethylpyridinium bromide.
- a-Picoline-fi-naphtholymethyl bromide 1 p-phenylcarbamoyloxyethyl-Z-picolinium bromide.
- 2-ethyl-l-phenethylpyridinium bromide 1-phenethyl-2,4,6-trimethylpyridinium bromide.
- l-n-heptyl-Z-picolinium bromide 2-isopropyl-l-phenethylpyridinium bromide. Tetraphenylammonium bromide. Tetraethylammonium bromide.
- N-ethylpyridinium bromide I N,N-diethy1piperidinium bromide. 1-phenethyl-3-picolinium bromide. Cetyltrimethylammonium bromide.v 3-methyl-2-ethylisoquinolinium bromide. 1-ethyl-2-methyl-3nphenethylbenzimidazolium bromide.
- Another suitable speed-increasing onium halideficor'npound is a quaternary phosphonium'halide compound, tetraethylphosphonium bromide, of the formular' l 9 ours-P 0 2115.
- Suitable speed-increasing quaternary phosphonium halide compounds which canbe employed in the practice of the invention include! I Ethylene-bis-oxymethylphosphonium bromide. Tetraphenylphosphonium bromide. 1 Trimethylphenylphosphonium bromide.
- Still another suitable speed-increasing onium halide compound is a tertiary sulfonium' halide compound, trimethylsulfonium iodide of the formula;
- Suitable speed-increasing tertiary sulfOl'lllJIl'l halide compounds which can be employed in the practice of the invention include:
- Butyldimethylsulfonium bromide Phenyldimethylsulfonium bromide.
- speed-increasing onium compounds are suitable-only in the form of a halide salt.
- concentration of onium halide in an element or composition as described will depend on several factors, such" as the particular image-forming combination, desired image, processing conditions, particular onium compound and the like.
- a suitable test to determine the speed-increasing capabilities of an onium halide compound is demonstrated in Example 3 wherein the speed-increasing onium compound is added as an addendum at various concentrations to a final coating dispersion. The test element is then coated on a suitable support and compared to an element which does not contain an onium halide compound.
- the test element does not show a relative speed increase of 10 or more units after testing at several concentration ranges, then the onium halide compound cannot be considered a speed-increasing addendum.
- the above speedincreasing onium compounds can be used alone or in combination.
- Photosensitive and thermosensitive elements which are suitable for dry processing with heat, can provide a developed image by physical development, such as described in U.S. Pat. No. 3,457,075 of Morgan et al. issued July 22, 1969.
- Other elements of this type are described, for example, in U.S. Pat. No. 3,429,706 of Shepard et al. issued Feb. 25, 1969, and U.S. Pat. No. 3,152,904 of Sorensen et a1. issued Oct. 13, 1964.
- Suitable organic reducing agents which can be employed in the described combination include, for example, substituted phenols and naphthols.
- the bis-naphthol which is preferred is a bis-,B-naphthol of the formula:
- each of R and/or R is hydrogen, alkyl with 1 to 3 carbon atoms, alkoxy, e.g., alkoxy containing 1 to 2 carbon atoms such as methoxy or ethoxy, halogen, nitro, amino or a diazonium halide salt, and n is 0 or 1.
- Suitable bis-B-naphthols which can be employed in the practice of the invention include:
- the described reducing agents are suitable in a range of concentration; however, they are especially suitable at a concentration from about 0.10 to about 0.75 mole of reducing agent per mole of oxidizing agent.
- Suitable silver halide developing agents include, for example, polyhydroxybenzenes such as hydroquinone developing agents, e.g., hydroquinone, alkyl-substituted hydroquinones as exemplified by tertiary butylhydroquinone, methylhydroquinone, 2,5-dimethylhydroquinone and 2,6-dirnethylhydroquinone; catechols and pyrogallol; halo-substituted hydroquinones such as chlorohydroquinone or dichlorohydroquinone; alkoxy-substituted hydroquinones such as methoxyhydroquinone or ethoxyhydroquinone; methylhydroxynaphthalene; phenylenediamine developing agents; methyl gallate; aminophenol developing agents such as 2,4diamino
- Patent 3,337,342 of Green issued Aug. 22, 1967 hydroxylamine developing agents such as N,N'-di(2- ethoxyethyl)hydroxylamine; 3-pyrazolidone developing agents such as 1-pheny1-3-pyrazolidone and 4-methyl-4- hydroxymethyl-l-phenyl-3-pyrazolidone including those described in British Patent 93 0,572 published July 3, 1963;
- reductone developing agents such as anhydrodihydropyrrolidino hexose reductone; and the like.
- a suitable activator-toning agent is a heterocyclic activator-toning agent containing at lea one nitrogen atom and of the formula:
- R is hydrogen, hydroxyl or a metal ion such as potassium, sodium, lithium, silver, gold or mercury
- Z represents atoms completing a heterocyclic nucleus, especially a 5- or 6-member heterocyclic nucleus.
- the atoms completing the heterocyclic nucleus can be, for example,
- heterocyclic nucleus can contain various substituent groups such as amino, alkyl amino, e.g., methylamino or ethylamino, hydroxyl, carbamyl and the like.
- An especially suitable activator-toning agent is a heterocyclic activator-toning agent containing at least one nitrogen atom which is preferably a cyclic-imide of the formula:
- R is hydrogen, hydroxyl, or a metal ion such as potassium, sodium, lithium, silver, gold or mercury
- Z represents carbon atoms of a series completing a cyclicimide nucleus, typically consisting of from 5 to 6 carbon atoms, e.g., a phthalimide or succinimide nucleus.
- the atoms of the cyclicimide nucleus can contain various substituent groups, especially amino, alkyl, such as alkyl containing 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl or pentyl or aryl, such as aryl containing 6 to 20 carbon atoms, such as phenyl, tolyl and xylyl.
- Suitable activator-toning agents which can be employed in the practice of the invention include:
- Phthalimide N-hydroxyphthalimide. N-potassium phthalimide. N-silver phthalimide. N-m'ercury phthalimide. Succinimide. N-hydroxysuccinimide.
- the described activator-toning agents are suitable in a range of concentration; however, they are especially suitable at a concentration from about 0.10 mole to about 1.05 moles of activator-toning agent per mole of oxidizing agent.
- activator-toning agents can be employed in combination with other components of the described photosensitive and thermosensitive element in the practice of the invention.
- a heterocyclic organic toning agent containing at least two hetero atoms in the heterocyclic ring of which at least one is a nitrogen atom is employed.
- Suitable toners include, for example, phthalazinone, phthalic anhydride, 2-acetylphthalazinone and Z-phthalylphthalazinone.
- Other suitable toners are described, for example, in U.S. Patent 3,446,648 of Workman issued May 27, 1969.
- a non-aqueous, polar, organic solvent such as a compound containing a -:i, -S- or -80 moiety, in a photosensitive and thermosensitive element suitablefor dry processing with heat can provide improved maximum image densities, e.g., tetrahydrothiophene-l,ldioxide, 4-hydroxybutanic acid lactone and methylsulfinylmethane.
- the described elements comprise a heavy metal salt oxidizing agent, especially a silver salt of an organic acid.
- the silver salt of the organic acid should be resistant to darkening under illumination to prevent undesired deterioration of a developed image.
- An especially suitable class of silver'salts of organic acids is represented by the water-insoluble silver salts of long-chain fatty acids which are stable to light.
- Compounds which are suitable silver salts include silver behenate, silver stearate, silver oleate, silver laurate, silver hydroxy-stearate, silver caprate, silver myristate and silver palmitate.
- oxidizing agents are silver benzoate, silver phthalazinone, silver benzotriazole, silver saccharin, silver 4'-n-octadecyloxydiphenyl-4-vcarboxylic acid, silver ortho-amino-benzoate, silver acetamidobenzoate, silver furoate, silver camphorate, silver p-phenylben'zoate, silver phenylacetate, silver salicylate, silver butyrate, silver terephthalate, silver phthalate, silver acetate'and silver acid phthalate.
- Oxidizing agents which are not silver salts can be employed if desired, such as zinc oxide, gold stearate, mercuric behenate, auric behenate and the like, but silver salts are preferred.
- the described element can contain a photosensitive salt, especially a photosensitive silver salt.
- a typical concentration range of photosensitive silver salt is from about 0.005 to about 0.50 mole of silver salt per mole of silver 7 salt of organic acid, e.g., per mole of silver behenate. Prechlorobromoiodide, or mixtures thereof.
- the photosensitive silver halide can be coarseor fine-grain, very finegrain emulsions being especially useful.
- the emulsion containing the photosensitive silver halide can be prepared by any of the well-known procedures in the photographic art,'such as single-jet emulsions, double-jet emulsions such as Lippman emulsions, ammoniacal emulsions, thiocyadate or thioether ripened emulsions, such as those described in U.S. Pat. 2,222,264 of Nietz et al., issued Nov. 14, 1940, U.S. Pat. 3,320,069 of Illingsworth, issued May 15, 1967, and U.S. Pat. 3,271,157 of McBride, issued Sept. 6, 1966.
- Surface-image silver halide emulsions can be used.
- mixtures of surfaceand internal-image silver halide emulsions can be used as described in U.S. Pat. 2,996,352 of Luckey et al., issued Apr. 16, 1961. Negative-type emulsions can be used.
- the silver halide emulsion can be a regular-grain emulsion such as described in Klein and Moisar, Journal of Photographic Science, volume 12, No. 5, September-October (1964), pages 242-251.
- the silver halide emulsions employed in the practice of the invention can be unwashed or washed to remove soluble salts.
- the soluble salts can be removed by chill-setting and leaching or the emulsion can be coagulation washed.
- the silver halide employed in the practice of the invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these. Suitable procedures are described, for example, in U.S. Pat. 1,623,499 of Shepard, issued 'Apr. 5,
- Photosensitive silver halide emulsions employed in the practice of the invention can be protected against the production of fog and can be stabilized'against lossof sensitivity during keeping.
- Suitable antifoggants and stabilizers e.g., used alone or in combination include, for example, thiazolium salts; azaindenes; mercury salts as described, for example, in U.S. Pat. 2,728,663 of Allen et al., issued Dec. 27, 1955; urazoles; sulfocatechols; oximes described, for example, in British Pat. 623,448; nitron; nitroindazoles; polyvalent metal salts described, for example, ln'U.S. Pat.
- a photosensitive and thermosensitive element and emulsions described and used in the practice of the invention can contain various colloids alone or in combination-as vehicles, binding agents and in various layers.
- Suitable, materials are typically hydrophobic, but hydrophilic materials can be also be employed. They are transparent or employed include dispersed vinyl compounds such asin latex form and particularly those which increase-dimensional stability of photographic materials.
- Suitablesyne thetic polymers include those described in U.S. Pat.
- Effective polymers include water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, and those which have cross-linking sites which facilitate hardening or curing, as well as those having recurring sulfobetaine units as described in Canadian Pat. 774,054.
- Preferred high-molecular-weight materials and resins include polyvinyl butyral, cellulose acetate butyrate, polymethyl methacrylate, poly(vinyl pyrrolidone), ethyl cellulose, polystyrene, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene-st'yrenecopolymers, vinyl chloride-vinyl acetate copolyme'rs, 'copolypolymers.
- Typicalsupports include cellulose nitrate film, celluloseester film, poly(vinylacetall-film,
- polystyrene film poly(ethylene terephthalat'e) .film, polycarbonate film and related films or resinousmaterialaas,
- a flexible support is employed, especially a paper support which.
- alpl1a-olefin polymer particularly vpolymer of i an alpha-olefin containing 2 to 10 carbon atoms such as poly ethylene, polypropylene, ethylene-butene copolymers and the like.
- the photosensitive and thermosensitive andother hard? enable layers of an element used in the practice of this in? vention can be hardened by various organic or inorganic hardeners, alone or in combination, such as aldehydes,. and blocked aldehydes, ketones, carbox'ylic andcarbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogenlcompounda'e'poxy compounds, aziridines, active olefins, isocyanates, carbodi-' imide's, mixed-function hardeners and polymeric harden-j ers such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like.
- various organic or inorganic hardeners such as aldehydes,. and blocked aldehydes, ketones, carbox'ylic andcarbonic acid derivatives, sulfonate esters, sulfonyl
- the photosensitive and thermosensitive elements used in the practice of the invention can contain antistatic or conducting layers.
- Such layers can comprise soluble salts such as chlorides, nitrates and the like, evaporated metal layers, ionic polymers such as those described in U.S. Pat. 2,861,056 of Minsk issued Nov. 18, 1958, and U.S. Pat. 3,206,312 of Sterman et al. issued Sept. 14, 1965, or insoluble inorganic salts such as those described in U.S. Pat. 3,428,451 of Trevoy issued Feb. 18, 1969.
- the photosensitive and thcrmosensitive elements can also contain antihalation materials and antihalation dyes.
- the photosensitive and thermosensitive layers or other layers employed in the practice of the invention can contain surfactants such as saponin; anionic compounds such as alkyl aryl sulfonates described, for example, in U.S. Pat. 2,600,831 of Baldsiefen issued June 17, 1962; amphoteric compounds such as those described in. U.S. Pat. 3,133,816 of Ben-Ezra issued May 19, 1964; and adducts of glycidol and an alkyl phenol such as those described in British Pat. 1,022,878.
- surfactants such as saponin
- anionic compounds such as alkyl aryl sulfonates described, for example, in U.S. Pat. 2,600,831 of Baldsiefen issued June 17, 1962
- amphoteric compounds such as those described in. U.S. Pat. 3,133,816 of Ben-Ezra issued May 19, 1964
- adducts of glycidol and an alkyl phenol such
- the photosensitive and thermosensitive layers or other layers employed in the practice of the invention can contain plasticizers and lubricants.
- plasticizers and lubricants include, for example, polyalcohols such as glycerin and diols described, for example, in U.S. Pat. 2,960,- 404 of Milton et al. issued Nov. 1, 1966; fatty acids or esters such as those described in U.S. Pat. 2,588,765 of Robijns issued Mar. 11, 1952; U.S. Pat. 3,121,060 of Duane issued Feb. 11, 1964; and silicone resins such as those described in British Pat. 955,061.
- the photosensitive and thermosensitive elements employed in the practice of the invention can contain matting agents such as starch, titaniumdioxide, zinc oxide,-silica, polymeric beads including beads described, for example in-U.S. Pat. 2,922,101 of Jelley et al. issued July 11, 1961, and U.S. Pat. 2,701,245 of Lynn issued Feb. 1, 1955.
- matting agents such as starch, titaniumdioxide, zinc oxide,-silica, polymeric beads including beads described, for example in-U.S. Pat. 2,922,101 of Jelley et al. issued July 11, 1961, and U.S. Pat. 2,701,245 of Lynn issued Feb. 1, 1955.
- the photosensitive and thermosensitive elements employed in the practice of the invention can contain brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents.
- Brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents.
- Water-soluble brightening agents can be used such as those described in German Pat. 972,067 and U.S. Pat. 2,933,390 of McFall et al. issued Apr. 19, 1960, or dispersion of brighteners can be used such as those described in German Pat. 1,150,274, U.S. Pat. 3,406,070 of Oetiker et al. issued Oct. 15, 19.68, and French Pat. 1,530,244.
- the various layers including the photosensitive and thermosensitive layers of an element employed in the practice of the invention can contain light-absorbing materials, filter dyes, antihalation dyes and absorbing dyes, such as those described in U.S. Pat. 3,253,921 of Sawdey issued May 31, 1966; U.S. Pat. 2,274,782 of Gaspar issued Mar. 3, 1942; U.S. Pat. 2,527,583 of Silberstein et al. issued Oct. 31, 1950; and U.S. Pat. 2,956,879 of Van- Campen issued Oct. 18, 1960.
- the dyes can be mordanted, for example, as described in U.S. Pat. 3, 282,- 699 of Jones et al. issued Nov. 1, 1966.
- the photosensitive and thermosensitive layers used in the practice of the invention can be coated by various coating procedures including dip coating, airknife coating, curtain coating or extrusion coating using hoppers such as described in U.S. Pat. 2,681,294 of Beguin issued June 15, 1954. If desired, two or more layers can be coated simultaneously such as by the procedures described in U.S. Pat. 2,761,791 of Russell issued Sept. 4, 1956, and British Pat. 837,095.
- the photosensitive silver halide can be prepared in situ in' the photosensitive and thermosensitive coatings of an element employed in the practice of the invention.
- a method is described, for example, in U.S. Pat. 3,457,075 of Morgan et al. issued July 22, 1969.
- a dilute solution of a halogen acid such as hydrochloric acid can be applied to the surface of a thin coating containing an organic silver salt, such as silver behenate, on a suitable substrate followed by removal of 10 the solvent if desired.
- Silver halide is thus formed in situ throughout the surface of the coating of the organic silver sa t.
- the photosensitive silver halide can be prepared on the oxidizing agent such as silver behenate or silver stearate or other organic silver salt prior to application of the silyer halide on the support employed. This is also described in U.S. Pat. 3,457,075 of Morgan et al. issued July 22, 1969; for example, a halogen acid such as hydrochloric acid or hydrobromic acid can be mixed with an organic silver salt in a suitable reaction medium. .A halide salt more soluble than the organic silver salt can be added to a suspension of the organic silver salt to form the silver halide.
- a suitable reaction medium includes water or other solutions which do not interfere with the reaction.
- Stability to print-out from light exposure is increased by employing highly purified materials; for example, freedom from halides and sulfides increases stability to light exposure.
- highly purified silver behenate can, for example, reduce propensity to print-out in background areas of an element prepared according to the invention.
- Spectral sensitizing dyes can be used conveniently to confer additional sensitivity to the light-sensitive silver halide employed in the practice of the invention.
- additional spectral sensitization can be obtained by treating the silver halide with a solution of a sensitizrng dye in an organic solvent or the dye can be added In the form of a dispersion as described in British Patent 1,154,781.
- the dye can either be atdded to the emulsion as a final step or at some earlier s age.
- Sensitizing dyes useful in sensitizing silver halide emulsions are described, for example, in U.S. Patent 2,526,- 632 of Brooker et al. issued Oct. 24, 1950; U.S. Patent 2,503,776 of Sprague issued Apr. 11, 1950; U.S. Patent 2,493,748 of Brooker et al. issued Jan. 10, 1950; and U.S. Patent 3,384,486 of Taber et al. issued May 21, 1968.
- Spectral sensitizers which can be used include the cyamnes, merocyanines, complex (trinuclear or tetranuclear) merocyanines, complex (trinuclear or tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines such as enamine, hemicyanines, oxonols and hemioxonols.
- Dyes of the cyanine classes can contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles.
- Such nuclei can contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups that can be fused to carbocyclic or heterocyclic-ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano or alkoxy groups.
- the dyes can be symmetrical or unsymmetrical and can contain alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethine chain.
- the merocyanine dyes can contain the basic nuclei described, as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones and malononitrile.
- acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups or heterocyclic nuclei. Combinations of these dyes can be used, if desired.
- supersensitizing addenda which do not absorb visible light may be included such as, for instance, ascorbic acid derivatives, ,azaindenes, cadmium salts and organic sulfonic acid as described in U.S. Patent 2,933,390 of McFall et al. issued Apr. 19, 1960, and U.S. Patent 2,937,089 of Jones et al. issued May 17, 1960.
- the sensitizing dyes and other addenda used in the practice of the invention can be added from water solutions or suitable organic solvent solutions can be used.
- the compounds can be added using various procedures including, for example, those described in U.S. Patent 2,912,343 of Collins et al. issued Nov. 10, 1959; U.S. Patent 3,342,605 of McCrossen et al. issued Sept. 19, 1967; U.S. Patent 2,996,287 of Audran issued Aug. 15,
- a range of concentration of dye can be employed in the practice of the invention.
- the desired concentration will be influenced by the desired spectral sensitivity, other components in the system, the desired image, processing conditions and the like.
- a concentration of the described sensitizing dye is about 0.05 to about 1 milligram per square foot of the described photographic and thermosensitive element, usually about 0.1 milligram per square foot of dye being employed.
- a support is provided with a light-stable organic silver salt oxidizing agent, an organic reducing agent and photosensitive silver salt, especially silver halide, which provides a photosensitive and thermosensitive element.
- a visible image on the photosensitive and thermosensitive element can be produced within a few seconds after exposure by heating the element to moderately elevated temperatures, e.g., about 80 to about 250 C. 7
- one embodiment of the invetnion is: in a photosensitive and thermosensitive element comprising a support, an oxidation-reduction image-forming combinationcomprising an oxidizing agent with a reducing agent, photographic silver halide and a binder; the improvement comprising a colorless, photographic, speed-increasing onium halide.
- the photosensitive and thermosensitive element can comprise:
- an oxidation-reduction image-forming combination .7 comprising: (i) an oxidizing agent with (ii) areducing agent, (b) photosensitive silver halide, (c) a binder and g (d) a colorless, photographic s d-increasing onium halide.
- the photosensitive and thermosensitive composition can comprise:
- the photosensitive and element as described can comprise:
- another embodiment of the invention is: in a process of developing a latent image in an exposed photosensitive and thermosensitive elementcomprising a support, an oxidation-reduction image-forming combination comprising an oxidizing agent with a reducing agent, photographic silver halide, a binder, an activator-toning agent and a colorless, photographic speed-increasing onium halide, comprising heating the described element from about C. to about 250 C.
- a temperature range of about C. to about C. is usually suitable for developing and stabilizing a desired image. By increasing or' decreasing the length of time of heating, a higher or lower temperature within the described range can be employed.
- a developed image is typically produced within a few seconds, such as about 0.5 second to about 60 seconds.
- the photographic process can comprise, for example, exposing to actinic radiation a photosensitive and thermosensitive element comprising asupport,
- an element can be prepared wherein the described silver halide can be in one layer and other components'in other layers.
- an element according to the invention can comprise a sup: port, a layer containing photographic silver halide and'a layer comprising a so-called processing composition comprising:
- thermosensitive (a) a silver salt of an organic acid
- a coating composition is prepared by mixing the following components:
- EXAMPLE 1 M1 This is a comparative example.
- Acetone containing 3.0% by weight 2,2'-dihydroxy- A photographic element is prepared as follows: 1,l'-binaphthyl
- a coating composition is prepared by mixing the fol- Acetone-toluene (1:1 by volume) to a total of 8.0 lowing components: The resulting dispersion is ,coated on a paper support at a wet thickness of about 0.004 inch, dried, exposed to g gig g sggi fgi' tungsten light for 2 seconds and developed by heating on a curved hot block for 15 seconds at 130 C.
- the g f g -z h n b h t f resulting jet-black images have an average maximum 0 mm ⁇ S 8 ver 6 mate 0 01m densit yof 1.01 with a minimum density of 0.18 and a silver bromide in s1tu-0.20 g. relative speed of Acetone'toluene 1)75'00 Additional photosensitive and thermosensitive elements After ball-mixing for about 18 hours, 2.0 milliliters of 25 are prepared, as described, with the exception that various the above dispersion is combined with the following speed-increasing, onium compounds are introduced as adsolutions: denda to the final dispersion within a concentration range Ml. based on the moles of silver bromide present.
- Acetone containing 5.0% by weight 2,2'-dihydroxy gives the relative speed, maximum density and minimum l,1'-binaphthyl 2.00 density obtained after coating trimethylphenylammonium
- the resulting jet-black image has a maximum density of 1.26 with a minimum density of 0.15 and is assigned a relative speed of 100;
- EXAMPLE 2 EXAMPLE 3 This illustrates the invention.
- a series of photographic elements is prepared as follows:
- Example 3 The procedure set out in Example 3 for the preparation of the final dispersion is repeated with the exception that 0.5 m1. of a methanol solution containing 0.01% by weight of the same spectral-sensitizing dye asdescribed in Example 1 is added to the final dispersion.
- the composition is repeated several times and coated on a paper support at a wet thickness of 0.004 inch, dried and heat-processed as in Example 3.
- the resulting jet-black images have an average maximum density of 1.10, a minimum density of 0.17 and a relative speed of 100.
- a photosensitive and thermosensitive element as in coating employmg' the following compounds: I claim 1 wherein said onium'halide is a compound of the- Trimethylphenylammonium bromide (I), formula: v Y 1-phenethyl-2-picolinium bromide (III), I a 1 1: Q Tetra-n-propylammoniurn bromide (IV) and 5 RPYDR4 6 I Tetra-n-propylammonium iodide (V). l Various concentrations as set out in Table II and processing as described in Example 3 are employed.
- sensitizing dye 3 ethyl-5-(3-ethy1-2(3H)-benzothiazylidene1sopropy1ldene) -2-thio-2,4 3,5) -oxazolidenedione.
- R R ⁇ R R R R R-,, R R, and R are exception that equimolar amounts of trimethylphenyleach selected from the group consisting of alkyl containa'mmonium benzenesulfonate (VI) is substituted for triing 1 to 20 carbon atoms, phenyl, naphthyl, benzyl, methylphenylammonium bromide (I) .in the finaldispe'r: phenethyland pheny1propyl;X is a halide ion; Y is nitrosion.
- the composition is coated on a paper supp rt at a gen or phosphorus; Z and Z, each represent the atoms wet thickness of 0.004 inch, dried and heat-processed as necessary to complete a heterocyclic nucleus.
- a photosensitive and thermosensitive element as in ple shows that the speed-increasing onium salt must be in claim 1 wherein said onium halide comprises about 0.10 thehalide form. mole to about 1.00 mole of l-phenethyl-Z-picolinium ARhOIISh the invention has been dsfibed ihcollsider: bromide per mole of said silver halide. able dfiail with Particular mfel'ence to mill Preferred 8.
- a photosensitive and thermosensitive element as in embodiments thereof, variations and modifications can claim 1 wherein said onium halide comprises about 0.01 he 8560M Within the spirit and Scope of the inventionto about 0.10 mole of trimethylphenylammonium bromide We claim: per mole of said silver halide.
- a photosensitive and thermosensitive element comprising a support having thereon an oxidation-reduction prising a t, having th r on image-forming combination comprising a heavy metal (a) an oxidation-reduction image-forming combinatio salt oxidizing agent with a reducing agent, photographic comprising (i) silver behenate with (ii) abis-naphthol silver halide and a binder; the improvement comprising. reducing a ent, I a substantially colorless, photographic speed-increasing, (b) photographic silver halide,
- a photosensitive and thermosensitive element as in tion comprising: I
- said onium halide is a quaternary phos- (a) an oxidation-reduction image-forming combination phoniumhalide. comprising (i) a heavy metal salt oxidizing agent with 5.
- a halide I (c) abinder; the improvement comprising (d) a colorless, photographic speed-increasing, onium halide.
- a photosensitive and thermosensitive composition as in claim 11 also comprising an activator-toning agent comprising phthalazinone, phthalimide or succinimide.
- a photosensitive and thermosensitive composition comprising:
- an oxidation-reduction image-forming combination comprising (i) silver behenate with (ii) a bis-naphthol reducing agent,
- a photosensitive and thermosensitive composition as in claim 11 comprising a spectral-sensitizing dye.
- a photosensitive and thermosensitive composition as in claim 11 wherein said onium halide comprises about 0.10 mole to about 1.00 mole of l-phenethyl-Z-picolinium bromide per mole of said silver halide.
- a photosensitive and thermosensitive composition as in claim 11 wherein said onium halide comprises about 0.01 to about 0.10 mole of trimethylphenylammonium bromide per mole of said silver halide.
- a process of developing a latent image in an exposed photosensitive and thermosensitive element comprising a support, an oxidation-reduction image-forming combination comprising a heavy metal salt oxidizing agent with a reducing agent, photographic silver halide, a binder, an activator-toning agent and a colorless, photographic speed-increasing, onium halide comprising heating said 18 element from about 80 C. t: about 250 C. to form a stable, developed image.
- a process as in claim 18 of developing a latent image comprising heating said element at about 80 C. to about 250 C. for about 0.5 to about seconds.
- a process of developing a latent image in an exposed photosensitive and thermosensitive element comprising a support, ha'ving thereon (a) an oxidation-reduction image-forming combination comprising (i) silver behenate with (ii) a bisnaphthol reducing agent,
- an activator-toning agent which comprises succinimide or phthalimide and (e) an alkyl ammonium halide, comprising heating said element to about C. to about 250 C. for about 0.5 to about 60 seconds.
Abstract
AN ONIUM HALIDE COMPOUND, SUCH A 1-PHENETHYL-2PICOLINIUM BROMIDE OR TRIMETHYLPHENYLAMMONIUM BROMIDE, WITH AN IMAGE-FORMING COMBINATION CONTAINING A HEAVY METAL SALT OXIDIZING AGENT, SUCH AS SILVER BEHENATE, AND A REDUCING AGENT, SUCH AS A BIS-NAPHTHOL REDUCING AGENT, IN A PHOTOSENSITIVE AND THERMOSENSITIVE ELEMENT SUITABLE FOR DRY PROCESSING WITH HEAT, PROVIDES INCREASED PHOTOSENSITIVITY AND IN SOME CASES REDUCED BACKGROUND DENSITIES. A COMBINATION OF A BIS-B-NAPHTHOL REDUCING AGENT AND A COLORLESS, SPEED-INCREASING, ONIOM HALIDE COMPOUND IN CONJUNCTION WITH A STABLE SOURCE OF SILVER FOR PHYSICAL DEVELOPMENT IS USEFUL IN PHOTOSENSITIVE ELEMENTS FOR DRY PROCESSING. THE ELEMENT CAN CONTAIN A SENSITIZING DYE AND AN ACTIVATOR-TONING AGENT. A STABLE, DEVELOPED IMAGE CAN BE PROVIDED BY HEATING THE ELEMENT AFTER EXPOSURE. THE PHOTOSENSITIVE COMPONENT CAN BE PHOTOGRAPHIC SILVER HALIDE OR OTHER SUITABLE PHOTOSENSITIVE METAL SALTS.
Description
United States Patent Rochester, N.Y. No Drawing. Filed June 3, 1970, Ser. No. 43,172 Int. Cl. G03c 1/28, 1/72 21 Claims US. Cl. 96-107 ABSTRACT OF THE DISCLOSURE An onium halide compound, such as 'l-phenethyl-Z- picolim'um bromide or trimethylphenylammonium bromide, with an image-forming combination containing a heavy metal salt oxidizing agent, such as silver behenate, and a reducing agent, such as a biS-naphthol reducing agent, in a photosensitive and thermosensitive element suitable for dry processing with heat, provides increased photosensitivity and in some cases reduced background densities. A combination of a bis-fl-naphthol reducing agent and a colorless, speed-increasing, onium halide compound in conjunction with a stable source of silver for physical development is useful in photosensitive elements for dry processing. The element can contain a sensitizing dye and an activator-toning agent. A stable, developed image can be provided by heating the element after exposure. The photosensitive component can be photographic silver halide or other suitable photosensitive metal salts.
BACKGROUND OF THE INVENTION Field of the invention This invention relates to photosensitive elements, compositions and processes for developing a latent image using so-called dry processing with heat. In one of its aspects, it relates to photosensitive elements suitable for dry processing with heat containing a reducing agent, especially a bis-naphtol reducing agent, an oxidizing agent, especially a heavy metal salt oxidizing agent, and a substantially colorless speed-increasing onium halide compound, especially one containing a quaternary ammonium halide salt which increases the photosensitivity of the element as described. In another of its aspects, it relates to a photosensitive composition suitable for dry processing with heat containing a bis-naphthol reducing compound and a speed-increasing addendum as described. Still another of its aspects involves a method of increasing the photographic speed of a photosensitive and thermosensitive composition comprising an oxidation-reduction imageforming combination, especially one containing a colorless speed-increasing onium halide compound. A further aspect relates to a dry process of developing and increasing the speed with a reduction of minimum density in some cases in a photosensitive and thermosensitive element containing a reducing agent, an oxidizing agent and a colorless onium halide speed-increasing compound as described.
Description of the state of the art It is known that, in an element containing a gelatinpeptized silver halide emulsion, tertiary and quaternary onium iodides can be used to inhibit the production of yellow (dichroic) fog which is due to the presence of physically developed silver as described in Dersch et al., US. Pat. 2,238,631 and US. Pat. 2,238,632 issued Apr. 15, 1941, and Dersch et al., US. Pat. 2,288,586 issued June 30, 1942. Some examples are trimethylsulfonium iodide, methyltriphenylphosphonium iodide and methyl-tri-(3- 3,679,422 Patented July 25, 1972 "ice active cycloammonium salts in photographic silver halideemulsions, such as silver bromide or silver chlorobromide,
emulsions, the sensitivity of these emulsions is increased measurably and is generally independent of spectral sensitization. Some examples are N-p-phenylethyl-u-picolinium bromide, N-ethylquinaldinium bromide and N-phydroxyethyl lepidinium perchlorate.
Quaternary ammonium salts have also been included in an aqueous post-fixation bath for silver halide gelatinpeptized elements as protection against sulfiding, staining, inadequate washing after fixing and image fading as shown in US. Pat. 3,093,479 of OlivaIes et al. published June 11, 1963. Some examples are laurylpyridinium chloride, lauryltrimethylammonium chloride and cetylpyridinium fluoride.
In color difiusion transfer processes, it has been found that image densities are enhanced by carrying out development in the presence of at least one onium compound selected from a group consisting of quaternary ammonium, quaternary phosphonium and tertiary sulfonium compounds. The onium compounds apparently react with dye developers to form salts which increase the solubility and dilfusibility of the dye developers from the unexposed areas of a negative and also inhibit the transfer of such developers from exposed areas, thereby improving the highlights as shown in US. Pat. 3,173,786 of Green et al. published Mar. 16, 1965, and polaroid British Pat. 938,865 published Oct. 9, 1963. Some examples are 1-(fl-phenethyl)-2-methylpyridinium bromide, lbenzyl-Z-methylpyridinium bromide, diethylcarboxymethyl sulfonium bromide and carboxymethyltriphenylphosphonium bromide.
Alkaline solutions of onium compounds are known to expedite the diffusion of dye developers from unexposed areas to the surface of a photographic element and the transfer of the resulting diffused positive image to a dye developer receiving sheet superimposed on the photographic element as described in US. Pat. 3,253,915 of Weyerts and Salminen issued May 31, 1966. Some examples of the onium compounds are 1-benzyl-2-pico-. linium bromide, 1-phenethyl-2-picolinium bromide, anhydro-l-(4-sulfobutyl)-2-picolinium hydroxide, lauryldimethtylsulfonium p-toluene sulfonate and tetraethylphosphonium bromide.
It is known that the addition of mercuric ion, e.g., in the form of mercuric acetate at about 0.005 to about 0.05 mole per mole of silver to a heat-developable photographic printing sheet containing photographic silver halide, an organic silver salt and a reducing agent causes a. significant increase in photographic speed as described in German Pat. 1,908,761 issued Feb. 18, 1969, or South African Pat. 903,080 published Feb. 27, 1969.
It is also known that tetrazolium salts such as blue tetrazolium or red tetrazolium can be employed as imageforrning compounds and as organic oxidizing agents in the top layer of a photosensitive non-silver halide element comprising zinc oxide as a photocatalyst and sodium oxalate as a reducing agent. The above described ele Feb. 25, 1969.
lampand fixed by washing away the'undev'eloped ii'nageforming blue tetrazolium along with the binder. The image consists of insoluble formazan absorbed or adsorbed on the surface of zinc oxide as described in US. Pat. 3,152,903 of Shepard et. a1. published Oct. 13, 1964, and US. Pat. 3,429,706 of Shepard'et al. published .For photosensitive elements suitable for so-called dry processing with heat, anmethod of obtaining increased photosensitivity has been to use sensitizing dyes as described inU.S. Pat. 3,152,904 of Sorensen et al. published'Oct. 13, 1964, and US. Pat. 3,457,075 of Morgan et :11. published July 22, 1969, or, more recently, mercuric ion, as described above in German Pat. 1,908,761.
'-Accordingly, there has been a continuing need for addenda suitable for use in photosensitive and thermosensitive elements which will result in an increase in photosensitivity, e.g., speed, and will not promote any reverse elfects such as increased minimum density and/ or background stain.
SUMMARY OF THE INVENTION It has been found, according to the invention, that the described improvements are provided in a photosensitive and thermosensitive element comprising a support, an oxidation-reduction image-forming combination comprising an oxidizing agent with a reducing agent, photographic silver halide, a binder and a substantially oolor1ess,.photographic speed-increasing onium halide.
, DETAILED DESCRIPTION OF THE INVENTION A range of colorless onium halides can be employed in the practice of the invention to cause an increase in photosensitity, i.e., speed, and in some cases to obtain a reduction in background density. A suitable speed-in? creasing onium halide compound is a quaternary onium halide salt or atertiary sulfonium halide salt of the Ilia 9 [Re-S ]X 10 wherein X is halide such as chloride, bromide or iodide; R to R are each alkyl such as alkyl containing 1 to 20 carbon atoms, e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and eicosyl, aryl such as phenyl and naphthyl,
arylalkyl such as benzyl, phenethyl and phenylpropyl;
gen or phosphorus.
r The described heterocyclic nucleus or groups I .can contain substituents which do not adversely atfect the de-' sired properties of the compound, such as halogen, lower alkyl'aiid halo lower alkyl.
An especially suitable speed-increasing quaternary ammonium compound is 1-phenethyl-2-picolinium bromide of the formula:
ammonium halide compounds which can be employed in the practice of the invention include:
Methapyrilene hydrochloride. Trimethylphenylammonium bromide Tetra-n-propylammonium bromide. Tetra-n-propylammonium. iodide. waHydroxydecylpyridinium-chloride.. 1-benzyl-2-picolinium bromide. 1-'y-phenylpropyl-2-picolinium bromide. 2,4-dimethyl-l-phenethylpyridinium bromide. 2,G-dimethyl-l-phenethylpyridinium bromide. S-ethyI-Z-methyl-l-phenethylpyridinium bromide. a-Picoline-fi-naphtholymethyl bromide. 1 p-phenylcarbamoyloxyethyl-Z-picolinium bromide. 2-ethyl-l-phenethylpyridinium bromide.- 1-phenethyl-2,4,6-trimethylpyridinium bromide. 1-phenethyl-4-n-propylpyridinium bromide. 4-y-hydroxypropyl-l-iphenethylpyridinium bromide. l-n-heptyl-Z-picolinium bromide. 2-isopropyl-l-phenethylpyridinium bromide. Tetraphenylammonium bromide. Tetraethylammonium bromide.
N-ethylpyridinium bromide. I N,N-diethy1piperidinium bromide. 1-phenethyl-3-picolinium bromide. Cetyltrimethylammonium bromide.v 3-methyl-2-ethylisoquinolinium bromide. 1-ethyl-2-methyl-3nphenethylbenzimidazolium bromide.
Another suitable speed-increasing onium halideficor'npound is a quaternary phosphonium'halide compound, tetraethylphosphonium bromide, of the formular' l 9 ours-P 0 2115. Br
. (52H, v a
Other examples of suitable speed-increasing quaternary phosphonium halide compoundswhich canbe employed in the practice of the invention include! I Ethylene-bis-oxymethylphosphonium bromide. Tetraphenylphosphonium bromide. 1 Trimethylphenylphosphonium bromide.
Still another suitable speed-increasing onium halide compound is a tertiary sulfonium' halide compound, trimethylsulfonium iodide of the formula;
Other examples of suitable speed-increasing tertiary sulfOl'lllJIl'l halide compounds which can be employed in the practice of the invention include:
Triethylsulfonium bromide.
Butyldimethylsulfonium bromide. Phenyldimethylsulfonium bromide.
described speed-increasing onium compounds are suitable-only in the form of a halide salt. The desired concentration of onium halide in an element or composition as described will depend on several factors, such" as the particular image-forming combination, desired image, processing conditions, particular onium compound and the like. A suitable test to determine the speed-increasing capabilities of an onium halide compound is demonstrated in Example 3 wherein the speed-increasing onium compound is added as an addendum at various concentrations to a final coating dispersion. The test element is then coated on a suitable support and compared to an element which does not contain an onium halide compound. If, after exposure and heat processing, the test element does not show a relative speed increase of 10 or more units after testing at several concentration ranges, then the onium halide compound cannot be considered a speed-increasing addendum. The above speedincreasing onium compounds can be used alone or in combination.
Photosensitive and thermosensitive elements, which are suitable for dry processing with heat, can provide a developed image by physical development, such as described in U.S. Pat. No. 3,457,075 of Morgan et al. issued July 22, 1969. Other elements of this type are described, for example, in U.S. Pat. No. 3,429,706 of Shepard et al. issued Feb. 25, 1969, and U.S. Pat. No. 3,152,904 of Sorensen et a1. issued Oct. 13, 1964.
Suitable organic reducing agents which can be employed in the described combination include, for example, substituted phenols and naphthols. The bis-naphthol which is preferred is a bis-,B-naphthol of the formula:
wherein each of R and/or R is hydrogen, alkyl with 1 to 3 carbon atoms, alkoxy, e.g., alkoxy containing 1 to 2 carbon atoms such as methoxy or ethoxy, halogen, nitro, amino or a diazonium halide salt, and n is 0 or 1. Suitable bis-B-naphthols which can be employed in the practice of the invention include:
2,2-dihydroxy-l,l'-binaphthyl, 6,6'-dibromo-2,2-dihydroxy-1,1'-binaphthyl, 6,6'-dinitro-2,2'-dihydroxy-l,l'-binaphthyl, and/or Bis-(2-hydroxy-1-naphthyl)methane.
The described reducing agents are suitable in a range of concentration; however, they are especially suitable at a concentration from about 0.10 to about 0.75 mole of reducing agent per mole of oxidizing agent.
Other reducing agents, which are typically silver halide developing agents, can be used alone or in conjunction with the above bis-naphthol reducing agents. Suitable silver halide developing agents include, for example, polyhydroxybenzenes such as hydroquinone developing agents, e.g., hydroquinone, alkyl-substituted hydroquinones as exemplified by tertiary butylhydroquinone, methylhydroquinone, 2,5-dimethylhydroquinone and 2,6-dirnethylhydroquinone; catechols and pyrogallol; halo-substituted hydroquinones such as chlorohydroquinone or dichlorohydroquinone; alkoxy-substituted hydroquinones such as methoxyhydroquinone or ethoxyhydroquinone; methylhydroxynaphthalene; phenylenediamine developing agents; methyl gallate; aminophenol developing agents such as 2,4diaminophenols and methylaminophenols; ascorbic acid developing agents such as ascorbic acid, ascorbic acid ketols and ascorbic acid derivatives such as those described in U.S. Patent 3,337,342 of Green issued Aug. 22, 1967; hydroxylamine developing agents such as N,N'-di(2- ethoxyethyl)hydroxylamine; 3-pyrazolidone developing agents such as 1-pheny1-3-pyrazolidone and 4-methyl-4- hydroxymethyl-l-phenyl-3-pyrazolidone including those described in British Patent 93 0,572 published July 3, 1963;
hydroxytetronic acid and hydroxytetronimide developing agents; reductone developing agents such as anhydrodihydropyrrolidino hexose reductone; and the like.
It is desirable to employ an activator-toning agent in the elements, compositions and processes of the invention to obtain a desired image, particularly when phenolic reducing agents are used. A suitable activator-toning agent is a heterocyclic activator-toning agent containing at lea one nitrogen atom and of the formula:
wherein R is hydrogen, hydroxyl or a metal ion such as potassium, sodium, lithium, silver, gold or mercury; Z represents atoms completing a heterocyclic nucleus, especially a 5- or 6-member heterocyclic nucleus. The atoms completing the heterocyclic nucleus can be, for example,
or an alkylene group containing 3 or 4 carbon atoms. The atoms completing the heterocyclic nucleus can contain various substituent groups such as amino, alkyl amino, e.g., methylamino or ethylamino, hydroxyl, carbamyl and the like.
An especially suitable activator-toning agent is a heterocyclic activator-toning agent containing at least one nitrogen atom which is preferably a cyclic-imide of the formula:
wherein R is hydrogen, hydroxyl, or a metal ion such as potassium, sodium, lithium, silver, gold or mercury; Z represents carbon atoms of a series completing a cyclicimide nucleus, typically consisting of from 5 to 6 carbon atoms, e.g., a phthalimide or succinimide nucleus. The atoms of the cyclicimide nucleus can contain various substituent groups, especially amino, alkyl, such as alkyl containing 1 to 5 carbon atoms, such as methyl, ethyl, propyl, butyl or pentyl or aryl, such as aryl containing 6 to 20 carbon atoms, such as phenyl, tolyl and xylyl. Suitable activator-toning agents which can be employed in the practice of the invention include:
Phthalimide. N-hydroxyphthalimide. N-potassium phthalimide. N-silver phthalimide. N-m'ercury phthalimide. Succinimide. N-hydroxysuccinimide.
The described activator-toning agents are suitable in a range of concentration; however, they are especially suitable at a concentration from about 0.10 mole to about 1.05 moles of activator-toning agent per mole of oxidizing agent.
Other so-called activator-toning agents can be employed in combination with other components of the described photosensitive and thermosensitive element in the practice of the invention. Typically, a heterocyclic organic toning agent containing at least two hetero atoms in the heterocyclic ring of which at least one is a nitrogen atom is employed. These are described, for example, in U.S. Patent 3,080,254 of Grant issued Mar. 5, 1963. Suitable toners include, for example, phthalazinone, phthalic anhydride, 2-acetylphthalazinone and Z-phthalylphthalazinone. Other suitable toners are described, for example, in U.S. Patent 3,446,648 of Workman issued May 27, 1969.
A non-aqueous, polar, organic solvent, such as a compound containing a -:i, -S- or -80 moiety, in a photosensitive and thermosensitive element suitablefor dry processing with heat can provide improved maximum image densities, e.g., tetrahydrothiophene-l,ldioxide, 4-hydroxybutanic acid lactone and methylsulfinylmethane.
The described elements comprise a heavy metal salt oxidizing agent, especially a silver salt of an organic acid. The silver salt of the organic acidshould be resistant to darkening under illumination to prevent undesired deterioration of a developed image. An especially suitable class of silver'salts of organic acids is represented by the water-insoluble silver salts of long-chain fatty acids which are stable to light. Compounds which are suitable silver salts include silver behenate, silver stearate, silver oleate, silver laurate, silver hydroxy-stearate, silver caprate, silver myristate and silver palmitate. Other suitable oxidizing agents are silver benzoate, silver phthalazinone, silver benzotriazole, silver saccharin, silver 4'-n-octadecyloxydiphenyl-4-vcarboxylic acid, silver ortho-amino-benzoate, silver acetamidobenzoate, silver furoate, silver camphorate, silver p-phenylben'zoate, silver phenylacetate, silver salicylate, silver butyrate, silver terephthalate, silver phthalate, silver acetate'and silver acid phthalate. Oxidizing agents which are not silver salts can be employed if desired, such as zinc oxide, gold stearate, mercuric behenate, auric behenate and the like, but silver salts are preferred.
The described element can contain a photosensitive salt, especially a photosensitive silver salt. A typical concentration range of photosensitive silver salt is from about 0.005 to about 0.50 mole of silver salt per mole of silver 7 salt of organic acid, e.g., per mole of silver behenate. Prechlorobromoiodide, or mixtures thereof. The photosensitive silver halide can be coarseor fine-grain, very finegrain emulsions being especially useful. The emulsion containing the photosensitive silver halide can be prepared by any of the well-known procedures in the photographic art,'such as single-jet emulsions, double-jet emulsions such as Lippman emulsions, ammoniacal emulsions, thiocyadate or thioether ripened emulsions, such as those described in U.S. Pat. 2,222,264 of Nietz et al., issued Nov. 14, 1940, U.S. Pat. 3,320,069 of Illingsworth, issued May 15, 1967, and U.S. Pat. 3,271,157 of McBride, issued Sept. 6, 1966. Surface-image silver halide emulsions can be used. If desired, mixtures of surfaceand internal-image silver halide emulsions can be used as described in U.S. Pat. 2,996,352 of Luckey et al., issued Apr. 16, 1961. Negative-type emulsions can be used. The silver halide emulsion can be a regular-grain emulsion such as described in Klein and Moisar, Journal of Photographic Science, volume 12, No. 5, September-October (1964), pages 242-251.
The silver halide emulsions employed in the practice of the invention can be unwashed or washed to remove soluble salts. In the latter case, the soluble salts can be removed by chill-setting and leaching or the emulsion can be coagulation washed.
The silver halide employed in the practice of the invention can be sensitized with chemical sensitizers, such as with reducing agents; sulfur, selenium or tellurium compounds; gold, platinum or palladium compounds; or combinations of these. Suitable procedures are described, for example, in U.S. Pat. 1,623,499 of Shepard, issued 'Apr. 5,
' 1927; U.S. Pat. 2,399,083 of Waller et al., issued Apr. .23, 1946; U.S. Pat. 3,297,447 of McVeigh, issued Ian; 10, g 1967; and U.S. Pat. 3,297,446 of Dunn, issued Jan. 10,
1967. Photosensitive silver halide emulsions employed in the practice of the invention can be protected against the production of fog and can be stabilized'against lossof sensitivity during keeping. Suitable antifoggants and stabilizers, e.g., used alone or in combination include, for example, thiazolium salts; azaindenes; mercury salts as described, for example, in U.S. Pat. 2,728,663 of Allen et al., issued Dec. 27, 1955; urazoles; sulfocatechols; oximes described, for example, in British Pat. 623,448; nitron; nitroindazoles; polyvalent metal salts described, for example, ln'U.S. Pat. 2,839,405 of Jones, issued June 17, 1958; platinum, palladium and gold salts described, for example,,in U.S. 'Pat. 2,566,263 of Trivelli et al., issued .Aug. 28, 1951, and U.S. Pat. 2,597,915 of Yutzy et al., issued May 27, 1952.
A photosensitive and thermosensitive element and emulsions described and used in the practice of the invention can contain various colloids alone or in combination-as vehicles, binding agents and in various layers. Suitable, materials are typically hydrophobic, but hydrophilic materials can be also be employed. They are transparent or employed include dispersed vinyl compounds such asin latex form and particularly those which increase-dimensional stability of photographic materials. Suitablesyne thetic polymers include those described in U.S. Pat.
3,142,586 of Nottorf, issued July 28, 1964; U.S. Pat. I
3,193,386 of White, issued July 6, 1955; U.S. Pat. 3,062,- 674 of Houck et al., issued Nov. 6, 1962; U.S. Pat. 3,220,- 844 of Houck et al., issued Nov. 30, 1965; U.S. Pat. 3,287,289 of Ream et al., issued -Nov.22, 1966; and U.S. Pat. 3,411,911 of Dykstra, issuedNov. 19, 1968. Effective polymers include water-insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, and those which have cross-linking sites which facilitate hardening or curing, as well as those having recurring sulfobetaine units as described in Canadian Pat. 774,054. Preferred high-molecular-weight materials and resins include polyvinyl butyral, cellulose acetate butyrate, polymethyl methacrylate, poly(vinyl pyrrolidone), ethyl cellulose, polystyrene, polyvinyl chloride, chlorinated rubber, polyisobutylene, butadiene-st'yrenecopolymers, vinyl chloride-vinyl acetate copolyme'rs, 'copolypolymers.
The photosensitive and thermosensitive layers and-other layers of an element employed in the practice of the invention and described herein can be coated on a wide variety of supports. Typicalsupports include cellulose nitrate film, celluloseester film, poly(vinylacetall-film,
polystyrene film, poly(ethylene terephthalat'e) .film, polycarbonate film and related films or resinousmaterialaas,
well as glass, paper, metal and the like. Typically, a flexible support is employed, especially a paper support which.
can, be partially acetylatedor coated with baryta and/or an alpl1a-olefin polymer, particularly vpolymer of i an alpha-olefin containing 2 to 10 carbon atoms such as poly ethylene, polypropylene, ethylene-butene copolymers and the like. Y
The photosensitive and thermosensitive andother hard? enable layers of an element used in the practice of this in? vention can be hardened by various organic or inorganic hardeners, alone or in combination, such as aldehydes,. and blocked aldehydes, ketones, carbox'ylic andcarbonic acid derivatives, sulfonate esters, sulfonyl halides and vinyl sulfonyl ethers, active halogenlcompounda'e'poxy compounds, aziridines, active olefins, isocyanates, carbodi-' imide's, mixed-function hardeners and polymeric harden-j ers such as oxidized polysaccharides like dialdehyde starch and oxyguargum and the like. I i
The photosensitive and thermosensitive elements used in the practice of the invention can contain antistatic or conducting layers. Such layers can comprise soluble salts such as chlorides, nitrates and the like, evaporated metal layers, ionic polymers such as those described in U.S. Pat. 2,861,056 of Minsk issued Nov. 18, 1958, and U.S. Pat. 3,206,312 of Sterman et al. issued Sept. 14, 1965, or insoluble inorganic salts such as those described in U.S. Pat. 3,428,451 of Trevoy issued Feb. 18, 1969. The photosensitive and thcrmosensitive elements can also contain antihalation materials and antihalation dyes.
The photosensitive and thermosensitive layers or other layers employed in the practice of the invention can contain surfactants such as saponin; anionic compounds such as alkyl aryl sulfonates described, for example, in U.S. Pat. 2,600,831 of Baldsiefen issued June 17, 1962; amphoteric compounds such as those described in. U.S. Pat. 3,133,816 of Ben-Ezra issued May 19, 1964; and adducts of glycidol and an alkyl phenol such as those described in British Pat. 1,022,878.
The photosensitive and thermosensitive layers or other layers employed in the practice of the invention can contain plasticizers and lubricants. Suitable plasticizers and lubricants include, for example, polyalcohols such as glycerin and diols described, for example, in U.S. Pat. 2,960,- 404 of Milton et al. issued Nov. 1, 1966; fatty acids or esters such as those described in U.S. Pat. 2,588,765 of Robijns issued Mar. 11, 1952; U.S. Pat. 3,121,060 of Duane issued Feb. 11, 1964; and silicone resins such as those described in British Pat. 955,061.
If desired, the photosensitive and thermosensitive elements employed in the practice of the invention can contain matting agents such as starch, titaniumdioxide, zinc oxide,-silica, polymeric beads including beads described, for example in-U.S. Pat. 2,922,101 of Jelley et al. issued July 11, 1961, and U.S. Pat. 2,701,245 of Lynn issued Feb. 1, 1955.
The photosensitive and thermosensitive elements employed in the practice of the invention can contain brightening agents including stilbenes, triazines, oxazoles and coumarin brightening agents. Water-soluble brightening agents can be used such as those described in German Pat. 972,067 and U.S. Pat. 2,933,390 of McFall et al. issued Apr. 19, 1960, or dispersion of brighteners can be used such as those described in German Pat. 1,150,274, U.S. Pat. 3,406,070 of Oetiker et al. issued Oct. 15, 19.68, and French Pat. 1,530,244.
The various layers including the photosensitive and thermosensitive layers of an element employed in the practice of the invention can contain light-absorbing materials, filter dyes, antihalation dyes and absorbing dyes, such as those described in U.S. Pat. 3,253,921 of Sawdey issued May 31, 1966; U.S. Pat. 2,274,782 of Gaspar issued Mar. 3, 1942; U.S. Pat. 2,527,583 of Silberstein et al. issued Oct. 31, 1950; and U.S. Pat. 2,956,879 of Van- Campen issued Oct. 18, 1960. If desired, the dyes can be mordanted, for example, as described in U.S. Pat. 3, 282,- 699 of Jones et al. issued Nov. 1, 1966.
The photosensitive and thermosensitive layers used in the practice of the invention can be coated by various coating procedures including dip coating, airknife coating, curtain coating or extrusion coating using hoppers such as described in U.S. Pat. 2,681,294 of Beguin issued June 15, 1954. If desired, two or more layers can be coated simultaneously such as by the procedures described in U.S. Pat. 2,761,791 of Russell issued Sept. 4, 1956, and British Pat. 837,095.
If desired, the photosensitive silver halide can be prepared in situ in' the photosensitive and thermosensitive coatings of an element employed in the practice of the invention. Such a method is described, for example, in U.S. Pat. 3,457,075 of Morgan et al. issued July 22, 1969. For example, a dilute solution of a halogen acid such as hydrochloric acid can be applied to the surface of a thin coating containing an organic silver salt, such as silver behenate, on a suitable substrate followed by removal of 10 the solvent if desired. Silver halide is thus formed in situ throughout the surface of the coating of the organic silver sa t.
The photosensitive silver halide can be prepared on the oxidizing agent such as silver behenate or silver stearate or other organic silver salt prior to application of the silyer halide on the support employed. This is also described in U.S. Pat. 3,457,075 of Morgan et al. issued July 22, 1969; for example, a halogen acid such as hydrochloric acid or hydrobromic acid can be mixed with an organic silver salt in a suitable reaction medium. .A halide salt more soluble than the organic silver salt can be added to a suspension of the organic silver salt to form the silver halide. A suitable reaction medium includes water or other solutions which do not interfere with the reaction.
Stability to print-out from light exposure is increased by employing highly purified materials; for example, freedom from halides and sulfides increases stability to light exposure. The use of highly purified silver behenate can, for example, reduce propensity to print-out in background areas of an element prepared according to the invention.
Spectral sensitizing dyes can be used conveniently to confer additional sensitivity to the light-sensitive silver halide employed in the practice of the invention. For instance, additional spectral sensitization can be obtained by treating the silver halide with a solution of a sensitizrng dye in an organic solvent or the dye can be added In the form of a dispersion as described in British Patent 1,154,781. For optimum results the dye can either be atdded to the emulsion as a final step or at some earlier s age.
Sensitizing dyes useful in sensitizing silver halide emulsions are described, for example, in U.S. Patent 2,526,- 632 of Brooker et al. issued Oct. 24, 1950; U.S. Patent 2,503,776 of Sprague issued Apr. 11, 1950; U.S. Patent 2,493,748 of Brooker et al. issued Jan. 10, 1950; and U.S. Patent 3,384,486 of Taber et al. issued May 21, 1968. Spectral sensitizers which can be used include the cyamnes, merocyanines, complex (trinuclear or tetranuclear) merocyanines, complex (trinuclear or tetranuclear) cyanines, holopolar cyanines, styryls, hemicyanines such as enamine, hemicyanines, oxonols and hemioxonols. Dyes of the cyanine classes can contain such basic nuclei as the thiazolines, oxazolines, pyrrolines, pyridines, oxazoles, thiazoles, selenazoles and imidazoles. Such nuclei can contain alkyl, alkylene, hydroxyalkyl, sulfoalkyl, carboxyalkyl, aminoalkyl and enamine groups that can be fused to carbocyclic or heterocyclic-ring systems either unsubstituted or substituted with halogen, phenyl, alkyl, haloalkyl, cyano or alkoxy groups. The dyes can be symmetrical or unsymmetrical and can contain alkyl, phenyl, enamine or heterocyclic substituents on the methine or polymethine chain. I
The merocyanine dyes can contain the basic nuclei described, as well as acid nuclei such as thiohydantoins, rhodanines, oxazolidenediones, thiazolidenediones, barbituric acids, thiazolineones and malononitrile. These acid nuclei can be substituted with alkyl, alkylene, phenyl, carboxyalkyl, sulfoalkyl, hydroxyalkyl, alkoxyalkyl, alkylamino groups or heterocyclic nuclei. Combinations of these dyes can be used, if desired. In addition, supersensitizing addenda which do not absorb visible light may be included such as, for instance, ascorbic acid derivatives, ,azaindenes, cadmium salts and organic sulfonic acid as described in U.S. Patent 2,933,390 of McFall et al. issued Apr. 19, 1960, and U.S. Patent 2,937,089 of Jones et al. issued May 17, 1960.
The sensitizing dyes and other addenda used in the practice of the invention can be added from water solutions or suitable organic solvent solutions can be used. The compounds can be added using various procedures including, for example, those described in U.S. Patent 2,912,343 of Collins et al. issued Nov. 10, 1959; U.S. Patent 3,342,605 of McCrossen et al. issued Sept. 19, 1967; U.S. Patent 2,996,287 of Audran issued Aug. 15,
11 1961; and US. Patent 3,425,835 of Johnson et a1. issued Feb. 4, 1969.
A range of concentration of dye can be employed in the practice of the invention. The desired concentration will be influenced by the desired spectral sensitivity, other components in the system, the desired image, processing conditions and the like. Typically, a concentration of the described sensitizing dye is about 0.05 to about 1 milligram per square foot of the described photographic and thermosensitive element, usually about 0.1 milligram per square foot of dye being employed. In elements, as described, typically a support is provided with a light-stable organic silver salt oxidizing agent, an organic reducing agent and photosensitive silver salt, especially silver halide, which provides a photosensitive and thermosensitive element. A visible image on the photosensitive and thermosensitive element can be produced within a few seconds after exposure by heating the element to moderately elevated temperatures, e.g., about 80 to about 250 C. 7 Accordingly, one embodiment of the invetnion is: in a photosensitive and thermosensitive element comprising a support, an oxidation-reduction image-forming combinationcomprising an oxidizing agent with a reducing agent, photographic silver halide and a binder; the improvement comprising a colorless, photographic, speed-increasing onium halide.
For example, the photosensitive and thermosensitive element, as described, can comprise:
' (a) polyvinyl butyral binder,
Another embodiment of the invention is a photosensitive and thermosensitive composition comprismg:
(a) an oxidation-reduction image-forming combination .7 comprising: (i) an oxidizing agent with (ii) areducing agent, (b) photosensitive silver halide, (c) a binder and g (d) a colorless, photographic s d-increasing onium halide.
For example, the photosensitive and thermosensitive composition can comprise:
(a) about 0.10 to about 0.30 mole of l-phenethyl-Z- picolinium bromide or about 0.20 to about 0.50 mole of trimethylphenylammonium bromide per mole of silver halide,
(b) about 0.10 to about 0.75 mole of 2,2'-dihydroxy- 1,l'-binaphthyl per mole of silver behenate oxidizing agent,
(c) about 0.005 to about 0.50 mole of photosensitive silver halide per mole of silver behenate oxidizing agent and a (d) about 0.10 mole to about 1.05 moles of phthalimide activator-toning agent per mole of oxidizing agent.
Another embodiment of the invention is a method of increasing the photographic speed of a photosensitive and thermosensitive composition comprising:
(a) an oxidation-reduction image-forming combination comprising:
(i) an oxidizing agent with (ii) a reducing agent, (b) photographic silver halide, (c) a binder and 12 (d) an activator-toning agent, comprising adding to the described composition a colorless, photographic speedincreasing onium halide.
For example, the photosensitive and element as described can comprise:
(a) polyvinyl butyral binder, (b) photographic silver halide, (c) phthalimide, ((1) silver behenate, (e) 2,2-dihydroxy-1,1'-binaphthyl and v, '(f) l-phenethyl-Z-picolinium bromide or trimethylphenyl ammonium bromide.
After exposure of the described photosensitive and thermosensitive element, the resulting latent irnagewis developed .merely by heating the element: Accordingly, another embodiment of the invention is: in a process of developing a latent image in an exposed photosensitive and thermosensitive elementcomprising a support, an oxidation-reduction image-forming combination comprising an oxidizing agent with a reducing agent, photographic silver halide, a binder, an activator-toning agent and a colorless, photographic speed-increasing onium halide, comprising heating the described element from about C. to about 250 C.
.A temperature range of about C. to about C. is usually suitable for developing and stabilizing a desired image. By increasing or' decreasing the length of time of heating, a higher or lower temperature within the described range can be employed. A developed image is typically produced within a few seconds, such as about 0.5 second to about 60 seconds. The photographic process can comprise, for example, exposing to actinic radiation a photosensitive and thermosensitive element comprising asupport,
(a) an oxidation-reduction image-forming combination comprising:
(i) silver behenate with (ii) a bis-naphthol reducing agent,
(b) photographic silver halide, (c) polyvinyl butyral, I (d) an activator-toning agent which comprises phthalimide or succinimide and (e) an alkyl ammonium halide,
and heating the described element from about 80 'C. to about 250 C. for about 0.5 second to about 60 seconds.
Prooessing is usually carried out under ambient'oonditions of pressure and humidity. A temperature, pressure and humidity outside normal atmosphericconditions can the employed if desired; however, normal atmospheric c'onditions arepreferred. r In some cases, if desired, an element can be prepared wherein the described silver halide can be in one layer and other components'in other layers. For example, an element according to the invention can comprise a sup: port, a layer containing photographic silver halide and'a layer comprising a so-called processing composition comprising:
thermosensitive (a) a silver salt of an organic acid,
(b) a reducing agent, as described,
(0) an activator-toning agent, -as described, and (d) a speed-increasing onium halide, as described.
13 trimethylphenylammonium bromide or 1-phenethyl-2- picolinium bromide speed-increasing onium halide in a 14 A coating composition is prepared by mixing the following components:
polyvinylbutyral or cellulose ester binder and coat the G. resulting composition as an antiabrasion overcoat on the Silver behenate 42.00 element as described. Behenic acid 32.00 Other addenda known to be useful in photosensitive Polyvinyl butyral 15.00 and thermosensitive elements of this type, such as de- Sodium bromide 2.50 scribed in British Pat. 1,161,777 published Aug. 20, 1969, Phthalimide 8.50 and U.S. Pat. 3,152,904 of Sorensen et a1. issued Oct. 13, Acetone-toluene (1:1 by volume) to 500.00 ml. 1964, can be employed in the practice of the invention.
The following examples are included for a further After ball-mixing for about 18 hours, 2.0 ml. of the above understanding of the invention. dispersion is combined with the following solutions:
EXAMPLE 1 M1. This is a comparative example. Acetone containing 3.0% by weight 2,2'-dihydroxy- A photographic element is prepared as follows: 1,l'-binaphthyl A coating composition is prepared by mixing the fol- Acetone-toluene (1:1 by volume) to a total of 8.0 lowing components: The resulting dispersion is ,coated on a paper support at a wet thickness of about 0.004 inch, dried, exposed to g gig g sggi fgi' tungsten light for 2 seconds and developed by heating on a curved hot block for 15 seconds at 130 C. The g f g -z h n b h t f resulting jet-black images have an average maximum 0 mm} S 8 ver 6 mate 0 01m densit yof 1.01 with a minimum density of 0.18 and a silver bromide in s1tu-0.20 g. relative speed of Acetone'toluene 1)75'00 Additional photosensitive and thermosensitive elements After ball-mixing for about 18 hours, 2.0 milliliters of 25 are prepared, as described, with the exception that various the above dispersion is combined with the following speed-increasing, onium compounds are introduced as adsolutions: denda to the final dispersion within a concentration range Ml. based on the moles of silver bromide present. Table I Acetone containing 5.0% by weight 2,2'-dihydroxy gives the relative speed, maximum density and minimum l,1'-binaphthyl 2.00 density obtained after coating trimethylphenylammonium Acetone containing 1.0% 'by weight phthalimide 2.00 bromide (I), w-hydroxydecylpyridinium chloride (II) and Acetone containing 0.01% by weight 3-ethyl-5- 1-phenethyl-2-picolinium bromide (HI) at various con- (3-ethyl-2(3H)-benzothiazylideneisopropylidene)- centrations and processing with heat as described above. d e 35 From Table I, it can be seen that the speed-increasing Acetone-toluene y v01111116) to a total Volume onium compounds are concentration-dependent and that of the most eifective onium compound is 1-phenethyl-2- The above final dispersion is coated on a paper support Picolinium bromide! at a Concentration of mole at a wet thickness of about 0.004 inch, dried, exposed per mole of silver bromide.
TABLE I Concentration of onium compound Onium Relative Grams] Mole/ Example compound speed Dmin- Dmu. mole AgBr mole AgBr Control 25 0.18 1. 01 I as 0.20 1.24 5.4 .024 75 0. 1s 0. 78 10.8 .048 88 0. 10 0. 92 53. 5 0. 19 88 0. 12 0. 92 107. 0 0.38 75 0. 1o 1. 04 214. 0 0. 70 100 0. 10 1. 14 53. 5 0. 19 75 0. 12 1. 14 101. 0 0.38
No'm.I=Trlmethy1phenylammonlum bromide; II=u-Hydr0xydecylpyrldlnium chloride; III=1-phenethyl-2-picolinium bromide.
for 1 second to tungsten light and developed by heating on a curved hot block for 10 seconds at a temperature of 140 C. The resulting jet-black image has a maximum density of 1.26 with a minimum density of 0.15 and is assigned a relative speed of 100;
EXAMPLE 2 EXAMPLE 3 This illustrates the invention. A series of photographic elements is prepared as follows:
No spectral-sensitizing dye.
EXAMPLE 4 This illustrates the invention.
The procedure set out in Example 3 for the preparation of the final dispersion is repeated with the exception that 0.5 m1. of a methanol solution containing 0.01% by weight of the same spectral-sensitizing dye asdescribed in Example 1 is added to the final dispersion. The composition is repeated several times and coated on a paper support at a wet thickness of 0.004 inch, dried and heat-processed as in Example 3. The resulting jet-black images have an average maximum density of 1.10, a minimum density of 0.17 and a relative speed of 100.
Additional spectrally sensitized, photosensitive and thermosensitive elements are prepared as described above with the exception that various speed-increasing onium compounds are introduced as addenda to the final dispersion within a concentration range based on the moles of silver bromide present. Table 11 gives the relative speed,
15 16 m aximum density and minim um density obtained after 6. A photosensitive and thermosensitive element as in coating, employmg' the following compounds: I claim 1 wherein said onium'halide is a compound of the- Trimethylphenylammonium bromide (I), formula: v Y 1-phenethyl-2-picolinium bromide (III), I a 1 1: Q Tetra-n-propylammoniurn bromide (IV) and 5 RPYDR4 6 I Tetra-n-propylammonium iodide (V). l Various concentrations as set out in Table II and processing as described in Example 3 are employed. From Table II f 9 II, it can be seen that compound I, trimethylphenylam-- 10 9 monium bromide, is the most effective at the lowest concentration, i.e., at 0.024 mole per mole of silver bromide 1 R1 in the presence of a spectral-sensitizing dye.
TABLE II Concentration of onium compound Onlum Relative Grams] Mole/ Example compound speed Dani. Dmlx. mole AgBr mole AgBr 4 a ControL--.- 100 0.17 1.10 43--.. L 138 0.20 1.20 5.4 0. 024 4 132 0.10 1. 22 10.3 0.048 4 D--- 113 0. 1e 1. 24 1e. 2 0. 072 4 E. 137 o. 10 1. s4 53. 0. 19 4 F- 125 0. 1s 1. 36 74. 9 0. 21 4 G- 125 0.20 1.18 107.0 o. 40 4 H- 137 o. 26 1. 16 214. 0 0. so 4 1-- 125 0. 1s 1. 320. o 1. 4 1-- 125 0. 1s 1. 20 107. 0 0. a4 4 K- 137 0.16 1.18 214. 0 0. 68 4 L. 137 0.18 1.12 m 0 1. as 4 M 125 0.18 1.12 I 0 2. 02
sensitizing dye: 3 ethyl-5-(3-ethy1-2(3H)-benzothiazylidene1sopropy1ldene) -2-thio-2,4 3,5) -oxazolidenedione.
EXAMPLE 5 I f m I I .-z'. e Similar results are obtained as in Example 4 also em- --N x ploying tetraethylphosphonium bromide or trimethylsulfonium iodide, as a colorless speed-increasing onium hal- H ide compound,inthedescribed element. I IV I I R1 0;
. I I 9 EXAMPLE 6 RPS x .Thisisacomparative example. .I
The procedure set out in 4A-4D is repeated with the wherein R R \R R R R R-,, R R, and R are exception that equimolar amounts of trimethylphenyleach selected from the group consisting of alkyl containa'mmonium benzenesulfonate (VI) is substituted for triing 1 to 20 carbon atoms, phenyl, naphthyl, benzyl, methylphenylammonium bromide (I) .in the finaldispe'r: phenethyland pheny1propyl;X is a halide ion; Y is nitrosion. The composition is coated on a paper supp rt at a gen or phosphorus; Z and Z, each represent the atoms wet thickness of 0.004 inch, dried and heat-processed as necessary to complete a heterocyclic nucleus.
in Example 3. No speed increase is observed. This exam- .7. A photosensitive and thermosensitive element as in ple shows that the speed-increasing onium salt must be in claim 1 wherein said onium halide comprises about 0.10 thehalide form. mole to about 1.00 mole of l-phenethyl-Z-picolinium ARhOIISh the invention has been dsfibed ihcollsider: bromide per mole of said silver halide. able dfiail with Particular mfel'ence to mill Preferred 8. A photosensitive and thermosensitive element as in embodiments thereof, variations and modifications can claim 1 wherein said onium halide comprises about 0.01 he 8560M Within the spirit and Scope of the inventionto about 0.10 mole of trimethylphenylammonium bromide We claim: per mole of said silver halide.
In a PhOtOSOBSitil/c and thclmosensitive element 00m? 9. A photosensitive and thermosensitive element comprising a support having thereon an oxidation-reduction prising a t, having th r on image-forming combination comprising a heavy metal (a) an oxidation-reduction image-forming combinatio salt oxidizing agent with a reducing agent, photographic comprising (i) silver behenate with (ii) abis-naphthol silver halide and a binder; the improvement comprising. reducing a ent, I a substantially colorless, photographic speed-increasing, (b) photographic silver halide,
onium halide. (c) polyvinyl butyral, I
2.-A photosensitive and thermosensitive element as in '(d) an activator-toningv agent which comprises succlaim 1 also comprising an activator-toning agent comcinimide or phthalimide, and prising phthalazinone, phthalimide or succinimide. (e) an alkyl quaternary ammonium halide. I I
v 3. A photosensitive and thermosensitive element as in 10. A photosensitive and thermosensitive element as in claim [wherein said onium halide is an alkylquaternary claim 1 comprising a spectral-sensitizing dye. I ammonium halide. I 11. In a photosensitive and thermosensitive composi- 4. A photosensitive and thermosensitive element as in tion comprising: I
claim 1 wherein said onium halide is a quaternary phos- (a) an oxidation-reduction image-forming combination phoniumhalide. comprising (i) a heavy metal salt oxidizing agent with 5. A photosensitive and thermosensitive element as in (ii) a reducing agent, a claim 1 wherein said onium halide is a tertiary sulfonium (b) photosensitivesilver halide, and.
A halide. I (c) abinder; the improvement comprising (d) a colorless, photographic speed-increasing, onium halide.
12. A photosensitive and thermosensitive composition as in claim 11 also comprising an activator-toning agent comprising phthalazinone, phthalimide or succinimide.
13. A photosensitive and thermosensitive composition as in claim 11 wherein said onium halide is an alkyl quaternary ammonium halide.
14. A photosensitive and thermosensitive composition comprising:
(a) an oxidation-reduction image-forming combination comprising (i) silver behenate with (ii) a bis-naphthol reducing agent,
(b) photographic silver halide,
(c) poly-vinyl butyral,
(d) succinimide or phthalimide and (e) l-phenethyl-Z-picolinium bromide or trimethylphenylammonium bromide.
15. A photosensitive and thermosensitive composition as in claim 11 comprising a spectral-sensitizing dye.
16. A photosensitive and thermosensitive composition as in claim 11 wherein said onium halide comprises about 0.10 mole to about 1.00 mole of l-phenethyl-Z-picolinium bromide per mole of said silver halide.
17. A photosensitive and thermosensitive composition as in claim 11 wherein said onium halide comprises about 0.01 to about 0.10 mole of trimethylphenylammonium bromide per mole of said silver halide.
18. A process of developing a latent image in an exposed photosensitive and thermosensitive element comprising a support, an oxidation-reduction image-forming combination comprising a heavy metal salt oxidizing agent with a reducing agent, photographic silver halide, a binder, an activator-toning agent and a colorless, photographic speed-increasing, onium halide comprising heating said 18 element from about 80 C. t: about 250 C. to form a stable, developed image.
19. A process as in claim 18 of developing a latent image comprising heating said element at about 80 C. to about 250 C. for about 0.5 to about seconds.
20. A process as in claim 18 of developing a latent image in said exposed photosensitive and thermosensitive element wherein said onium halide is an alkyl quaternary ammonium halide.
21. A process of developing a latent image in an exposed photosensitive and thermosensitive element comprising a support, ha'ving thereon (a) an oxidation-reduction image-forming combination comprising (i) silver behenate with (ii) a bisnaphthol reducing agent,
(b) photographic silver halide,
(c) polyvinyl butyral,
(d) an activator-toning agent which comprises succinimide or phthalimide and (e) an alkyl ammonium halide, comprising heating said element to about C. to about 250 C. for about 0.5 to about 60 seconds.
References Cited UNITED STATES PATENTS 3,457,075 7/1969 Morgan et al. 96114.1 X 2,756,146 7/1956 Levy 961 14.1 X 3,017,271 1/1962 Piper 96107 3,220,846 11/1965 Tinker et al 96-1 14.1 X
NORMAN G. TORCHIN, Primary Examiner W. H. LOUIE, 1a., Assistant Examiner US. Cl. X.R.
" UNETED PATENT @FECE (5/691) n P m n '1 A: v 1 1 m CERTL EFEQA i in QM; 2565M Patent No. 39 7934 Dated y 5, 9,7
' Inventor(s) Richard A. DeMauriac and Gary L, Hiller It is certified that error appears in theebove-identified'patent and that said Letters Patent are hereby corrected as shown below:
Column 2, line 40, polemroid should read --Polaroid--. Line 56, "methtylsulfonium" should read ---methylsulfonium--.-.
Column 3, line 20, "reverse should read ---adverse---. Line 3%, photosens:Ltnity should read --photosensitivity.
Column L, line 27, I naphtholymethyl should read --naphthoylmethyl-.
Column 5, line A "2,2-" should read 2,2-
Column ll, line 21, :'Lm/'e'1' 1r1io1r1 should read ---invention---.
Column 1M, line 16, "total of" should read total volume of--. Line 22, "densit you? should read density of---.
Column 15, Table 11, line LL 1, "320.0" should read ---321.0---.
Signed and sealed this 29th day of May 1973.
(SEAL) V Attest:
EDWARD M.FLETCHER,JR.. ROBERT GOTTSCHALK Attesting Officer Commissioner of Patents
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US4317270A | 1970-06-03 | 1970-06-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3679422A true US3679422A (en) | 1972-07-25 |
Family
ID=21925858
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US43172A Expired - Lifetime US3679422A (en) | 1970-06-03 | 1970-06-03 | Photothermic composition containing onium halide sensitizer and the use thereof |
Country Status (5)
Country | Link |
---|---|
US (1) | US3679422A (en) |
BE (1) | BE768072A (en) |
CA (1) | CA972612A (en) |
FR (1) | FR2095787A5 (en) |
GB (1) | GB1342525A (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3839041A (en) * | 1970-06-03 | 1974-10-01 | Eastman Kodak Co | Stabilizer precursors in photothermographic elements and compositions |
US3877943A (en) * | 1973-02-06 | 1975-04-15 | Fuji Photo Film Co Ltd | Heat developable photographic material |
DE2460547A1 (en) * | 1974-01-02 | 1975-07-03 | Eastman Kodak Co | METHOD FOR PRODUCING A PHOTOTHERMOGRAPHIC COATING COMPOSITE AND PHOTOTHERMOGRAPHIC RECORDING MATERIAL |
US3957517A (en) * | 1972-12-08 | 1976-05-18 | Fuji Photo Film Co., Ltd. | Dry stabilization of a silver halide photographic material |
US3992209A (en) * | 1973-10-10 | 1976-11-16 | Monsanto Company | Imagewise distribution of sulfate group on substrate polymer by photographic techniques |
WO1980002751A1 (en) * | 1979-06-05 | 1980-12-11 | Minnesota Mining & Mfg | Photothermographic stabilizers |
US4260677A (en) * | 1976-03-12 | 1981-04-07 | Minnesota Mining And Manufacturing Company | Thermographic and photothermographic materials having silver salt complexes therein |
US4411985A (en) * | 1981-09-17 | 1983-10-25 | Eastman Kodak Company | Heat stabilizable photographic silver halide material and process |
US5464736A (en) * | 1994-04-28 | 1995-11-07 | Eastman Kodak Company | Photographic elements containing particular sensitizing dyes |
EP1315032A1 (en) * | 2001-11-21 | 2003-05-28 | Eastman Kodak Company | Ionic liquids as addenda in photothermographic systems |
US20060093974A1 (en) * | 2004-11-02 | 2006-05-04 | Eastman Kodak Company | Thermally developable materials processable at lower temperatures |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB9121795D0 (en) * | 1991-10-14 | 1991-11-27 | Minnesota Mining & Mfg | Positive-acting photothermographic materials |
JP3718235B2 (en) * | 1996-06-13 | 2005-11-24 | アグフア―ゲヴエルト・ナームローゼ・フエンノートシヤツプ | Manufacturing method and recording method of photothermographic materials |
BR9709999A (en) | 1996-06-25 | 1999-08-10 | Mitsubishi Int Gmbh | Process for and establishing a radio link |
-
1970
- 1970-06-03 US US43172A patent/US3679422A/en not_active Expired - Lifetime
-
1971
- 1971-05-07 CA CA112,434A patent/CA972612A/en not_active Expired
- 1971-05-27 GB GB1763271A patent/GB1342525A/en not_active Expired
- 1971-06-02 FR FR7119914A patent/FR2095787A5/fr not_active Expired
- 1971-06-03 BE BE768072A patent/BE768072A/en unknown
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3839041A (en) * | 1970-06-03 | 1974-10-01 | Eastman Kodak Co | Stabilizer precursors in photothermographic elements and compositions |
US3957517A (en) * | 1972-12-08 | 1976-05-18 | Fuji Photo Film Co., Ltd. | Dry stabilization of a silver halide photographic material |
US3877943A (en) * | 1973-02-06 | 1975-04-15 | Fuji Photo Film Co Ltd | Heat developable photographic material |
US3992209A (en) * | 1973-10-10 | 1976-11-16 | Monsanto Company | Imagewise distribution of sulfate group on substrate polymer by photographic techniques |
DE2460547A1 (en) * | 1974-01-02 | 1975-07-03 | Eastman Kodak Co | METHOD FOR PRODUCING A PHOTOTHERMOGRAPHIC COATING COMPOSITE AND PHOTOTHERMOGRAPHIC RECORDING MATERIAL |
US4260677A (en) * | 1976-03-12 | 1981-04-07 | Minnesota Mining And Manufacturing Company | Thermographic and photothermographic materials having silver salt complexes therein |
WO1980002751A1 (en) * | 1979-06-05 | 1980-12-11 | Minnesota Mining & Mfg | Photothermographic stabilizers |
US4288536A (en) * | 1979-06-05 | 1981-09-08 | Minnesota Mining And Manufacturing Company | Photothermographic stabilizers |
US4411985A (en) * | 1981-09-17 | 1983-10-25 | Eastman Kodak Company | Heat stabilizable photographic silver halide material and process |
US5464736A (en) * | 1994-04-28 | 1995-11-07 | Eastman Kodak Company | Photographic elements containing particular sensitizing dyes |
EP1315032A1 (en) * | 2001-11-21 | 2003-05-28 | Eastman Kodak Company | Ionic liquids as addenda in photothermographic systems |
US20060093974A1 (en) * | 2004-11-02 | 2006-05-04 | Eastman Kodak Company | Thermally developable materials processable at lower temperatures |
Also Published As
Publication number | Publication date |
---|---|
FR2095787A5 (en) | 1972-02-11 |
BE768072A (en) | 1971-11-03 |
CA972612A (en) | 1975-08-12 |
GB1342525A (en) | 1974-01-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3761270A (en) | Photographic element composition and process | |
US3700458A (en) | Chemical process | |
US3667959A (en) | Photosensitive and thermosensitive element,compositions and process | |
US3839041A (en) | Stabilizer precursors in photothermographic elements and compositions | |
US4022617A (en) | Photothermographic element, composition and process for producing a color image from leuco dye | |
US3846136A (en) | Certain activator-toners in photosensitive and thermosensitive elements,compositions and processes | |
US3782949A (en) | Photographic element comprising a hydroxy substituted aliphatic carboxylic acid aryl hydrazide | |
US3672904A (en) | Photothermographic elements containing bis-beta-naphthols | |
US3785830A (en) | Photothermographic element,composition and process | |
US3667958A (en) | Photosensitive and thermosensitive elements,compositions and processes | |
US3985565A (en) | Photothermographic, composition using a phenolic leuco dye as a reducing agent | |
US3679422A (en) | Photothermic composition containing onium halide sensitizer and the use thereof | |
US3666477A (en) | Element,composition and process | |
US3730727A (en) | Photographic element comprising an aliphatic carboxylic acid aryl hydrazide and ascorbic acid | |
US3761279A (en) | Photothermographic element | |
US3700457A (en) | Use of development inhibitor releasing compounds in photothermographic elements | |
US3877940A (en) | Photothermographic element, composition and process | |
US3893860A (en) | Photothermographic element and process | |
US3871887A (en) | Photothermographic composition, element and process | |
US3751249A (en) | Photothermic silver halide element containing a bis-beta-naphthol reducing agent and a 1, 3-dihydroxy-benzene reducing agent | |
US3751252A (en) | Photothermographic element and process | |
US4105451A (en) | Photothermographic material, composition and process | |
JP2002202575A (en) | Photothermographic material | |
US4124387A (en) | Positive images in photothermographic materials containing nitroxyl compounds | |
US3690872A (en) | Photographic developing process with amino hydroxy cycloalkenone |