US3649275A - Photographic elements and processes - Google Patents
Photographic elements and processes Download PDFInfo
- Publication number
- US3649275A US3649275A US854719A US3649275DA US3649275A US 3649275 A US3649275 A US 3649275A US 854719 A US854719 A US 854719A US 3649275D A US3649275D A US 3649275DA US 3649275 A US3649275 A US 3649275A
- Authority
- US
- United States
- Prior art keywords
- group
- radical
- nucleating agent
- nucleus
- agent precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000008569 process Effects 0.000 title claims abstract description 29
- 150000003839 salts Chemical class 0.000 claims abstract description 74
- 229910052751 metal Inorganic materials 0.000 claims abstract description 50
- 239000002184 metal Substances 0.000 claims abstract description 50
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- -1 alkyl radical Chemical class 0.000 claims description 82
- 239000002667 nucleating agent Substances 0.000 claims description 42
- 239000002243 precursor Substances 0.000 claims description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 125000001434 methanylylidene group Chemical group [H]C#[*] 0.000 claims description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 20
- 125000004429 atom Chemical group 0.000 claims description 17
- 125000000623 heterocyclic group Chemical group 0.000 claims description 16
- 230000005855 radiation Effects 0.000 claims description 16
- 239000000975 dye Substances 0.000 claims description 15
- 125000006569 (C5-C6) heterocyclic group Chemical group 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 150000005840 aryl radicals Chemical class 0.000 claims description 11
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
- 229910052737 gold Inorganic materials 0.000 claims description 11
- 239000010931 gold Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 10
- 150000001450 anions Chemical class 0.000 claims description 10
- 229910052804 chromium Inorganic materials 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229910052802 copper Inorganic materials 0.000 claims description 10
- 239000010949 copper Substances 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 10
- 229910052753 mercury Inorganic materials 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 229910052725 zinc Inorganic materials 0.000 claims description 9
- 239000011701 zinc Substances 0.000 claims description 9
- QGKMIGUHVLGJBR-UHFFFAOYSA-M (4z)-1-(3-methylbutyl)-4-[[1-(3-methylbutyl)quinolin-1-ium-4-yl]methylidene]quinoline;iodide Chemical compound [I-].C12=CC=CC=C2N(CCC(C)C)C=CC1=CC1=CC=[N+](CCC(C)C)C2=CC=CC=C12 QGKMIGUHVLGJBR-UHFFFAOYSA-M 0.000 claims description 8
- 125000004423 acyloxy group Chemical group 0.000 claims description 8
- 125000003172 aldehyde group Chemical group 0.000 claims description 7
- 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 claims description 7
- 150000003222 pyridines Chemical class 0.000 claims description 7
- 150000003248 quinolines Chemical class 0.000 claims description 7
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical group [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims description 2
- 230000001235 sensitizing effect Effects 0.000 abstract description 4
- 230000009471 action Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 18
- 229910001385 heavy metal Inorganic materials 0.000 description 15
- 239000008139 complexing agent Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000003638 chemical reducing agent Substances 0.000 description 12
- XSCHRSMBECNVNS-UHFFFAOYSA-N quinoxaline Chemical compound N1=CC=NC2=CC=CC=C21 XSCHRSMBECNVNS-UHFFFAOYSA-N 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 229940107218 chromium Drugs 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 230000033458 reproduction Effects 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 4
- 239000008199 coating composition Substances 0.000 description 4
- 150000007524 organic acids Chemical class 0.000 description 4
- 235000005985 organic acids Nutrition 0.000 description 4
- 239000000123 paper Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000001419 dependent effect Effects 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 3
- QMHIMXFNBOYPND-UHFFFAOYSA-N 4-methylthiazole Chemical compound CC1=CSC=N1 QMHIMXFNBOYPND-UHFFFAOYSA-N 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical class C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 239000003929 acidic solution Substances 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 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
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 230000000737 periodic effect Effects 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 125000000547 substituted alkyl group Chemical group 0.000 description 2
- 125000004964 sulfoalkyl group Chemical group 0.000 description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FUOSTELFLYZQCW-UHFFFAOYSA-N 1,2-oxazol-3-one Chemical class OC=1C=CON=1 FUOSTELFLYZQCW-UHFFFAOYSA-N 0.000 description 1
- ZRHUHDUEXWHZMA-UHFFFAOYSA-N 1,4-dihydropyrazol-5-one Chemical class O=C1CC=NN1 ZRHUHDUEXWHZMA-UHFFFAOYSA-N 0.000 description 1
- FCTIZUUFUMDWEH-UHFFFAOYSA-N 1h-imidazo[4,5-b]quinoxaline Chemical class C1=CC=C2N=C(NC=N3)C3=NC2=C1 FCTIZUUFUMDWEH-UHFFFAOYSA-N 0.000 description 1
- OWIRVNDMYDSKIJ-UHFFFAOYSA-N 2,4-dichloro-1h-benzimidazole Chemical compound C1=CC=C2NC(Cl)=NC2=C1Cl OWIRVNDMYDSKIJ-UHFFFAOYSA-N 0.000 description 1
- YSUIQYOGTINQIN-UZFYAQMZSA-N 2-amino-9-[(1S,6R,8R,9S,10R,15R,17R,18R)-8-(6-aminopurin-9-yl)-9,18-difluoro-3,12-dihydroxy-3,12-bis(sulfanylidene)-2,4,7,11,13,16-hexaoxa-3lambda5,12lambda5-diphosphatricyclo[13.2.1.06,10]octadecan-17-yl]-1H-purin-6-one Chemical compound NC1=NC2=C(N=CN2[C@@H]2O[C@@H]3COP(S)(=O)O[C@@H]4[C@@H](COP(S)(=O)O[C@@H]2[C@@H]3F)O[C@H]([C@H]4F)N2C=NC3=C2N=CN=C3N)C(=O)N1 YSUIQYOGTINQIN-UZFYAQMZSA-N 0.000 description 1
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 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
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- GMYSJXCHTSBPCK-UHFFFAOYSA-N 3-ethyl-2h-1,3-thiazole Chemical compound CCN1CSC=C1 GMYSJXCHTSBPCK-UHFFFAOYSA-N 0.000 description 1
- PYUQCOIVVOLGJK-UHFFFAOYSA-N 3-methyl-4h-1,2-oxazol-5-one Chemical compound CC1=NOC(=O)C1 PYUQCOIVVOLGJK-UHFFFAOYSA-N 0.000 description 1
- IHKNLPPRTQQACK-UHFFFAOYSA-N 3-phenyl-4h-1,2-oxazol-5-one Chemical compound O1C(=O)CC(C=2C=CC=CC=2)=N1 IHKNLPPRTQQACK-UHFFFAOYSA-N 0.000 description 1
- UWSONZCNXUSTKW-UHFFFAOYSA-N 4,5-Dimethylthiazole Chemical compound CC=1N=CSC=1C UWSONZCNXUSTKW-UHFFFAOYSA-N 0.000 description 1
- IFEPGHPDQJOYGG-UHFFFAOYSA-N 4-chloro-1,3-benzothiazole Chemical compound ClC1=CC=CC2=C1N=CS2 IFEPGHPDQJOYGG-UHFFFAOYSA-N 0.000 description 1
- PIUXNZAIHQAHBY-UHFFFAOYSA-N 4-methyl-1,3-benzothiazole Chemical compound CC1=CC=CC2=C1N=CS2 PIUXNZAIHQAHBY-UHFFFAOYSA-N 0.000 description 1
- KXCQDIWJQBSUJF-UHFFFAOYSA-N 4-phenyl-1,3-thiazole Chemical compound S1C=NC(C=2C=CC=CC=2)=C1 KXCQDIWJQBSUJF-UHFFFAOYSA-N 0.000 description 1
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- YTSFYTDPSSFCLU-UHFFFAOYSA-N 5-chloro-1,3-benzothiazole Chemical compound ClC1=CC=C2SC=NC2=C1 YTSFYTDPSSFCLU-UHFFFAOYSA-N 0.000 description 1
- RLYUNPNLXMSXAX-UHFFFAOYSA-N 5-methylthiazole Chemical compound CC1=CN=CS1 RLYUNPNLXMSXAX-UHFFFAOYSA-N 0.000 description 1
- 125000004070 6 membered heterocyclic group Chemical group 0.000 description 1
- AIBQGOMAISTKSR-UHFFFAOYSA-N 6-chloro-1,3-benzothiazole Chemical compound ClC1=CC=C2N=CSC2=C1 AIBQGOMAISTKSR-UHFFFAOYSA-N 0.000 description 1
- QLUFBCVWKTWKBF-UHFFFAOYSA-N 6-nitro-1,3-benzothiazole Chemical compound [O-][N+](=O)C1=CC=C2N=CSC2=C1 QLUFBCVWKTWKBF-UHFFFAOYSA-N 0.000 description 1
- RXEDQOMFMWCKFW-UHFFFAOYSA-N 7-chloro-1,3-benzothiazole Chemical compound ClC1=CC=CC2=C1SC=N2 RXEDQOMFMWCKFW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VPLRCJUDJZSLKO-UHFFFAOYSA-N C(N=C1)=C[S+]1C1=CC=CC=C1 Chemical compound C(N=C1)=C[S+]1C1=CC=CC=C1 VPLRCJUDJZSLKO-UHFFFAOYSA-N 0.000 description 1
- SJLJHVITDDTVMW-UHFFFAOYSA-N C[S+]1C2=CC=CC=C2N=C1 Chemical compound C[S+]1C2=CC=CC=C2N=C1 SJLJHVITDDTVMW-UHFFFAOYSA-N 0.000 description 1
- 229910021555 Chromium Chloride Inorganic materials 0.000 description 1
- 229910021584 Cobalt(II) iodide Inorganic materials 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 229910052770 Uranium Inorganic materials 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
- OTNSELQCFOLCCA-UHFFFAOYSA-N [1,3]thiazolo[4,5-b]quinoline Chemical class C1=CC=C2C=C(SC=N3)C3=NC2=C1 OTNSELQCFOLCCA-UHFFFAOYSA-N 0.000 description 1
- CIUQDSCDWFSTQR-UHFFFAOYSA-N [C]1=CC=CC=C1 Chemical compound [C]1=CC=CC=C1 CIUQDSCDWFSTQR-UHFFFAOYSA-N 0.000 description 1
- YKZHWMWLKPZPFY-UHFFFAOYSA-N [O-][N+]([S+]1C(C=CC=C2)=C2N=C1)=O Chemical compound [O-][N+]([S+]1C(C=CC=C2)=C2N=C1)=O YKZHWMWLKPZPFY-UHFFFAOYSA-N 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 125000005041 acyloxyalkyl group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005078 alkoxycarbonylalkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003868 ammonium compounds Chemical class 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000008135 aqueous vehicle Substances 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
- HNYOPLTXPVRDBG-UHFFFAOYSA-N barbituric acid Chemical compound O=C1CC(=O)NC(=O)N1 HNYOPLTXPVRDBG-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910000085 borane Inorganic materials 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 125000004181 carboxyalkyl group Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 125000000068 chlorophenyl group Chemical group 0.000 description 1
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 description 1
- WYYQVWLEPYFFLP-UHFFFAOYSA-K chromium(3+);triacetate Chemical compound [Cr+3].CC([O-])=O.CC([O-])=O.CC([O-])=O WYYQVWLEPYFFLP-UHFFFAOYSA-K 0.000 description 1
- PPUZYFWVBLIDMP-UHFFFAOYSA-K chromium(3+);triiodide Chemical compound I[Cr](I)I PPUZYFWVBLIDMP-UHFFFAOYSA-K 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- XZQOHYZUWTWZBL-UHFFFAOYSA-L chromium(ii) bromide Chemical compound [Cr+2].[Br-].[Br-] XZQOHYZUWTWZBL-UHFFFAOYSA-L 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- 229940097267 cobaltous chloride Drugs 0.000 description 1
- 229940045032 cobaltous nitrate Drugs 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 description 1
- CPMVCRMQKZREQQ-UHFFFAOYSA-L ctk4c8528 Chemical compound [Ca+2].[O-]S(=O)S([O-])=O CPMVCRMQKZREQQ-UHFFFAOYSA-L 0.000 description 1
- JEVCWSUVFOYBFI-UHFFFAOYSA-N cyanyl Chemical compound N#[C] JEVCWSUVFOYBFI-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 238000000354 decomposition reaction Methods 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
- 125000004663 dialkyl amino group Chemical group 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- CVOQYKPWIVSMDC-UHFFFAOYSA-L dipotassium;butanedioate Chemical compound [K+].[K+].[O-]C(=O)CCC([O-])=O CVOQYKPWIVSMDC-UHFFFAOYSA-L 0.000 description 1
- GRWZHXKQBITJKP-UHFFFAOYSA-N dithionous acid Chemical class OS(=O)S(O)=O GRWZHXKQBITJKP-UHFFFAOYSA-N 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
- 229940046149 ferrous bromide Drugs 0.000 description 1
- 229960002089 ferrous chloride Drugs 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 150000004675 formic acid derivatives Chemical class 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 150000004820 halides 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
- 150000002429 hydrazines Chemical class 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- FLFJVPPJGJSHMF-UHFFFAOYSA-L manganese hypophosphite Chemical compound [Mn+2].[O-]P=O.[O-]P=O FLFJVPPJGJSHMF-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000004095 oxindolyl group Chemical class N1(C(CC2=CC=CC=C12)=O)* 0.000 description 1
- 125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 1
- PQTLYDQECILMMB-UHFFFAOYSA-L platinum(2+);sulfate Chemical compound [Pt+2].[O-]S([O-])(=O)=O PQTLYDQECILMMB-UHFFFAOYSA-L 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229960003975 potassium Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- HEZHYQDYRPUXNJ-UHFFFAOYSA-L potassium dithionite Chemical compound [K+].[K+].[O-]S(=O)S([O-])=O HEZHYQDYRPUXNJ-UHFFFAOYSA-L 0.000 description 1
- 229910001380 potassium hypophosphite Inorganic materials 0.000 description 1
- CRGPNLUFHHUKCM-UHFFFAOYSA-M potassium phosphinate Chemical compound [K+].[O-]P=O CRGPNLUFHHUKCM-UHFFFAOYSA-M 0.000 description 1
- FIJPWGLOBMXXSF-UHFFFAOYSA-M potassium;2-hydroxyacetate Chemical compound [K+].OCC([O-])=O FIJPWGLOBMXXSF-UHFFFAOYSA-M 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- HAAYBYDROVFKPU-UHFFFAOYSA-N silver;azane;nitrate Chemical compound N.N.[Ag+].[O-][N+]([O-])=O HAAYBYDROVFKPU-UHFFFAOYSA-N 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229960001790 sodium citrate Drugs 0.000 description 1
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 1
- 229940023144 sodium glycolate Drugs 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 229940074404 sodium succinate Drugs 0.000 description 1
- ZDQYSKICYIVCPN-UHFFFAOYSA-L sodium succinate (anhydrous) Chemical compound [Na+].[Na+].[O-]C(=O)CCC([O-])=O ZDQYSKICYIVCPN-UHFFFAOYSA-L 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- JEJAMASKDTUEBZ-UHFFFAOYSA-N tris(1,1,3-tribromo-2,2-dimethylpropyl) phosphate Chemical compound BrCC(C)(C)C(Br)(Br)OP(=O)(OC(Br)(Br)C(C)(C)CBr)OC(Br)(Br)C(C)(C)CBr JEJAMASKDTUEBZ-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 230000000007 visual effect Effects 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
- G03C1/72—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705
- G03C1/73—Photosensitive compositions not covered by the groups G03C1/005 - G03C1/705 containing organic compounds
-
- 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
- G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
- G03C5/58—Processes for obtaining metallic images by vapour deposition or physical development
Definitions
- Physical development comprises the intensification or development of catalytic nuclei e.g., by treating the nuclei with a developer solution which contains a reducible metal compound and a reducing agent.
- a developer solution which contains a reducible metal compound and a reducing agent.
- virtually all of the metal in the resultant visual image is formed by the selective reduction of metal ions supplied by the reducible metal compound in the developer solution.
- the physical developer solution be so formulated that it is stable under storage conditions, but that in the presence of a catalyst, such as a metallic latent image, it decomposes and deposits reduced metal on the catalytic sites.
- a catalyst such as a metallic latent image
- the catalytic nuclei used in the formation of the latent image are generated by several techniques.
- One method involves the formation of active sites for subsequent physical development by using a light sensitive metal salt as the nucleating agent precursor. When subjected to actinic radiation, the metal in the salt is reduced to zero valency, thus forming the nuclei or active sites for further physical development.
- a disadvantage in the use of this technique is that very often, long exposure times are required.
- a second method involves the use of metal salts as nucleating agent precursors which are not necessarily light sensitive.
- a light sensitive sensitizer is used in conjunction with these compounds. When subjected to actinic radiation, the sensitizer reduces the metal in the salt to the elemental state thus providing active sites for subsequent physical development. Difficulty has been encountered in finding sensitizers which are stable upon storing. Photographic elements containing such sensitizers frequently have exhibited extremely poor keeping characteristics.
- An additional object of the invention is to provide novel photographic elements having good keeping properties.
- photographic elements having a support which contains (a) a metallic salt nucleating agent precursor which is capable of forming active or catalytic sites for subsequent physical development and (b) a sensitizer which is a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by either an alkoxy group or an acyloxy group.
- a metallic salt nucleating agent precursor which is capable of forming active or catalytic sites for subsequent physical development
- a sensitizer which is a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by either an alkoxy group or an acyloxy group.
- the sensitizer causes the metallic salt nucleating agent precursor to form catalytic sites for physical development.
- the action of the light-struck sensitizer on the metal salt comprising the nucleating agent precursor causes reduction of the metal in the salt. It is the metal in reduced form which provides the active or catalytic sites.
- the subsequent physical development may be accomplished for example with any of the conventional physical developers.
- novel photographic elements of this invention provides reproductions having high resolution. Additionally, such elements are characterized by a high-inherent photolytic speed which is directly attributable to the high speeds of the sensitizers employed.
- Another advantage residing in the use of the described elements is their broad spectral response.
- the various sensitizers which can be used in the elements have varying spectral responses, as such, a particular sensitizer or combination of sensitizers can be used depending on the nature of the activating radiation.
- the sensitizers incorporated in the elements of the invention are relatively stable under ambient conditions and thus the novel elements have good keeping" properties.
- An additional advantage is that the metallic salt nucleating agent need not be a light sensitive material. Thus, a host of inexpensive metal salts can be used as nucleating agents provided they are responsive to the sensitizers described herein.
- Typical sensitizing compounds of this invention can have one of the general formulae:
- R can be any of the following:
- a methine linkage terminated by a heterocyclic nucleus of the type contained in cyanine dyes, e.g., those set forth in Mees and James, The Theory of the Photographic Process," MacMillan, 3rd ed., pp. 198-232;
- alkyl radical preferably containing one to eight carbon atoms including a substituted alkyl radical
- an aryl radical including a substituted aryl radical such as a phenyl radical, a naphthyl radical, a tolyl radical, etc.;
- acyl radical having the formula wherein R is hydrogen, acyl or alkyl;
- a styryl radical including substituted styryl radicals e.g.,
- R is hydrogen, alkyl, aryl, amino including dialkylamino such as dimethylamino;
- R can be either of the following:
- a methine linkage terminated by a heterocyclic nucleus of the type contained in merocyanine dyes, e.g., those set forth in Mees and James (cited above); the methine linkage can be substituted or unsubstituted; or
- an allylidene radical including a substituted allylidene radical such as a cyanoallylidene radical, an alkylcarboxy-allylidene radical or an alkylsulfonylallylidene radical;
- R can be either:
- an alkyl radical preferably having one to eight carbon atoms such as methyl, propyl, ethyl, butyl, etc., including a substituted alkyl radical such as sulfoalkyl, e.g., (CH an aralkyl, e.g., benzyl or pyridinato-oxyalkyl salt, e.g., (CH -OY wherein Y is substituted or unsubstituted pyridinium salt; or
- R is an alkyl radical preferably having one to eight carbon atoms or aryl radical, e.g., methyl, ethyl, propyl, butyl, phenyl, naphthyl, etc.
- Z represents the atoms necessary to complete a to 6 membered heterocyclic nucleus including a substituted heterocyclic nucleus which nucleus can contain at least one additional hetero atom such as oxygen, sulfur, selenium or nitrogen, e.g., a pyridine nucleus, a quinoline nucleus, etc and
- X represents an acid anion, e.g,, chloride, bromide, iodide, perchlorate, sulfamate, thiocyanate, p-toluenesulfonate. methyl sulfate, tetrafluoroborate, etc.
- the preferred sentitizing compounds of the invention have one of the following structures:
- Q Q and Q each represent the nonmetallic atoms necessary to complete a sensitizing or desensitizing nucleus containing five or six atoms in the heterocyclic ring, which nucleus can contain at least one additional hetero atom such as oxygen, sulfur, selenium or nitrogen, i.e., a nucleus of the type used in the production of cyanine dyes, such as the following representative nuclei: a thiazole nucleus, e.g., thiazole, 4-methylthiazole, 3-ethylthiazole, 4-phenylthiazole, 5- methylthiazole, S-phenylthiazole, 4,5-dimethylthiazole, 4,5-
- imidazole l-alkylimidazole, l-alkyl-4-phenylimida2ole, lalkyl-4,S-dimethylimidazole, benzimidazole, l-alkylbenzimidazole, l-alkyl- 5-nitrobenzimidazole, l-aryl-5,6-
- dichlorobenzimidazole 1-alkyl-a-naphthimidazole, l-aryl-flnaphthimidazole, l-alkyl-5-methoxy-a-naphthimidazole, or, an imidazo[4,5-b]quinoxaline nucleus, e.g., l-alkylimidazo[4,5-b]quinoxaline such as 1-ethylimidazo[4,5- blquinoxaline, 6-chloro-l-ethylimidazo[4,5-b1-quinoxaline, etc., l-alkenylimidazo[4,5-b]quinoxaline such as l-allylimidazo[4,S-blquinoxaline, 6-chloro-l-allylimidazo-[4,5- b]quinoxaline, etc., l-arylimidazo[4,5-blquinoxaline, such as l-phenylimidazol
- nucleating agent precursor Any metallic salt capable of being reduced by the lightstruck sensitizer to form active or catalytic sites for physical development can be used as the nucleating agent precursor.
- nucleating agent includes the metal salt in reduced form which furnishes the active or catalytic sites for subsequent physical development.
- Typical metal salts include salts of those metals in (a) Group VIII such as nickel, cobalt, iron, platinum, palladium, etc., (b) Group 11) such as copper, silver, gold, etc., (c) llb e.g., zinc, mercury, etc., (d) lVa e.g., tin, lead, etc., and (e) Vlb e.g., chromium (in accordance with the Periodic Table of the Elements, Handbook of Chemistry and Physics, 38th edition, pp. 394-95).
- the anions employed with the metals are generally chosen based on the desired solubility of the metal salt.
- Typical anions include halides, e.g., chloride, bromide, iodide, etc., sulfates, nitrates, salts of organic acids, e.g., acetate, formates, etc., oxides, hydroxides, etc.
- Typical metal salts useful in the elements of this invention are further described in any of the literature sources regarding physical development. Typical descriptions are found in patents such as U.S. Pat. No. 3,404,980; British Pat. No. 1,143,021, U.S. Ser. No. 653,025 filed July 13, 1967 by Yudelson et a]; U.S. Ser. No. 723,278 filed Apr. 22, 1968 by Yudelson; U.S. Ser. No. 778,323 filed Nov. 22, 1968 by Yudelson et al, Photographic Science and Engineering, Volume 13, No. 1.
- the mechanism or theory pertaining to the function of the sensitizer on the metal salt is not completely understood. However, it is believed that when the sensitizer is struck by actinic radiation, it is decomposed or fragmented to several different factions. Some of these factions are reducing agents for the metal salt. The particular route of the fragmentation reac tion is believed to be somewhat dependent upon the structure of the original compound. However, based upon observations, it is believed that the route followed, when a sensitizer of this invention (such as the one given below) is exposed to actinic radiation, is the following:
- aldehyde fragment is believed to cause the reduction of the metal salt so as to form active sites for physical development.
- a sensitizer is dispersed in a suitable binder and then the mixture coated on a support using any of the known coating methods.
- Supporting materials can be any of the known materials for this purpose, such as film base (e.g., cellulose nitrate film, cellulose ester film, etc), plastic supports (e.g., polyethylene, polyethylene terephthalate, etc.) paper including resin treated papers, metal, glass, and the like.
- Suitable binders for incorporating the organic compounds include any of the water-permeable materials, such as gelatin or other hydrophilic materials. such as collodion, albumin, cellulose derivatives, synthetic resins such as poly(vinyl alcohol) and the like.
- the binder and sensitizer are dispersed in a suitable aqueous vehicle such as water.
- a suitable aqueous vehicle such as water.
- the amount of sensitizer employed ranges from about 0.1% to about 5.0% by weight based on the weight of the total coating composition.
- the amount of vehicle employed ranges from about 5.0% to about 60% by weight, based on the weight of the total coating composition.
- Coating thicknesses of the composition on a support can vary widely. Normally, a wet coating thickness in the range of about 0.001 inch to about 0.01 inch is useful in the practice of this invention. A preferred range of coating thickness is from about 0.002 inch to about 0,006 inch before drying although such thicknesses can vary widely depending on the particular application desired for the photographic element. After the composition is coated, the elements are dried at slightly elevated temperatures for one hour or more.
- the photographic elements prepared in the manner described above are then exposed in an imagewise manner to a pattern of actinic radiation.
- the radiation causes the sensitizer to become an active reducing agent in the areas which have been exposed.
- the exposure time varies depending on the nature of the light source and the sensitizer used. Generally, however, exposure times vary from about 0.1 to about 60 or more seconds.
- the element is contacted with a solution of one of the metallic salt nucleating agent precursors described above.
- the contacting can be accomplished by any of several known techniques such as swabbing the solution on the surface of the element or by immersing the element in the solution.
- the metal salt is reduced by the sensitizer in the exposed areas of the element thus creating active or catalytic sites for subsequent physical development.
- the photographic element is prepared by coating a composition containing a binder, a sensitizer, a carrier and the metallic salt nucleating agent precursor.
- the nucleating agent precursor is present in an amount ranging from about 0.1% to about 5.0% by weight of the total coating composition. Exposure of an element of this type causes activation of the sensitizer in the light struck regions and immediate successive reduction of the metal salt to form active nuclei. In this embodiment, a separate solution containing the nucleating agent precursor is not necessary.
- the exposed element containing the active or catalytic sites is then developed by any of the known physical development processes.
- the particular process or physical developer employed is dependent on the nature of the active sites-created, certain physical developers being more suitable for specific classes of reduced metallic salts than others.
- Typical physical developers are described in U.S. Pat. No. 3,404,980, British Pat. No. 1,143,021, U.S. Ser. No. 653,025 filed July 13, 1967 by Yudelson et al, U.S. Ser. No. 723,278 filed Apr. 22, 1968 by Yudelson, U.S. Ser. No. 778,323 filed Nov. 22, 1968 by Yudelson et al.
- the purpose of the physical development is to amplify the image generated by the catalytic sites.
- the physical developer which is used to produce a visible image can comprise an aqueous bath in which is dissolved a salt of a heavy metal, a complexing agent for the metal ion, and a reducing agent.
- the physical developer bath is chosen so that deposition of the heavy metal from the bath is catalyzed by the active sites.
- the heavy metal deposited from the bath must itself be autocatalytic; that is, it must act as a catalyst for further deposition of metal from the developer. This is necessary in order that deposition and development will continue after the active sites are enveloped with heavy metal.
- suitable heavy metals can be selected from Group Vlll metals such as nickel, cobalt, iron, palladium and platinum, Group VIB metals such as chromium and Group [B metals such as copper, silver and gold. Almost any heavy metal salt which is a source of the desired heavy metal ions can be employed.
- Suitable heavy metal salts useful in the invention include heavy metal halides such as cobaltous bromide, cobaltous chloride, cobaltous iodide, ferrous bromide, ferrous chloride, chromium bromide, chromium chloride, chromium iodide, copper chloride, silver bromide, silver chloride, silver iodide, gold chloride, palladium chloride and platinum chloride, heavy metal sulfates such as nickel sulfate, ferrous sulfate, cobaltous sulfate, chromium sulfate, copper sulfate, palladium sulfate and platinum sulfate, heavy metal nitrates such as nickel nitrate, ferrous nitrate, cobaltous nitrate, chromium nitrate and copper nitrate, and heavy metal salts of organic acids such as ferrous acetate, cobaltous acetate, chromium
- Baths can be formulated based on a single heavy metal or based on mixtures of heavy metals. When more than one heavy metal is employed in the bath, the image which is deposited will generally be an alloy of the two metals.
- Physical developers based on noble metals such as silver, gold and platinum are relatively unstable and cannot be stored for long periods oftime. However, such physical developers are operative in the processes of this invention and can be employed if the developer bath is prepared shortly before use.
- the complexing agent employed in the physical developer bath should tie up the metal ions so that they show a lessened tendency to be reduced spontaneously. However, the complexing agent should not bind the metal ions so tightly that they will be unable to be reduced and deposited on the latent image sites in the presence of the catalyst.
- Suitable complexing agents include ammonium compounds such as ammonium hydroxide or chloride, organic acids such as aspartic acid, malic acid, citric acid, glycolic acid, salts of organic acids such as sodium citrate, potassium citrate, sodium glycolate, potassium glycolate, sodium succinate, potassium succinate, potassiurn sodium tartrate, etc.
- a single complexing agent can be used or a combination of more than one complexing agent can be incorporated in the physical developer bath.
- the reducing agent can be any compound which provides a ready source of electrons for the reduction of the metal ions and which does not otherwise interfere with development.
- a general criteria for a reducing agent useful in the physical developers of the present invention is that the potential of the chemical coupler of the reducing agent, written as follows:
- Ni 2 Ni 2 electrons is +0.277 volts for acidic solutions. It is necessary for the reducing agent to possess a potential that is greater, i.e., more positive, than +0.277 volts in order that it be capable of reducing nickel ions in the bath.
- Suitable reducing agents include formaldehyde, hypophosphites such as sodium hypophosphite, manganous hypophosphite, potassium hypophosphite, etc., hydrosulfites such as sodium hydrosulfite, potassium hydrosulfite, calcium hydrosulfite, etc., borohydrides such as sodium borohydride, potassium borohydride, etc., borane amines such as dimethylborane amine, etc., hydrazines, and the like.
- hypophosphites such as sodium hypophosphite, manganous hypophosphite, potassium hypophosphite, etc.
- hydrosulfites such as sodium hydrosulfite, potassium hydrosulfite, calcium hydrosulfite, etc.
- borohydrides such as sodium borohydride, potassium borohydride, etc.
- borane amines such as dimethylborane amine, etc., hydrazines, and the like.
- the proportions in which the various components of the physical developer are present in the bath can vary over a wide range. Suitable concentrations of metal salt in the developer bath are in the range of from about 0.01 to about 1.0 mole of metal salt per liter of bath. The upper limit of concentration is controlled by the solubility of the particular metal salt employed. Preferably, the bath is between about 0.05 molar and 0.25 molar with respect to metal salt.
- the relative proportions of metal salt and complexing agent are dependent upon the particular metal salt or salts and the particular complexing agent or agents which are employed. As a general rule sufficient complexing agent should be incorporated to bind the metal ions and lessen the tendency of the metal ions to be reduced prior to use of the developer.
- the amount of complexing agent present can vary from about 0.2 mole to about 10 moles of complexing agent per mole of metal salt present.
- the reducing agent can be present in amounts of from about 0.1 moles to about 5 moles of reducing agent per mole of metal salt present.
- EXAMPLE 1 A solution containing 0.025 grams of 2-B-anilinovinyl-lmethoxypyridinium p-toluenesulfonate (Compound 26) and 5.0 grams of a 10 percent aqueous gelatin solution is coated on paper using a 3 mil coating knife. The element is dried and then exposed to a negative image transparency for about 10 seconds using a 400 watt mercury light source at a distance of 1.5 inch. The exposed element is then swabbed with an ammoniacal silver nitrate solution (prepared by adding 0.lN AgNO solution to a 28% NH OH solution in an amount suffcient to cause the resultant cloudy mixture to become clear), washed with water and dried. The active sites thus created are next physically developed by immersing the element in a silver physical developer such as that described in U.S. Pat. No. 3,409,432 (Example 2). A dark brown image is obtained in those areas which had been initially exposed.
- a silver physical developer such as
- Example 1 is repeated except the active sites are formed by swabbing the surface of the exposed element with an acidic solution of palladium chloride (0.10 gm. PdCl 4.0 ml. of 0.01 N HCl). After drying, the element is physically developed in the same manner as described in Example I. A sharp, dark image is obtained in those areas which had been initially exposed.
- an acidic solution of palladium chloride (0.10 gm. PdCl 4.0 ml. of 0.01 N HCl.
- Example 2 is repeated except that the active sites are physically developed using a nickel developer as described in Example 4 of U.S. Ser. No. 778,323 filed Nov. 22, 1968 by Yudelson et al. The reproduction once again has a sharp dark image.
- Example 2 is repeated except the sensitizer employed is 3- ethyll -methoxyoxa-2 '-pyridocarbocyanine perchlorate (Compound 1), Again a reproduction is obtained having sharp, dark images.
- the sensitizer employed is 3- ethyll -methoxyoxa-2 '-pyridocarbocyanine perchlorate (Compound 1), Again a reproduction is obtained having sharp, dark images.
- Example 1 is repeated using 3'-ethyl-l-methoxy-2- pyridothiacyanine iodide (Compound 3) as the sensitizer. A very satisfactory reproduction is obtained.
- Compound 3 3'-ethyl-l-methoxy-2- pyridothiacyanine iodide
- Example 3 is repeated using various sensitizers.
- the sensitizer used and the quality of the reproduction are described in the following Table I.
- Example Compound image Quality 6 6 Good 7 9 Good 8 14 Good 9 14 Good l 16 Good l l 18 Good l2 19 Good
- EXAMPLE 13 A solution containing 0.025 grams of 2-B-anilinovnyl-lmethoxypyridinium p-toluenesulfonate, 5.0 grams of a percent aqueous gelatin solution and 0.10 grams of palladium chloride is coated on paper using a 3 mil. coating knife. The element is dried and then exposed in a manner described in Example 1. The active sites created by the exposure are physically developed with the developer described in Example 6 of U.S. Pat. No. 3,404,980. A good dense image is obtained.
- a photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group.
- a photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound having a formula selected from the group consisting of:
- R is selected from the group consisting of:
- R is selected from the group consisting of:
- R is selected from the group consisting of:
- X is an acid anion
- Z represents the atoms necessary to complete a 5 to 6 membered heterocyclic nucleus.
- Z represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus and a quinoline nucleus.
- R is a methine linkage terminated by a 5 to 6 membered heterocyclic nucleus.
- nucleating agent precursor is a salt of a metal selected from the group consisting of silver, gold, copper, platinum, palladium, iron, nickel, cobalt, chromium, mercury, lead, tin and zinc.
- a photographic element comprising 7 a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosen- 0,, Q Q and Q each represent the nonmetallic atoms necessary to complete a 5 to 6 membered heterocyclic nucleus;
- n is a positive integer from i to 4.
- n is a positive integer from 1 to 3;
- R is an alkyleneoxy radical having one to eight carbon atoms in the alkylene chain
- g is a positive integer from 1 to 2;
- X- is an acid anion
- L is a methine linkage
- R is selected from the group consisting of an alkyl radical and an acyl radical
- R and R are each selected from the group consisting of an aryl radical, a hydrogen atom and an alkyl radical;
- R is selected from the group consisting of an alkyl radical, an alkenyl radical, an aryl radical and an alkoxy radical
- G is selected from the group consisting of an anilinovinyl radical and an aryl radical
- R and R are each a cyano radical.
- R, R R;,, Q Q L, X, g and n are defined in claim 6.
- R R 0,, Q X and R are defined in claim 6.
- said metallic salt nucleating agent precursor is a salt of a metal selected from the group consisting of silver, gold, copper, platinum, palladium, iron, nickel, cobalt, chromium, mercury, lead, tin and zinc.
- a photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound which is a Z-B-anilinovinyl-l-methoX- ypyridinium salt.
- a process for forming a physically developable latent image comprising (a) providing a photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group, and (b) exposing said element to a pattern of actinic radiation thus forming a physically developable latent image.
- a process for forming a physically developable latent image comprising (a) providing a photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound having a formula selected from the group consisting of:
- R is selected from the group consisting of:
- R is selected from the group consisting of:
- Z represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus and a quinoline nucleus.
- R is a methine linkage terminated by a 5 to 6 membered heterocyclic nucleus.
- nucleating agent precursor is a salt of a metal selected from the group consisting of silver, gold, copper, platinum, palladium, iron, nickel, cobalt, chromium, mercury, lead, tin and zinc.
- a process for forming a physically developable latent image comprising (a) providing a photographic element comprising a support having thereon a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group, (b) exposing said element to a pattern of actinic radiation, and (c) contacting the exposed element with a solution of a metallic salt nucleating agent precursor thus forming a physically developable latent image.
- a process for forming a physically developable latent image comprising (a) providing a photographic element comprising a support having thereon a photosensitive compound having a formula selected from the group consisting of:
- R is selected from the group consisting of:
- R is selected from the group consisting of:
- R is selected from the group consisting of:
- X is an acid anion
- Z represents the atoms necessary to complete a 5 to 6 membered heterocyclic nucleus, (b) exposing said element to a pattern of actinic radiation and (c) contacting the exposed element with a solution of a metallic salt nucleating agent precursor thus forming a physically developable latent image.
- Z represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus and a quinoline nucleus.
- R is a methine linkage terminated by a 5 to 6 membered heterocyclic nucleus.
- nucleating agent precursor is a salt of a metal selected from the group consisting of silver, gold, copper, platinum, palladium, iron, nickel, cobalt, chromium, mercury, lead, tin and zinc.
- a photographic composition comprising a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group.
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Abstract
Novel photographic elements and processes are described. Active sites for physical development are created by the action of a sensitizing compound on a reducible metal salt.
Description
United States Patent McNally, Jr. et a1.
[54] PHOTOGRAPHIC ELEMENTS AND 211 App]. No.: 854,719
[52] US. Cl. ..96/48 PD, 96/66, 96/88 [51] Int. Cl [58] Field of Search ..96/48 PD, 66, 27, 64, 88
[4 1 Mar. 14, 1972 [56] References Cited UNITED STATES PATENTS 3,149,970 9/1964 Weyde ..96/48 3,291,608 12/1966 Elins ..96/66 3,404,980 10/1968 Gilman et al. ..96/48 3,409,432 11/1968 Gilman ..96/48 Primary Examiner-John T. Goolkasian Assistant Examiner-M. E. McCamish Att0rney-Wi1liam H. .l. Kline, James R. Frederick and Fred L. Denson [57] ABSTRACT Novel photographic elements and processes are described. Active sites for physical development are created by the action of a sensitizing compound on a reducible metal salt.
25 Claims, No Drawings This invention relates to novel photographic elements, compositions and processes.
Physical development comprises the intensification or development of catalytic nuclei e.g., by treating the nuclei with a developer solution which contains a reducible metal compound and a reducing agent. In physical development, virtually all of the metal in the resultant visual image is formed by the selective reduction of metal ions supplied by the reducible metal compound in the developer solution. It is desirable that the physical developer solution be so formulated that it is stable under storage conditions, but that in the presence of a catalyst, such as a metallic latent image, it decomposes and deposits reduced metal on the catalytic sites. Once a catalytic site is enveloped with metal deposited from developer solution, it is essential that the reduced metal be autocatalytic, that is it too must catalyze the decomposition of the physical developer solution.
The catalytic nuclei used in the formation of the latent image are generated by several techniques. One method involves the formation of active sites for subsequent physical development by using a light sensitive metal salt as the nucleating agent precursor. When subjected to actinic radiation, the metal in the salt is reduced to zero valency, thus forming the nuclei or active sites for further physical development. A disadvantage in the use of this technique is that very often, long exposure times are required. A second method involves the use of metal salts as nucleating agent precursors which are not necessarily light sensitive. A light sensitive sensitizer is used in conjunction with these compounds. When subjected to actinic radiation, the sensitizer reduces the metal in the salt to the elemental state thus providing active sites for subsequent physical development. Difficulty has been encountered in finding sensitizers which are stable upon storing. Photographic elements containing such sensitizers frequently have exhibited extremely poor keeping characteristics.
It is therefore an object of this invention to provide novel photographic elements which are developable with physical developers.
It is a further object of this invention to provide photographic processes utilizing the novel elements described herein.
It is a further object of this invention to provide novel photographic compositions.
An additional object of the invention is to provide novel photographic elements having good keeping properties.
It is still another object of this invention to provide novel elements having good photographic speeds.
These and other objects are accomplished with photographic elements having a support which contains (a) a metallic salt nucleating agent precursor which is capable of forming active or catalytic sites for subsequent physical development and (b) a sensitizer which is a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by either an alkoxy group or an acyloxy group. When such an element is exposed to actinic radiation, the sensitizer causes the metallic salt nucleating agent precursor to form catalytic sites for physical development. The action of the light-struck sensitizer on the metal salt comprising the nucleating agent precursor causes reduction of the metal in the salt. It is the metal in reduced form which provides the active or catalytic sites. The subsequent physical development may be accomplished for example with any of the conventional physical developers.
The use of the novel photographic elements of this invention provides reproductions having high resolution. Additionally, such elements are characterized by a high-inherent photolytic speed which is directly attributable to the high speeds of the sensitizers employed. Another advantage residing in the use of the described elements is their broad spectral response. The various sensitizers which can be used in the elements have varying spectral responses, as such, a particular sensitizer or combination of sensitizers can be used depending on the nature of the activating radiation. The sensitizers incorporated in the elements of the invention are relatively stable under ambient conditions and thus the novel elements have good keeping" properties. An additional advantage is that the metallic salt nucleating agent need not be a light sensitive material. Thus, a host of inexpensive metal salts can be used as nucleating agents provided they are responsive to the sensitizers described herein.
Typical sensitizing compounds of this invention can have one of the general formulae:
wherein:
R can be any of the following:
a. a methine linkage terminated by a heterocyclic nucleus of the type contained in cyanine dyes, e.g., those set forth in Mees and James, The Theory of the Photographic Process," MacMillan, 3rd ed., pp. 198-232; the methine linkage can be substituted or unsubstituted, e.g., CH= C(CH;,)= C(C H,)= CH CH--, CH CH-CH= etc.;
b. an alkyl radical preferably containing one to eight carbon atoms including a substituted alkyl radical;
c. an aryl radical including a substituted aryl radical such as a phenyl radical, a naphthyl radical, a tolyl radical, etc.;
d. a hydrogen atom;
e. an acyl radical having the formula wherein R is hydrogen, acyl or alkyl; or
g. a styryl radical including substituted styryl radicals, e.g.,
wherein R is hydrogen, alkyl, aryl, amino including dialkylamino such as dimethylamino;
R, can be either of the following:
a. a methine linkage terminated by a heterocyclic nucleus of the type contained in merocyanine dyes, e.g., those set forth in Mees and James (cited above); the methine linkage can be substituted or unsubstituted; or
b. an allylidene radical including a substituted allylidene radical such as a cyanoallylidene radical, an alkylcarboxy-allylidene radical or an alkylsulfonylallylidene radical;
R can be either:
a. an alkyl radical preferably having one to eight carbon atoms such as methyl, propyl, ethyl, butyl, etc., including a substituted alkyl radical such as sulfoalkyl, e.g., (CH an aralkyl, e.g., benzyl or pyridinato-oxyalkyl salt, e.g., (CH -OY wherein Y is substituted or unsubstituted pyridinium salt; or
b. an acyl radical, e.g.,
wherein R is an alkyl radical preferably having one to eight carbon atoms or aryl radical, e.g., methyl, ethyl, propyl, butyl, phenyl, naphthyl, etc.
Z represents the atoms necessary to complete a to 6 membered heterocyclic nucleus including a substituted heterocyclic nucleus which nucleus can contain at least one additional hetero atom such as oxygen, sulfur, selenium or nitrogen, e.g., a pyridine nucleus, a quinoline nucleus, etc and X represents an acid anion, e.g,, chloride, bromide, iodide, perchlorate, sulfamate, thiocyanate, p-toluenesulfonate. methyl sulfate, tetrafluoroborate, etc.,
The preferred sentitizing compounds of the invention have one of the following structures:
wherein Q Q and Q each represent the nonmetallic atoms necessary to complete a sensitizing or desensitizing nucleus containing five or six atoms in the heterocyclic ring, which nucleus can contain at least one additional hetero atom such as oxygen, sulfur, selenium or nitrogen, i.e., a nucleus of the type used in the production of cyanine dyes, such as the following representative nuclei: a thiazole nucleus, e.g., thiazole, 4-methylthiazole, 3-ethylthiazole, 4-phenylthiazole, 5- methylthiazole, S-phenylthiazole, 4,5-dimethylthiazole, 4,5-
diphenyithiazole, 4-(Z-thienyl)thiazole, benzothiazole, 4- chlorobenzothiazole, 4- or S-nitrobenzothiazole, 5- chlorobenzothiazole, 6-chlorobenzothiazole, 7- chlorobenzothiazole, 4-methylbenzothiazole, S-methylbenzothiazole, -methylbenzothiazole, 6-nitrobenzothiazole,
5 -bromobenzothiazole, -bromobenzothiazole, 5 -chloro-6- nitrobenzothiazole, 4-phenylbenzothiazole, 4-methoxybenzothiazole, S-rnetho xybenzothiazole 6-methoxbenzoxazole, S-phenylbenzoxazole, S- or -nitrobenzoxazole, 5-chloro-6-nitrobenzoxazole, G-methylbenzoxazolc, 5,6- dimethylbenzoxazole, 4,6-dimethylbenzoxazole, S-methoxybenzoxazole, S-ethoxybenzoxazole, S-chlorobenzoxazole, 6- methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, a-naphthoxazole, ,B-naphthoxazole, nitro group substituted naphthoxazoles, etc.; a selenazole nucleus, eg, 4- methylselenazole, 4-nitroselenazole, 4-phenylselenazole, benzoselenazole, S-chlorobenzoselenazole, S-methoxybenzoselenazole, S-hydroxybenzoselenazole, 5- or 6- nitrobenzoselenazole, 5-chloro-6-nitrobenzoselenazole, tetrahydrobenzoselenazole, a-naphthoselenazole, ,8- naphthoselenazole, nitro group substituted naphthoselenazoles, etc.; a thiazoline nucleus, e.g., thiazoline, 4-methylthiazoline, etc.; a pyridine nucleus, e.g., Z-pyridine, S-methyl-Z-pyridine, 4-pyridine, 3-methyl-4-pyridine, nitro group substituted pyridines, etc.; a quinoline nucleus, e.g., 2- quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6 chloro-2-quinoline, 6-nitro-2-quinoline, 8-chloro-2-quinoline, G-methoxy-Z-quinoline, 8-ethoxy-2-quinoline, 8-hydroxy-2- quinoline, 4-quinoline, 6-methoxy-4-quinoline, 6-nitro-4- quinoline, 7-methyl-4-quinoline, 8-chloro-4-quinoline, lisoquinoline, -nitro-l-isoquinoline, 3 ,4-dihydrol -isoquinoline, 3-isoquinoline, etc.; a 3,3-dialkylindolenine nucleus, preferably having a nitro or cyano substituent, e.g., 3,3- dimethyl-S or 6nitroindolenine, 3,393 -dimethyl-5- or 6- cyano-indolenine, etc.; and, an imidazole nucleus, e.g.,
imidazole, l-alkylimidazole, l-alkyl-4-phenylimida2ole, lalkyl-4,S-dimethylimidazole, benzimidazole, l-alkylbenzimidazole, l-alkyl- 5-nitrobenzimidazole, l-aryl-5,6-
dichlorobenzimidazole, 1-alkyl-a-naphthimidazole, l-aryl-flnaphthimidazole, l-alkyl-5-methoxy-a-naphthimidazole, or, an imidazo[4,5-b]quinoxaline nucleus, e.g., l-alkylimidazo[4,5-b]quinoxaline such as 1-ethylimidazo[4,5- blquinoxaline, 6-chloro-l-ethylimidazo[4,5-b1-quinoxaline, etc., l-alkenylimidazo[4,5-b]quinoxaline such as l-allylimidazo[4,S-blquinoxaline, 6-chloro-l-allylimidazo-[4,5- b]quinoxaline, etc., l-arylimidazo[4,5-blquinoxaline, such as l-phenylimidazol 4,5-b]quinoxaline, 6-chlorol-phenylimidazo[4,5-blquinoxaline, etc.; a 3,3-dialkyl-3H-pyrrolo-[ 2,3-b]pyridine nucleus, e.g., 3,3-dimethyl-3H-pyrrolo[2,3-b1- pyridine, 3,3-diethyl-3H-pyrrolo[2,3-b1pyridine, etc.; a thiazolo[4,5-b]quinoline nucleus; R represents an alkyl group, including substituted alkyl (preferably a lower alkyl containing from one to four carbon atoms), e.g., methyl, ethyl, propyl, isopropyl, butyl, hexyl, cyclohexyl, decyl, dodecyl, etc., and substituted alkyl groups (preferably a substituted lower alkyl containing from one to four carbon atoms), such as a hydroxyalkyl group, e.g., ,B-hydroxyethyl, w-hydroxybutyl, etc., an alkoxyalkyl group, e.g., B-methoxyethyl, w-butoxybutyl, etc., a carboxyalkyl group, e.g., fi-carboxyethyl, m-carboxybutyl, etc., an alkoxy group, e.g., methoxy, ethoxy, etc., a sulfoalkyl group, e.g., B-sulfoethyl, m-sulfobutyl, etc., a sulfatoalkyl group, eg, ,B-sulfatoethyl, w-sulfatobutyl, etc., an acyloxyalkyl group, e.g., B-acetoxyethyl, 'y-acetoxypropyl, o)- butyryloxybutyl, etc,, an alkoxycarbonylalkyl group, e.g., B- methoxycarbonylethyl, w-ethoxycarbonylbutyl, etc., or an aralkyl group, eg, benzyl, phenethyl, etc.; an alkenyl group, e.g., allyl, l-propenyl, Z-butenyl, etc., or an aryl group, eg., phenyl, tolyl, naphthyl, methoxyphenyl, chlorophenyl, etc.; 0, represents the nonmetallic atoms required to complete a 5 to 6 membered heterocyclic nucleus, typically containing a hetero atom selected from nitrogen, sulfur, selenium, and oxygen, such as a 2-pyrazolin-5-one nucleus (e.g,, 3-methyl-lphenyl-2-pyrazolin-5-one, l-phenyl-2-pyrazolin-5-one, l-(2- benzothiazolyl)-3-methyl-2-pyrazolin-5-one, etc.); an isoxazolone nucleus (e.g., 3-phenyl-5-(4H)-isoxazolone, 3- methyl-5-(4H )-isoxazolone, 3-methy1-5-( 4H)-isoxazolone, etc.); an oxindole nucleus (e.g., l-alkyl-2,3-dihydro-2-oxindoles, etc), a 2,4,-triketohexahydropyrimidine nucleus (e.g., barbituric acid or Z-thiobarbituric acid as well as their l-alkyl (e.g,, l-methyl, l-ethyl, l-propyl, l-heptyl, etc.) or l,3-dialkyl (e.g., l,3-dimethyl, l,3-diethyl, l,3-dipropy], l,3-diisopropyl, l,3-dicyclohexyl, l,3di(B-methoxyethyl), etc.) or l,3-diaryl (e.g., l,3-diphenyl, 1,3-di(p-chlorophenyl), l,3-di(p-ethox- 39. 3-ethyl-5-[( l-methoxy-2( 1H )-pyridylidene)ethylidene1rhodanine 40. l,3-diethyl--I( l-methoxy-2( 1H )-pyridylidene)ethylidene ]-barbituric acid 41. 2-( 3 ,3-dicyanoalkylidene l -methoxyl ,2- dihydropyridine 42. 2-[( l-methoxy-2( l H )-pyridylidene )-ethylidene]benzo [b]-thiophen-3 2H )-one- 1 ,1 -dioxide 43. 3-cyano-5-{( l-methoxy-2( 1H )-pyridylidene )ethylidene 4-phenyl-2(5l-l)-furanone Any metallic salt capable of being reduced by the lightstruck sensitizer to form active or catalytic sites for physical development can be used as the nucleating agent precursor. The term nucleating agent" as used herein includes the metal salt in reduced form which furnishes the active or catalytic sites for subsequent physical development. Typical metal salts include salts of those metals in (a) Group VIII such as nickel, cobalt, iron, platinum, palladium, etc., (b) Group 11) such as copper, silver, gold, etc., (c) llb e.g., zinc, mercury, etc., (d) lVa e.g., tin, lead, etc., and (e) Vlb e.g., chromium (in accordance with the Periodic Table of the Elements, Handbook of Chemistry and Physics, 38th edition, pp. 394-95). The anions employed with the metals are generally chosen based on the desired solubility of the metal salt. Typical anions include halides, e.g., chloride, bromide, iodide, etc., sulfates, nitrates, salts of organic acids, e.g., acetate, formates, etc., oxides, hydroxides, etc. Typical metal salts useful in the elements of this invention are further described in any of the literature sources regarding physical development. Typical descriptions are found in patents such as U.S. Pat. No. 3,404,980; British Pat. No. 1,143,021, U.S. Ser. No. 653,025 filed July 13, 1967 by Yudelson et a]; U.S. Ser. No. 723,278 filed Apr. 22, 1968 by Yudelson; U.S. Ser. No. 778,323 filed Nov. 22, 1968 by Yudelson et al, Photographic Science and Engineering, Volume 13, No. 1.
The mechanism or theory pertaining to the function of the sensitizer on the metal salt is not completely understood. However, it is believed that when the sensitizer is struck by actinic radiation, it is decomposed or fragmented to several different factions. Some of these factions are reducing agents for the metal salt. The particular route of the fragmentation reac tion is believed to be somewhat dependent upon the structure of the original compound. However, based upon observations, it is believed that the route followed, when a sensitizer of this invention (such as the one given below) is exposed to actinic radiation, is the following:
1+ CHaO' CHaO I In this instance the aldehyde fragment is believed to cause the reduction of the metal salt so as to form active sites for physical development.
In preparing the photographic elements of this invention, a sensitizer is dispersed in a suitable binder and then the mixture coated on a support using any of the known coating methods. Supporting materials can be any of the known materials for this purpose, such as film base (e.g., cellulose nitrate film, cellulose ester film, etc), plastic supports (e.g., polyethylene, polyethylene terephthalate, etc.) paper including resin treated papers, metal, glass, and the like.
Suitable binders for incorporating the organic compounds include any of the water-permeable materials, such as gelatin or other hydrophilic materials. such as collodion, albumin, cellulose derivatives, synthetic resins such as poly(vinyl alcohol) and the like.
In preparing the coating compositions described herein, the binder and sensitizer are dispersed in a suitable aqueous vehicle such as water. The amount of sensitizer employed ranges from about 0.1% to about 5.0% by weight based on the weight of the total coating composition. The amount of vehicle employed ranges from about 5.0% to about 60% by weight, based on the weight of the total coating composition.
Coating thicknesses of the composition on a support can vary widely. Normally, a wet coating thickness in the range of about 0.001 inch to about 0.01 inch is useful in the practice of this invention. A preferred range of coating thickness is from about 0.002 inch to about 0,006 inch before drying although such thicknesses can vary widely depending on the particular application desired for the photographic element. After the composition is coated, the elements are dried at slightly elevated temperatures for one hour or more.
The photographic elements prepared in the manner described above are then exposed in an imagewise manner to a pattern of actinic radiation. The radiation causes the sensitizer to become an active reducing agent in the areas which have been exposed. The exposure time varies depending on the nature of the light source and the sensitizer used. Generally, however, exposure times vary from about 0.1 to about 60 or more seconds. Upon completion of the exposure step, the element is contacted with a solution of one of the metallic salt nucleating agent precursors described above. The contacting can be accomplished by any of several known techniques such as swabbing the solution on the surface of the element or by immersing the element in the solution. The metal salt is reduced by the sensitizer in the exposed areas of the element thus creating active or catalytic sites for subsequent physical development.
In an alternative embodiment, the photographic element is prepared by coating a composition containing a binder, a sensitizer, a carrier and the metallic salt nucleating agent precursor. In situations of this type, the nucleating agent precursor is present in an amount ranging from about 0.1% to about 5.0% by weight of the total coating composition. Exposure of an element of this type causes activation of the sensitizer in the light struck regions and immediate successive reduction of the metal salt to form active nuclei. In this embodiment, a separate solution containing the nucleating agent precursor is not necessary.
The exposed element containing the active or catalytic sites is then developed by any of the known physical development processes. The particular process or physical developer employed is dependent on the nature of the active sites-created, certain physical developers being more suitable for specific classes of reduced metallic salts than others. Typical physical developers are described in U.S. Pat. No. 3,404,980, British Pat. No. 1,143,021, U.S. Ser. No. 653,025 filed July 13, 1967 by Yudelson et al, U.S. Ser. No. 723,278 filed Apr. 22, 1968 by Yudelson, U.S. Ser. No. 778,323 filed Nov. 22, 1968 by Yudelson et al. The purpose of the physical development is to amplify the image generated by the catalytic sites.
The physical developer which is used to produce a visible image can comprise an aqueous bath in which is dissolved a salt of a heavy metal, a complexing agent for the metal ion, and a reducing agent. The physical developer bath is chosen so that deposition of the heavy metal from the bath is catalyzed by the active sites. The heavy metal deposited from the bath must itself be autocatalytic; that is, it must act as a catalyst for further deposition of metal from the developer. This is necessary in order that deposition and development will continue after the active sites are enveloped with heavy metal. With respect to the Periodic Table, suitable heavy metals can be selected from Group Vlll metals such as nickel, cobalt, iron, palladium and platinum, Group VIB metals such as chromium and Group [B metals such as copper, silver and gold. Almost any heavy metal salt which is a source of the desired heavy metal ions can be employed. Suitable heavy metal salts useful in the invention include heavy metal halides such as cobaltous bromide, cobaltous chloride, cobaltous iodide, ferrous bromide, ferrous chloride, chromium bromide, chromium chloride, chromium iodide, copper chloride, silver bromide, silver chloride, silver iodide, gold chloride, palladium chloride and platinum chloride, heavy metal sulfates such as nickel sulfate, ferrous sulfate, cobaltous sulfate, chromium sulfate, copper sulfate, palladium sulfate and platinum sulfate, heavy metal nitrates such as nickel nitrate, ferrous nitrate, cobaltous nitrate, chromium nitrate and copper nitrate, and heavy metal salts of organic acids such as ferrous acetate, cobaltous acetate, chromium acetate and copper formate. Baths can be formulated based on a single heavy metal or based on mixtures of heavy metals. When more than one heavy metal is employed in the bath, the image which is deposited will generally be an alloy of the two metals. Physical developers based on noble metals such as silver, gold and platinum are relatively unstable and cannot be stored for long periods oftime. However, such physical developers are operative in the processes of this invention and can be employed if the developer bath is prepared shortly before use.
The complexing agent employed in the physical developer bath should tie up the metal ions so that they show a lessened tendency to be reduced spontaneously. However, the complexing agent should not bind the metal ions so tightly that they will be unable to be reduced and deposited on the latent image sites in the presence of the catalyst. Suitable complexing agents include ammonium compounds such as ammonium hydroxide or chloride, organic acids such as aspartic acid, malic acid, citric acid, glycolic acid, salts of organic acids such as sodium citrate, potassium citrate, sodium glycolate, potassium glycolate, sodium succinate, potassium succinate, potassiurn sodium tartrate, etc. A single complexing agent can be used or a combination of more than one complexing agent can be incorporated in the physical developer bath.
The reducing agent can be any compound which provides a ready source of electrons for the reduction of the metal ions and which does not otherwise interfere with development. A general criteria for a reducing agent useful in the physical developers of the present invention is that the potential of the chemical coupler of the reducing agent, written as follows:
Reducing agent 2 Products electrons must be more positive than that for the metal or metals which are to be deposited from the bath. For example, the potential for-the nickel coupler:
Ni 2 Ni 2 electrons is +0.277 volts for acidic solutions. It is necessary for the reducing agent to possess a potential that is greater, i.e., more positive, than +0.277 volts in order that it be capable of reducing nickel ions in the bath. Suitable reducing agents include formaldehyde, hypophosphites such as sodium hypophosphite, manganous hypophosphite, potassium hypophosphite, etc., hydrosulfites such as sodium hydrosulfite, potassium hydrosulfite, calcium hydrosulfite, etc., borohydrides such as sodium borohydride, potassium borohydride, etc., borane amines such as dimethylborane amine, etc., hydrazines, and the like.
There can be added to the physical developer bath a variety of other materials such as buffering agents, acid or base to adjust the pH, preservatives, etc., in accordance with usual practices.
The proportions in which the various components of the physical developer are present in the bath can vary over a wide range. Suitable concentrations of metal salt in the developer bath are in the range of from about 0.01 to about 1.0 mole of metal salt per liter of bath. The upper limit of concentration is controlled by the solubility of the particular metal salt employed. Preferably, the bath is between about 0.05 molar and 0.25 molar with respect to metal salt. The relative proportions of metal salt and complexing agent are dependent upon the particular metal salt or salts and the particular complexing agent or agents which are employed. As a general rule sufficient complexing agent should be incorporated to bind the metal ions and lessen the tendency of the metal ions to be reduced prior to use of the developer. Depending upon the particular metal salt and complexing agent employed, the amount of complexing agent present can vary from about 0.2 mole to about 10 moles of complexing agent per mole of metal salt present. The reducing agent can be present in amounts of from about 0.1 moles to about 5 moles of reducing agent per mole of metal salt present.
The following examples are included for a further understanding of the invention.
EXAMPLE 1 A solution containing 0.025 grams of 2-B-anilinovinyl-lmethoxypyridinium p-toluenesulfonate (Compound 26) and 5.0 grams of a 10 percent aqueous gelatin solution is coated on paper using a 3 mil coating knife. The element is dried and then exposed to a negative image transparency for about 10 seconds using a 400 watt mercury light source at a distance of 1.5 inch. The exposed element is then swabbed with an ammoniacal silver nitrate solution (prepared by adding 0.lN AgNO solution to a 28% NH OH solution in an amount suffcient to cause the resultant cloudy mixture to become clear), washed with water and dried. The active sites thus created are next physically developed by immersing the element in a silver physical developer such as that described in U.S. Pat. No. 3,409,432 (Example 2). A dark brown image is obtained in those areas which had been initially exposed.
EXAMPLE 2 Example 1 is repeated except the active sites are formed by swabbing the surface of the exposed element with an acidic solution of palladium chloride (0.10 gm. PdCl 4.0 ml. of 0.01 N HCl). After drying, the element is physically developed in the same manner as described in Example I. A sharp, dark image is obtained in those areas which had been initially exposed.
EXAMPLE 3 Example 2 is repeated except that the active sites are physically developed using a nickel developer as described in Example 4 of U.S. Ser. No. 778,323 filed Nov. 22, 1968 by Yudelson et al. The reproduction once again has a sharp dark image.
EXAMPLE 4 Example 2 is repeated except the sensitizer employed is 3- ethyll -methoxyoxa-2 '-pyridocarbocyanine perchlorate (Compound 1), Again a reproduction is obtained having sharp, dark images.
EXAMPLE 5 Example 1 is repeated using 3'-ethyl-l-methoxy-2- pyridothiacyanine iodide (Compound 3) as the sensitizer. A very satisfactory reproduction is obtained.
EXAMPLES 6-12 Example 3 is repeated using various sensitizers. The sensitizer used and the quality of the reproduction are described in the following Table I.
TABLE I Example Compound image Quality 6 6 Good 7 9 Good 8 14 Good 9 14 Good l 16 Good l l 18 Good l2 19 Good EXAMPLE 13 A solution containing 0.025 grams of 2-B-anilinovnyl-lmethoxypyridinium p-toluenesulfonate, 5.0 grams of a percent aqueous gelatin solution and 0.10 grams of palladium chloride is coated on paper using a 3 mil. coating knife. The element is dried and then exposed in a manner described in Example 1. The active sites created by the exposure are physically developed with the developer described in Example 6 of U.S. Pat. No. 3,404,980. A good dense image is obtained.
The invention has been described in detail with particular reference to preferred embodiments thereof, but, it will be understood that variations and modifications can be effected within the spirit and scope of the invention.
We claim:
1. A photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group.
2. A photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound having a formula selected from the group consisting of:
(llB. 6R
wherein:
R is selected from the group consisting of:
a. a methine linkage terminated by a heterocyclic nucleus of the type contained in cyanine dyes,
b. an alkyl radical,
c. an anilinovinyl radical,
d. a hydrogen atom,
e-. an aryl radical,
f. an aldehyde group, and
g. a styryl radical;
R is selected from the group consisting of:
a. a methine linkage terminated by a heterocyclic nucleus of the type contained in merocyanine dyes and b. an allylidene radical; R is selected from the group consisting of:
a. an alkyl radical and b. an acyl radical;
X is an acid anion; and,
Z represents the atoms necessary to complete a 5 to 6 membered heterocyclic nucleus.
3. The element as defined in claim 2 wherein Z represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus and a quinoline nucleus.
4. The element as defined in claim 2 wherein R is a methine linkage terminated by a 5 to 6 membered heterocyclic nucleus.
5. The element as defined in claim 2 wherein said nucleating agent precursor is a salt of a metal selected from the group consisting of silver, gold, copper, platinum, palladium, iron, nickel, cobalt, chromium, mercury, lead, tin and zinc.
6. A photographic element comprising 7 a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosen- 0,, Q Q and Q each represent the nonmetallic atoms necessary to complete a 5 to 6 membered heterocyclic nucleus;
n is a positive integer from i to 4;
m is a positive integer from 1 to 3;
R is an alkyleneoxy radical having one to eight carbon atoms in the alkylene chain;
g is a positive integer from 1 to 2;
X- is an acid anion;
L is a methine linkage;
R is selected from the group consisting of an alkyl radical and an acyl radical;
R and R are each selected from the group consisting of an aryl radical, a hydrogen atom and an alkyl radical;
R is selected from the group consisting of an alkyl radical, an alkenyl radical, an aryl radical and an alkoxy radical; G is selected from the group consisting of an anilinovinyl radical and an aryl radical; and
R and R are each a cyano radical.
7. The photographic element of claim 6 wherein said photosensitive compound has the formula:
wherein R, R R;,, Q Q L, X, g and n are defined in claim 6.
8. The photographic element of claim 6 wherein said photosensitive compound has the formula:
wherein R, R 0,, L, G, X, m and g are defined in claim 6.
9. The photographic element of claim 6 wherein said photosensitive compound has the formula:
wherein R, R R,, Q and X are defined in claim 6.
10. The photographic element of claim 6 wherein said photosensitive compound has the formula:
wherein R R 0,, Q X and R are defined in claim 6.
11. The photographic element of claim 6 wherein said metallic salt nucleating agent precursor is a salt of a metal selected from the group consisting of silver, gold, copper, platinum, palladium, iron, nickel, cobalt, chromium, mercury, lead, tin and zinc.
12. A photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound which is a Z-B-anilinovinyl-l-methoX- ypyridinium salt.
13. The element of claim 12 wherein said metallic salt nucleating agent precursor is a silver salt.
14. The element of claim 12 wherein said metallic salt nucleating agent precursor is a palladium salt.
15. A process for forming a physically developable latent image comprising (a) providing a photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group, and (b) exposing said element to a pattern of actinic radiation thus forming a physically developable latent image.
16. A process for forming a physically developable latent image comprising (a) providing a photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound having a formula selected from the group consisting of:
wherein:
R, is selected from the group consisting of:
a. a methine linkage terminated by a heterocyclic nucleus of the type contained in cyanine dyes, b. an alkyl radical, c. an anilinovinyl radical, d. a hydrogen atom, e. an aryl radical, f. an aldehyde group, and g. a styryl radical; R, is selected from the group consisting of:
a. a methine linkage terminated by a heterocyclic nucleus of the type contained in merocyanine dyes and b. an allylidene radical; R is selected from the group consisting of:
a. an alkyl radical and b. an acyl radical; X is an acid anion; and,
2 represents the atoms necessary to complete a 5 to 6 membered heterocyclic nucleus, and (b) exposing said element to a pattern of actinic radiation thus forming a physically developable latent image.
17. The process of claim 16 wherein Z represents the atoms necessary to complete a member selected from the group consisting ofa pyridine nucleus and a quinoline nucleus.
18. The process as defined in claim 16 wherein R, is a methine linkage terminated by a 5 to 6 membered heterocyclic nucleus.
19. The process as defined in claim 16 wherein said nucleating agent precursor is a salt of a metal selected from the group consisting of silver, gold, copper, platinum, palladium, iron, nickel, cobalt, chromium, mercury, lead, tin and zinc.
20. A process for forming a physically developable latent image comprising (a) providing a photographic element comprising a support having thereon a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group, (b) exposing said element to a pattern of actinic radiation, and (c) contacting the exposed element with a solution of a metallic salt nucleating agent precursor thus forming a physically developable latent image.
21. A process for forming a physically developable latent image comprising (a) providing a photographic element comprising a support having thereon a photosensitive compound having a formula selected from the group consisting of:
on on wherein:
R, is selected from the group consisting of:
a. a methine linkage terminated by a heterocyclic nucleus of the type contained in cyanine dyes, b. an alkyl radical, c. an anilinovinyl radical, d. a hydrogen atom, e. an aryl radical, f. an aldehyde group, and g. a styryl radical; R is selected from the group consisting of:
a. a methine linkage terminated by a heterocyclic nucleus of the type contained in merocyanine dyes and b. an allylidene radical;
R is selected from the group consisting of:
a. an alkyl radical and b. an acyl radical;
X is an acid anion; and
Z represents the atoms necessary to complete a 5 to 6 membered heterocyclic nucleus, (b) exposing said element to a pattern of actinic radiation and (c) contacting the exposed element with a solution of a metallic salt nucleating agent precursor thus forming a physically developable latent image.
22. The process of claim 21 wherein Z represents the atoms necessary to complete a member selected from the group consisting ofa pyridine nucleus and a quinoline nucleus.
23. The process as defined in claim 21 wherein R, is a methine linkage terminated by a 5 to 6 membered heterocyclic nucleus.
24. The process as defined in claim 21 wherein said nucleating agent precursor is a salt of a metal selected from the group consisting of silver, gold, copper, platinum, palladium, iron, nickel, cobalt, chromium, mercury, lead, tin and zinc.
25. A photographic composition comprising a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group.
Claims (24)
- 2. A photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound having a formula selected from the group consisting of: wherein: R1 is selected from the group consisting of: a. a methine linkage terminated by a heterocyclic nucleus of the type contained in cyanine dyes, b. an alkyl radical, c. an anilinovinyl radical, d. a hydrogen atom, e. an aryl radical, f. an aldehyde group, and g. a styryl radical; R8 is selected from the group consisting of: a. a methine linkage terminated by a heterocyclic nucleus of the type contained in merocyanine dyes and b. an allylidene radical; R is selected from the group consisting of: a. an alkyl radical and b. an acyl radical; X is an acid anion; and, Z represents the atoms necessary to complete a 5 to 6 membered heterocyclic nucleus.
- 3. The element as defined in claim 2 wherein Z represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus and a quinoline nucleus.
- 4. The element as defined in claim 2 wherein R1 is a methine linkage terminated by a 5 to 6 membered heterocyclic nucleus.
- 5. The element as defined in claim 2 wherein said nucleating agent precursor is a salt of a metal selected from the group consisting of silver, gold, copper, platinum, palladium, iron, nickel, cobalt, chromium, mercury, lead, tin and zinc.
- 6. A photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound having a formula selected from the group consisting of:
- 7. The photographic element of claim 6 wherein said photosensitive compound has the formula: wherein R, R2, R3, Q1, Q2, L, X, g and n are defined in claim 6.
- 8. The photographic element of claim 6 wherein said photosensitive compound has the formula: wherein R, R2, Q2, L, G, X, m and g are defined in claim 6.
- 9. The photographic element of claim 6 wherein said photosensitive compound has the formula: wherein R, R2, R4, Q2 and X are defined in claim 6.
- 10. The photographic element of claim 6 wherein said photosensitive compound has the formula: wherein R2, R4, Q2, Q9, X and R5 are defined in claim 6.
- 11. The photographic element of claim 6 wherein said metallic salt nucleating agent precursor is a salt of a metal selected from the group consisting of silver, gold, copper, platinum, palladium, iron, nickel, cobalt, chromium, mercury, lead, tin and zinc.
- 12. A photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound which is a 2- Beta -anilinovinyl-1-methoxypyridinium salt.
- 13. The element of claim 12 wherein said metallic salt nucleating agent precursor is a silver salt.
- 14. The element of claim 12 wherein said metallic salt nucleating agent precursor is a palladium salt.
- 15. A process for forming a physically developable latent image comprising (a) providing a photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group, and (b) exposing said element to a pattern of actinic radiation thus forming a physically developable latent image.
- 16. A process for forming a physically developable latent image comprising (a) providing a photographic element comprising a support having thereon a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound having a formula selected from the group consisting of: wherein: R1 is selected from the group consisting of: a. a methine linkage terminated by a heterocyclic nucleus of the type contained in cyanine dyes, b. an alkyl radicaL, c. an anilinovinyl radical, d. a hydrogen atom, e. an aryl radical, f. an aldehyde group, and g. a styryl radical; R8 is selected from the group consisting of: a. a methine linkage terminated by a heterocyclic nucleus of the type contained in merocyanine dyes and b. an allylidene radical; R is selected from the group consisting of: a. an alkyl radical and b. an acyl radical; X is an acid anion; and, Z represents the atoms necessary to complete a 5 to 6 membered heterocyclic nucleus, and (b) exposing said element to a pattern of actinic radiation thus forming a physically developable latent image.
- 17. The process of claim 16 wherein Z represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus and a quinoline nucleus.
- 18. The process as defined in claim 16 wherein R1 is a methine linkage terminated by a 5 to 6 membered heterocyclic nucleus.
- 19. The process as defined in claim 16 wherein said nucleating agent precursor is a salt of a metal selected from the group consisting of silver, gold, copper, platinum, palladium, iron, nickel, cobalt, chromium, mercury, lead, tin and zinc.
- 20. A process for forming a physically developable latent image comprising (a) providing a photographic element comprising a support having thereon a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group, (b) exposing said element to a pattern of actinic radiation, and (c) contacting the exposed element with a solution of a metallic salt nucleating agent precursor thus forming a physically developable latent image.
- 21. A process for forming a physically developable latent image comprising (a) providing a photographic element comprising a support having thereon a photosensitive compound having a formula selected from the group consisting of: wherein: R1 is selected from the group consisting of: a. a methine linkage terminated by a heterocyclic nucleus of the type contained in cyanine dyes, b. an alkyl radical, c. an anilinovinyl radical, d. a hydrogen atom, e. an aryl radical, f. an aldehyde group, and g. a styryl radical; R8 is selected from the group consisting of: a. a methine linkage terminated by a heterocyclic nucleus of the type contained in merocyanine dyes and b. an allylidene radical; R is selected from the group consisting of: a. an alkyl radical and b. an acyl radical; X is an acid anion; and Z represents the atoms necessary to complete a 5 to 6 membered heterocyclic nucleus, (b) exposing said element to a pattern of actinic radiation and (c) contacting the exposed element with a solution of a metallic salt nucleating agent precursor thus forming a physically developable latent image.
- 22. The process of claim 21 wherein Z represents the atoms necessary to complete a member selected from the group consisting of a pyridine nucleus and a quinoline nucleus.
- 23. The process as defined in claim 21 wherein R1 is a methine linkage terminated by a 5 to 6 membered heterocyclic nucleus.
- 24. The process as defined in claim 21 wherein said nucleating agent precursor is a salt of a metal selected from the group consisting of silver, gold, copper, platinum, palladium, iron, nickel, cobalt, chromium, mercury, lead, tin and zinc.
- 25. A photographic composition comprising a metallic salt nucleating agent precursor capable of forming active sites for physical development and a photosensitive compound containing a heterocyclic nitrogen atom which is substituted by a member selected from the group consisting of an alkoxy group and an acyloxy group.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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US85471969A | 1969-09-02 | 1969-09-02 |
Publications (1)
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US3649275A true US3649275A (en) | 1972-03-14 |
Family
ID=25319393
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US854719A Expired - Lifetime US3649275A (en) | 1969-09-02 | 1969-09-02 | Photographic elements and processes |
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US (1) | US3649275A (en) |
CA (1) | CA942563A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4075017A (en) * | 1976-05-24 | 1978-02-21 | Eastman Kodak Company | Photothermographic material containing a combination of energy-sensitive organic dyes and process of forming a positive or negative image with the material |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3149970A (en) * | 1959-01-10 | 1964-09-22 | Agfa Ag | Production of photographic silver images by physical development |
US3291608A (en) * | 1964-02-03 | 1966-12-13 | Eastman Kodak Co | Enhanced activity of nuclei for physical development |
US3404980A (en) * | 1962-12-13 | 1968-10-08 | Eastman Kodak Co | Silver images in light-sensitive print-forming layers |
US3409432A (en) * | 1965-10-24 | 1968-11-05 | Eastman Kodak Co | Chemical amplification of photosensitive layers |
-
1969
- 1969-09-02 US US854719A patent/US3649275A/en not_active Expired - Lifetime
-
1970
- 1970-08-06 CA CA090,088A patent/CA942563A/en not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3149970A (en) * | 1959-01-10 | 1964-09-22 | Agfa Ag | Production of photographic silver images by physical development |
US3404980A (en) * | 1962-12-13 | 1968-10-08 | Eastman Kodak Co | Silver images in light-sensitive print-forming layers |
US3291608A (en) * | 1964-02-03 | 1966-12-13 | Eastman Kodak Co | Enhanced activity of nuclei for physical development |
US3409432A (en) * | 1965-10-24 | 1968-11-05 | Eastman Kodak Co | Chemical amplification of photosensitive layers |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4075017A (en) * | 1976-05-24 | 1978-02-21 | Eastman Kodak Company | Photothermographic material containing a combination of energy-sensitive organic dyes and process of forming a positive or negative image with the material |
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