US3825426A - Development of exposed photographic silver halide elements - Google Patents
Development of exposed photographic silver halide elements Download PDFInfo
- Publication number
- US3825426A US3825426A US00303404A US30340472A US3825426A US 3825426 A US3825426 A US 3825426A US 00303404 A US00303404 A US 00303404A US 30340472 A US30340472 A US 30340472A US 3825426 A US3825426 A US 3825426A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- compounds
- emulsion
- emulsions
- photographic
- 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
- -1 silver halide Chemical class 0.000 title abstract description 45
- 229910052709 silver Inorganic materials 0.000 title abstract description 33
- 239000004332 silver Substances 0.000 title abstract description 33
- 238000011161 development Methods 0.000 title abstract description 10
- 239000000839 emulsion Substances 0.000 abstract description 59
- 150000001875 compounds Chemical class 0.000 abstract description 29
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 8
- 239000001257 hydrogen Substances 0.000 abstract description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 7
- 229910052736 halogen Inorganic materials 0.000 abstract description 6
- 150000002367 halogens Chemical class 0.000 abstract description 6
- 238000010186 staining Methods 0.000 abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000002360 preparation method Methods 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 125000003118 aryl group Chemical group 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 8
- 239000000975 dye Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 8
- 125000002252 acyl group Chemical group 0.000 description 7
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000000084 colloidal system Substances 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 150000002431 hydrogen Chemical group 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 238000004377 microelectronic Methods 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 235000010265 sodium sulphite Nutrition 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- 229940125898 compound 5 Drugs 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
- 125000005252 haloacyl group Chemical group 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 3
- WOAHJDHKFWSLKE-UHFFFAOYSA-N 1,2-benzoquinone Chemical compound O=C1C=CC=CC1=O WOAHJDHKFWSLKE-UHFFFAOYSA-N 0.000 description 2
- 150000004055 1,2-benzoquinones Chemical class 0.000 description 2
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- 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 2
- DJVAOKPGUYIELQ-UHFFFAOYSA-N 4-amino-2-methylphenol;benzene-1,4-diol Chemical compound OC1=CC=C(O)C=C1.CC1=CC(N)=CC=C1O DJVAOKPGUYIELQ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical group C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910021612 Silver iodide Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 2
- IFVYHJRLWCUVBB-UHFFFAOYSA-N allyl thiocyanate Chemical compound C=CCSC#N IFVYHJRLWCUVBB-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical group O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 150000002731 mercury compounds Chemical class 0.000 description 2
- DZVCFNFOPIZQKX-LTHRDKTGSA-M merocyanine Chemical compound [Na+].O=C1N(CCCC)C(=O)N(CCCC)C(=O)C1=C\C=C\C=C/1N(CCCS([O-])(=O)=O)C2=CC=CC=C2O\1 DZVCFNFOPIZQKX-LTHRDKTGSA-M 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229940045105 silver iodide Drugs 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 125000004149 thio group Chemical group *S* 0.000 description 2
- NCNYEGJDGNOYJX-NSCUHMNNSA-N (e)-2,3-dibromo-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Br)=C(/Br)C=O NCNYEGJDGNOYJX-NSCUHMNNSA-N 0.000 description 1
- LUMLZKVIXLWTCI-NSCUHMNNSA-N (e)-2,3-dichloro-4-oxobut-2-enoic acid Chemical compound OC(=O)C(\Cl)=C(/Cl)C=O LUMLZKVIXLWTCI-NSCUHMNNSA-N 0.000 description 1
- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical class C1NCNCN1 LKLLNYWECKEQIB-UHFFFAOYSA-N 0.000 description 1
- VMWMDCNYXKAFDN-UHFFFAOYSA-N 1,3,5-tris(ethenylsulfonyl)benzene Chemical compound C=CS(=O)(=O)C1=CC(S(=O)(=O)C=C)=CC(S(=O)(=O)C=C)=C1 VMWMDCNYXKAFDN-UHFFFAOYSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- MZFSRQQVIKFYON-UHFFFAOYSA-N 1-(3-acetyl-5-prop-2-enoyl-1,3,5-triazinan-1-yl)prop-2-en-1-one Chemical compound CC(=O)N1CN(C(=O)C=C)CN(C(=O)C=C)C1 MZFSRQQVIKFYON-UHFFFAOYSA-N 0.000 description 1
- GGZHVNZHFYCSEV-UHFFFAOYSA-N 1-Phenyl-5-mercaptotetrazole Chemical compound SC1=NN=NN1C1=CC=CC=C1 GGZHVNZHFYCSEV-UHFFFAOYSA-N 0.000 description 1
- ODPJQZNJZWLTJH-UHFFFAOYSA-N 2,3-dihydrotriazolo[4,5-d]pyrimidin-5-one Chemical compound O=C1N=CC2=NNNC2=N1 ODPJQZNJZWLTJH-UHFFFAOYSA-N 0.000 description 1
- HDGMAACKJSBLMW-UHFFFAOYSA-N 4-amino-2-methylphenol Chemical compound CC1=CC(N)=CC=C1O HDGMAACKJSBLMW-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 108010076119 Caseins Proteins 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 244000287680 Garcinia dulcis Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000004133 Sodium thiosulphate Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229920002494 Zein Polymers 0.000 description 1
- 108010055615 Zein Proteins 0.000 description 1
- SJOOOZPMQAWAOP-UHFFFAOYSA-N [Ag].BrCl Chemical compound [Ag].BrCl SJOOOZPMQAWAOP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 150000004781 alginic acids Chemical class 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- HTKFORQRBXIQHD-UHFFFAOYSA-N allylthiourea Chemical compound NC(=S)NCC=C HTKFORQRBXIQHD-UHFFFAOYSA-N 0.000 description 1
- 229960001748 allylthiourea Drugs 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 229940105329 carboxymethylcellulose Drugs 0.000 description 1
- 239000005018 casein Substances 0.000 description 1
- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
- 235000021240 caseins Nutrition 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 238000013500 data storage Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical group C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000005179 haloacetyl group Chemical group 0.000 description 1
- 238000001093 holography Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- PKDBSOOYVOEUQR-UHFFFAOYSA-N mucobromic acid Natural products OC1OC(=O)C(Br)=C1Br PKDBSOOYVOEUQR-UHFFFAOYSA-N 0.000 description 1
- ZAKLKBFCSHJIRI-UHFFFAOYSA-N mucochloric acid Natural products OC1OC(=O)C(Cl)=C1Cl ZAKLKBFCSHJIRI-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- UCUUFSAXZMGPGH-UHFFFAOYSA-N penta-1,4-dien-3-one Chemical compound C=CC(=O)C=C UCUUFSAXZMGPGH-UHFFFAOYSA-N 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000191 poly(N-vinyl pyrrolidone) Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000011158 quantitative evaluation Methods 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 230000005070 ripening Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- ZUNKMNLKJXRCDM-UHFFFAOYSA-N silver bromoiodide Chemical compound [Ag].IBr ZUNKMNLKJXRCDM-UHFFFAOYSA-N 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000003107 substituted aryl group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- FYOWZTWVYZOZSI-UHFFFAOYSA-N thiourea dioxide Chemical class NC(=N)S(O)=O FYOWZTWVYZOZSI-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 230000004304 visual acuity Effects 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- 239000005019 zein Substances 0.000 description 1
- 229940093612 zein Drugs 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
- C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D257/04—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
- C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D249/12—Oxygen or sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/60—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings condensed with carbocyclic rings or ring systems
- C07D277/62—Benzothiazoles
- C07D277/68—Benzothiazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached in position 2
- C07D277/70—Sulfur atoms
- C07D277/74—Sulfur atoms substituted by carbon atoms
-
- 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/08—Sensitivity-increasing substances
- G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
-
- 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
- G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
- G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium
-
- 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
- G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
- G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
- G03C7/305—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers
- G03C7/30511—Substances liberating photographically active agents, e.g. development-inhibiting releasing couplers characterised by the releasing group
-
- 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
- G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
- G03C1/035—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein characterised by the crystal form or composition, e.g. mixed grain
- G03C2001/03511—Bromide content
-
- 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
- G03C2200/00—Details
- G03C2200/38—Lippmann (fine grain) emulsion
-
- 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
- G03C2200/00—Details
- G03C2200/45—Polyhydroxybenzene
Definitions
- R is hydrogen, acyl, haloacyl or acyl carrying a quaternary ammonium group
- R is hydrogen, alkyl, aryl, halogen or alkoxy
- R is an aliphatic, aromatic or heterocyclic group.
- the compounds are especially useful in Lippmannemulsions to reduce distortions of image details, to enhance image sharpness and to reduce yellow staining upon reversal development.
- the present invention relates to the use in silver halide photography of compounds which on development release aliphatic, aromatic or heterocyclic mercaptans and to the use of these compounds in silver halide emulsions, especially silver halide emulsions of the Lippmann type.
- Lippmann emulsions normally having an average grainsize of less than 100 nm., are of particular importance for the preparation of photographic plates or films with high resolution, for use in micro-photography, for recording nucleophysical phenomenons, for the preparation of masks in the production of microelectronic integrated circuits, for use in holography, for high-density data storage, etc.
- the photographic materials for use in the production of masks as described above should have a high resolving power and accutance, and allow a correct reproduction of the dimensions of the image.
- Lippmann-materials special problems are encountered both on reversal and negative processing. For instance, the images produced often show at certain areas distortions of image details by mutual influence of closely adjacent image details and the image-sharpness does not always meet the requirements.
- R stands for hydrogen, acyl, e.g. acetyl, haloacyl, e.g. haloacetyl or acyl carrying a quaternary ammonium p,
- R is hydrogen, alkyl, aryl, halogen or alkoxy
- R is an aliphatic group, more particularly alkyl including substituted alkyl e.g. alkyl substituted with carboxy, with aryl or with a heterocycle, an aromatic group more particularly aryl including substituted aryl e.g. aryl substituted with halogen or with C -C alkyl, or preferably a heterocyclic group e.g. a l-substituted S-tetrazolyl or 3-triazolyl group or a Z-beuzothiazolyl group.
- R is not H
- the compounds of the above general formula wherein R is not H are the chemically masked forms of those wherein R is H and can be prepared from the latter by methods described in the literature e.g. U.S. Pat. 3,246,988 and Belgian Patent Specification 734,140.
- the pyrocatechol derivatives that besides the thio group carry a group R other than H e.g. alkyl, aryl, alkoxy etc. can be prepared as is illustrated in J. Org. Chem. 29 (1964) 589 by allowing to react the correspondingly substituted o-benzoquinone with the appropriate aliphatic, aromatic or heterocyclic thiol.
- Preparation 1 Compound 5 To a solution of 13 g. (0.118 mole) of pyrocatechol, 17.8 g. (0.1 mole) of 1-phenyl-S-mercaptotetrazole add 50 g. of sodium acetate-3 water in 180 ml. of water, a solution of 65 g. (0.2 mole) of potassium hexacyanoferrate(III) and 50 g. of sodium acetate-3-water in ml.
- Preparation 2 Compound 6 To a mixture of 13 g. (0.118 mole) of pyrocatechol and 16.7 g. (0.1 mole) of 2-mercaptobenzothiazole in 150 ml. of acetone and 50 g. of sodium acetate-3-water in 50 ml. of water, a solution of 65 g. (0.2 mole) of potassium hexacyanoferrate(III) and 50 g. of sodium acetate-3-water in 150 ml. of water was added with stirring at 15 C. The mixture was stirred for 30 min. whereupon the precipitated salts were filtered off and the filtrate poured into water. The precipitate was purified by continuous extraction with methylene chloride/methanol (10:1).
- Preparation 3 Compound 7 To a suspension of 17.7 g. (0.1 mole) of 1-pheny1-3- mercapto-1,2,4-triazole in 400 ml. of methanol, a solution of 0.114 mole of o-benzoquinone (Ber. 37, 4745) in 750 ml. of anhydrous ether is dropwise added in 20 min. with stirring at 10 C. The quinone solution decolorized and the precipitate dissolved almost completely. After 1 hour the solution was filtered and concentrated by evaporation. The residue was recrystallized from a minimum amount of methanol.
- o-benzoquinone o-benzoquinone
- Preparation 4 Compound 8 To a solution of 28.6 g. (0.1 mole) of compound 5 in 120 ml. of dioxan comprising 2.4 g. (0.1 mole) of magnesium curlings, 39 g. (0.5 mole) of acetyl chloride were dropwise added in 30 min. with stirring and while refiuxing. The mixture was refluxed for 24 hours and then filtered. The filtrate was evaporated and the residue extracted with 100 ml. of benzene. The non-soluble residue was isolated whereas the benzene solution was filtered and evaporated.
- the compounds for use in accordance with the present invention are incorporated in the emulsion layer by addition, as a solution or dispersion, to the coating compositions of the Lippmann emulsion.
- the concentration of the compounds used according to the invention depends on the characteristics of both the chosen compound and the emulsion and is therefore best determined by trial. In most cases the optimum concentration in the silver halide emulsion is between about 20 mg. and about 2 g., preferably between about 100 mg. and 1 g. per mole of silver halide.
- the thickness of the emulsion layer of a photographic material according to the present invention is generally comprised between about 3 microns and about 8 microns, and the average grain size of the silver halide grains is generally less than 80 nm.
- the ratio of silver halide to hydrophilic colloid binder in the Lippmann emulsion according to the present invention is preferably at least 1:2 and at most 4: 1.
- the silver halide Lippmann emulsions may be prepared according to methods well known in the art and described in the literature (see e.g. P. Glafkides Photographic Chemistry, Vol. I, 1958, pages 365-368, Mees/ James The theory of the Photographic Process, 1966, p. 36 and National Physical Laboratory Notes on Applied Science No. 20: Small Scale Preparation of Fine- Grain (Colloidal) Photographic Emulsions, B. H. Crawford, London, 1960). They may also be prepared according to the technique described in co-pending United Kingdom Patent Application 15,948/70.
- Silver halide Lippmann-emulsions with very fine grain can be obtained by effecting the precipitation of the silver halide in the presence of heterocyclic mercapto compounds as described in United Kingdom Patent Specification 1,204,623 or in the presence of compounds as described in co-pending United Kingdom Patent Applications 53,025/69 and 54,539/69.
- the hydrophilic colloid used as the vehicle for the silver halide may be any of the common hydrophilic colloids employed in photographic light-sensitive emulsions for example, gelatin, albumin, zein, casein, alginic acid, a cellulose derivative such as carboxy-methyl cellulose, a synthetic hydrophilic colloid such as polyvinyl alcohol and poly-N-vinylpyrrolidone, etc. If desired compatible mixtures of two or more colloids may be employed for dispersing the silver halide.
- silver salts may be used as the light-sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide, silver bromoiodide and silver chlorobromoiodide.
- Silver bromide emulsions which may have an iodide content of at most 8 mole percent and having an average grain-size of at most nm. are favoured.
- the emulsions may be coated on a wide variety of photographic emulsion supports.
- Typical supports include cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film and related films of resinous materials as well as paper and glass.
- glass supports are most advantageously used in view of their high dimensional stability.
- the light-sensitive silver halide emulsions of use in the preparation of a photographic material according to the present invention may be chemically as well as spectrally sensitized.
- the silver halide emulsions for microelectronic mask making according to the present invention are most advantageously sensitized for the green region of the spectrum.
- the exposure light is preferably chosen so that it radiates light of a wavelength to which the emulsion has been spectrally sensitized.
- sulphur containing compounds such as allyl thiocyanate, allyl thiourea, sodium thiosulphate, etc.
- the emulsions may also be sensitized by means of reductors for instance tin compounds as described in French Patent Specification 1,146,955 and in Belgian Patent Specification 568,687, imino-amino methane sulphinic acid compounds as described in United Kingdom Patent Specification 789,823 and small amounts of noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium.
- the said emulsions may also comprise compounds which sensitize the emulsion by development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in US. Pats. 2,531,832 and 2,533,990, in United Kingdom Patent Specification 920,637, 940,051, 945,340 and 991,608 and in Belgian Patent Specification 648,710 and the known onium compounds including quaternary ammonium, quaternary phosphonium and ternary sulphonium compounds as well as onium derivatives of amino-N-oxides as described in United Kingdom Patent Specification 1,121,696.
- compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in US. Pats. 2,531,832 and 2,533,990
- United Kingdom Patent Specification 920,637, 940,051, 945,340 and 991,608 and in Belgian Patent Specification 648,710
- the known onium compounds including quaternary am
- the emulsions may comprise stabilizers e.g. heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-Z-thione and 1-phenyl-2-tetrazoline-5- thione and compounds of the hydroxytriazolopyrimidine type. They can also be stabilized with mercury compounds such as the mercury compounds described in Belgian Patent Specifications 524,121 and 677,337, United Kingdom Patent Specification 1,173,609 and in US. Pat. 3,179,520.
- stabilizers e.g. heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-Z-thione and 1-phenyl-2-tetrazoline-5- thione and compounds of the hydroxytriazolopyrimidine type. They can also be stabilized with mercury compounds such as the mercury compounds described in Belgian Patent Specifications 524,121 and 677,337, United Kingdom Patent Specification 1,173,609 and in US. Pat. 3,179,520.
- the emulsions may also comprise light-absorbing dyes which are so chosen that they absorb light of the Wavelength to which the material is exposed so that scattering and reflection of light within the photographic material is reduced.
- light-absorbing dyes which are so chosen that they absorb light of the Wavelength to which the material is exposed so that scattering and reflection of light within the photographic material is reduced.
- the dyes are preferably used in such amounts that per micron of emulsion layer thickness a density comprised between 0.05 and 0.20, measured in the spectral region of the exposure light, is obtained.
- any of the hardening agents for hydrophilic colloids may be used in the emulsions according to the present invention such as chromium, aluminium, and zirconium salts, formaldehyde, dialdehydes, hydroxy aldehydes, acrolein, glyoxal, halogen substituted aldehyde acids such as mucochloric acid and mucobromic acid, diketones such as divinyl ketone, compounds carrying one or more vinylsulphonyl groups such as divinyl sulphone, 1,3,5- trivinylsulphonyl benzene, hexahydro-s-triazines carrying vinylcarbonyl, halogenoacetyl and/or acyl groups such as 1,3,S-triacryloyl-hexahydro-1,3,5-triazine, 1,3 diacryloyl 5 acetylhexahydro 1,3,5 triazine, 1,3,5 trichloro
- the light-sensitive emulsions may also comprise all other kinds of ingredients such as plasticizers, coating aids, etc.
- the compounds corresponding to the above general formula have been particularly described for use in Lippmann-emulsions they can also be used in other light-sensitive silver halide emulsions to promote enhanced sharpness.
- the compounds of the invention are silver halide developing agents and release development inhibiting mercaptans. Thus, they may be used in X-ray and other non-optically sensitized emulsions as well as in orthochromatic, panchromatic and infrared-sensitive emulsions. Further, they may be used in emulsions intended for use in the well known silver complex diffusion transfer process.
- EXAMPLE 1 A silver bromide emulsion comprising per kg. 72 g. of silver bromide and 93 g. of gelatin was prepared by simultaneous addition of a silver nitrate solution and a potassium bromide solution to a 3% aqueous solution of gelatin. The conditions of precipitation were adjusted so that a Lippmann emulsion with an average grain size of 70 nm. was obtained. Details as to the preparation of Lippmann-emulsions can be found amongst others in P. Glafkides Photographic Chemistry, Vol. I, 1958, Fountain Press, London.
- the emulsion was sensitized by addition of 150 mg. per g. of silver halide of a merocyanine dye by means of which a strong spectral sensitization in the region of 520-550 nm. was obtained. Then, an amount of the light-absorbing dye having the following structural formula:
- the emulsion was divided into 2 portions and to one of these portions compound 5 was added in an amount of 500 mg. per mole of silver halide.
- the emulsion portions were coated on glass plates pro rata of 230 ml. per sq. In. so as to obtain after drying a layer thickness of 6 microns.
- the 2 plate materials A and B were then exposed under identical circumstances by means of monochromatic light, the spectral composition of which corresponds with the absorption region of the light-absorbing dye used, through a test pattern, as normally used for the quantitative evaluation of materials for use in microelectronics mask-making, consisting of lines which are separated by spaces of the samewidth as the lines themselves and with a width varying from 1 to 20
- the exposure was of such an intensity so as to limit the density in the transparent areas of the images produced, which correspond with the white lines of the test pattern, to the fog value.
- Example 1 was repeated with the dilference that materials A and B were processed so as to obtain a negative image by means of a developing liquid of the following composition:
- material B showed improved image-sharpness and less distortions in line-reproduction.
- Photographic silver halide emulsion comprising a compound of the general formula:
- R is hydrogen, acyl, haloacyl or acyl carrying a quaternary ammonium group, R, is hydrogen, alkyl, aryl, halogen or alkoxy, and R is an aliphatic, aromatic or heterocyclic group.
- Photographic emulsion according to claim 3, wherein the said emulsion is a silver bromide emulsion which may comprise silver iodide in an amount of at most 8 mole percent and which has an average grainsize of at most nm.
- Photographic material comprising a support and an emulsion according to claim 1.
- Photographic material according to claim 9, wherein the said support is a glass support.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Silver Salt Photography Or Processing Solution Therefor (AREA)
- Thiazole And Isothizaole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
Abstract
A PHOTOGRAPHIC SILVER HALIDE EMULSION IS DESCRIBED WHICH COMPRISES A COMPOUND OF THE FORMULA:
1,2-DI(RO-),(R2-S-),R1-BENZENE
WHEREIN: R IS HYDROGEN, ACYL, HALOACYL OR ACYL CARRYING A QUARTERNARY AMMONIUM GROUP, R1 IS HYDROGEN, ALKYL, ARYL, HALOGEN OR ALKOXY, AND R2 IS AN ALIPHATIC, AROMATIC OR HETERCYCLIC GROUP. THE COMPOUNDS ARE ESPECIALLY USEFUL IN LIPPMANNEMULSIONS TO REDUCE DISTORTIONS OF IMAGE DETAILS, TO ENHANCE IMAGE SHARPNESS AND TO REDUCE YELLOW STAINING UPON REVERSAL DEVELOPMENT.
1,2-DI(RO-),(R2-S-),R1-BENZENE
WHEREIN: R IS HYDROGEN, ACYL, HALOACYL OR ACYL CARRYING A QUARTERNARY AMMONIUM GROUP, R1 IS HYDROGEN, ALKYL, ARYL, HALOGEN OR ALKOXY, AND R2 IS AN ALIPHATIC, AROMATIC OR HETERCYCLIC GROUP. THE COMPOUNDS ARE ESPECIALLY USEFUL IN LIPPMANNEMULSIONS TO REDUCE DISTORTIONS OF IMAGE DETAILS, TO ENHANCE IMAGE SHARPNESS AND TO REDUCE YELLOW STAINING UPON REVERSAL DEVELOPMENT.
Description
United States Patent 3,825,426 DEVELOPMENT OF EXPOSED PHOTOGRAPHIC SILVER HALIDE ELEMENTS Robert Joseph Pollett, Vremde, Herman Adelbert Philippaerts, Edegem, Antoon Leon Vandenberghe, Hove, and Jozef Frans Willems, Wilrijk, Belgium, assignors to AGFA-Gevaert N.V., Mortsel, Belgium No Drawing. Filed Nov. 3, 1972, Ser. 110. 303,404 Claims priority, application Great Britain, Nov. 10, 1971, 52,290/71 Int. Cl. G03c 1/34, 1/78 U.S. CI. 96-76 R 8 Claims ABSTRACT OF THE DISCLOSURE A photographic silver halide emulsion is described which comprises a compound of the formula:
S-Rz
wherein:
R is hydrogen, acyl, haloacyl or acyl carrying a quaternary ammonium group,
R is hydrogen, alkyl, aryl, halogen or alkoxy, and
R is an aliphatic, aromatic or heterocyclic group.
The compounds are especially useful in Lippmannemulsions to reduce distortions of image details, to enhance image sharpness and to reduce yellow staining upon reversal development.
The present invention relates to the use in silver halide photography of compounds which on development release aliphatic, aromatic or heterocyclic mercaptans and to the use of these compounds in silver halide emulsions, especially silver halide emulsions of the Lippmann type.
Lippmann emulsions, normally having an average grainsize of less than 100 nm., are of particular importance for the preparation of photographic plates or films with high resolution, for use in micro-photography, for recording nucleophysical phenomenons, for the preparation of masks in the production of microelectronic integrated circuits, for use in holography, for high-density data storage, etc.
In the production of microelectronic integrated circuits, drawings are made on highly enlarged scale of the various successive masks necessary to produce one integrated circuit whereupon the drawings are reduced if necessary in successive steps, and reproduced on a photographic Lippmann plate or film material forming thereby the mask ready for use. By various photographic and chemical steps (photo-etching of lacquered plates) the images of the masks thus produced are transferred to the surface on which the integrated circuit is to be made, in order to produce the required circuit elements.
The photographic materials for use in the production of masks as described above should have a high resolving power and accutance, and allow a correct reproduction of the dimensions of the image. However, with highresolution Lippmann-materials special problems are encountered both on reversal and negative processing. For instance, the images produced often show at certain areas distortions of image details by mutual influence of closely adjacent image details and the image-sharpness does not always meet the requirements.
It has now been found that the above disadvantageous effects can be reduced or eliminated by incorporating in Patented July 23, 1974 the Lippmann-emulsions pyrocatechol derivatives corresponding to the following general formula:
S-Rz wherein:
R stands for hydrogen, acyl, e.g. acetyl, haloacyl, e.g. haloacetyl or acyl carrying a quaternary ammonium p,
R is hydrogen, alkyl, aryl, halogen or alkoxy, and
R is an aliphatic group, more particularly alkyl including substituted alkyl e.g. alkyl substituted with carboxy, with aryl or with a heterocycle, an aromatic group more particularly aryl including substituted aryl e.g. aryl substituted with halogen or with C -C alkyl, or preferably a heterocyclic group e.g. a l-substituted S-tetrazolyl or 3-triazolyl group or a Z-beuzothiazolyl group.
Representative examples of compounds corresponding to the above general formula and suitable for use according to the present invention are:
Compounds 6 and 7 are of incompletely determined structure as to the position of the heterocyclic thio group; this is indicated by the use of x instead of an integer in the structure, though it is presumed that the position is the 4-position.
The compounds of the above general formula wherein R is not H are the chemically masked forms of those wherein R is H and can be prepared from the latter by methods described in the literature e.g. U.S. Pat. 3,246,988 and Belgian Patent Specification 734,140. The pyrocatechol derivatives that besides the thio group carry a group R other than H e.g. alkyl, aryl, alkoxy etc. can be prepared as is illustrated in J. Org. Chem. 29 (1964) 589 by allowing to react the correspondingly substituted o-benzoquinone with the appropriate aliphatic, aromatic or heterocyclic thiol. Since the unsubstituted o-benzoquinone (R H) is unstable this method is less satisfactory for the preparation of the hitherto unknown pyrocatechol derivatives wherein R is H. It was found that the novel pyrocatechol derivatives wherein R is H and R is a heterocycle can be prepared satisfactorily by reaction of the heterocyclic mercapto compound with o-benzoquinone formed in situ from pyrocatechol and an oxidizing agent, e.g. potassium hexacyanoferrate(III).
In the following preparations it is illustrated how compounds 5 to 8 were prepared.
Preparation 1: Compound 5 To a solution of 13 g. (0.118 mole) of pyrocatechol, 17.8 g. (0.1 mole) of 1-phenyl-S-mercaptotetrazole add 50 g. of sodium acetate-3 water in 180 ml. of water, a solution of 65 g. (0.2 mole) of potassium hexacyanoferrate(III) and 50 g. of sodium acetate-3-water in ml.
of water was added at room temperature with stirring. The mixture Was stirred for 1 hour whereupon the precipitate was filtered off by suction and recrystallized from 200 ml. of methanol.
Yield: 20 g. (70%). Melting point: 164 C.
Preparation 2: Compound 6 To a mixture of 13 g. (0.118 mole) of pyrocatechol and 16.7 g. (0.1 mole) of 2-mercaptobenzothiazole in 150 ml. of acetone and 50 g. of sodium acetate-3-water in 50 ml. of water, a solution of 65 g. (0.2 mole) of potassium hexacyanoferrate(III) and 50 g. of sodium acetate-3-water in 150 ml. of water was added with stirring at 15 C. The mixture was stirred for 30 min. whereupon the precipitated salts were filtered off and the filtrate poured into water. The precipitate was purified by continuous extraction with methylene chloride/methanol (10:1).
Yield: 14 g. (51%). Melting point: 196 C.
Preparation 3: Compound 7 To a suspension of 17.7 g. (0.1 mole) of 1-pheny1-3- mercapto-1,2,4-triazole in 400 ml. of methanol, a solution of 0.114 mole of o-benzoquinone (Ber. 37, 4745) in 750 ml. of anhydrous ether is dropwise added in 20 min. with stirring at 10 C. The quinone solution decolorized and the precipitate dissolved almost completely. After 1 hour the solution was filtered and concentrated by evaporation. The residue was recrystallized from a minimum amount of methanol.
Yield: 11.5 g. (40%). Melting point: 198 C.
Preparation 4: Compound 8 To a solution of 28.6 g. (0.1 mole) of compound 5 in 120 ml. of dioxan comprising 2.4 g. (0.1 mole) of magnesium curlings, 39 g. (0.5 mole) of acetyl chloride were dropwise added in 30 min. with stirring and while refiuxing. The mixture was refluxed for 24 hours and then filtered. The filtrate was evaporated and the residue extracted with 100 ml. of benzene. The non-soluble residue was isolated whereas the benzene solution was filtered and evaporated.
Yield: 34 g. (92%). Melting point: 50 C.
Both in reversal and negative development the use of the compounds of the above formula results in an enhancement of the image sharpness, particularly sharpness of fine detail, and in a favourable effect on the distortions of image-details. In addition thereto, where reversal processing of Lippmann material is very critical and often gives rise to yellow staining, probably owing to residual oxidation products of the developing agent, it was found that the compounds of the above general formula counteract said yellowing.
The compounds for use in accordance with the present invention are incorporated in the emulsion layer by addition, as a solution or dispersion, to the coating compositions of the Lippmann emulsion.
The concentration of the compounds used according to the invention depends on the characteristics of both the chosen compound and the emulsion and is therefore best determined by trial. In most cases the optimum concentration in the silver halide emulsion is between about 20 mg. and about 2 g., preferably between about 100 mg. and 1 g. per mole of silver halide.
The thickness of the emulsion layer of a photographic material according to the present invention is generally comprised between about 3 microns and about 8 microns, and the average grain size of the silver halide grains is generally less than 80 nm. The ratio of silver halide to hydrophilic colloid binder in the Lippmann emulsion according to the present invention is preferably at least 1:2 and at most 4: 1.
The silver halide Lippmann emulsions may be prepared according to methods well known in the art and described in the literature (see e.g. P. Glafkides Photographic Chemistry, Vol. I, 1958, pages 365-368, Mees/ James The theory of the Photographic Process, 1966, p. 36 and National Physical Laboratory Notes on Applied Science No. 20: Small Scale Preparation of Fine- Grain (Colloidal) Photographic Emulsions, B. H. Crawford, London, 1960). They may also be prepared according to the technique described in co-pending United Kingdom Patent Application 15,948/70.
Silver halide Lippmann-emulsions with very fine grain can be obtained by effecting the precipitation of the silver halide in the presence of heterocyclic mercapto compounds as described in United Kingdom Patent Specification 1,204,623 or in the presence of compounds as described in co-pending United Kingdom Patent Applications 53,025/69 and 54,539/69.
The hydrophilic colloid used as the vehicle for the silver halide may be any of the common hydrophilic colloids employed in photographic light-sensitive emulsions for example, gelatin, albumin, zein, casein, alginic acid, a cellulose derivative such as carboxy-methyl cellulose, a synthetic hydrophilic colloid such as polyvinyl alcohol and poly-N-vinylpyrrolidone, etc. If desired compatible mixtures of two or more colloids may be employed for dispersing the silver halide.
Various silver salts may be used as the light-sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide, silver bromoiodide and silver chlorobromoiodide. Silver bromide emulsions which may have an iodide content of at most 8 mole percent and having an average grain-size of at most nm. are favoured.
The emulsions may be coated on a wide variety of photographic emulsion supports. Typical supports include cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film and related films of resinous materials as well as paper and glass. In the manufacture of high-resolution plate materials for the preparation of masks for use in the electronic industry, glass supports are most advantageously used in view of their high dimensional stability.
The light-sensitive silver halide emulsions of use in the preparation of a photographic material according to the present invention may be chemically as well as spectrally sensitized.
They may be spectrally sensitized by any of the known spectral sensitizers such as cyanines and merocyanine dyes for photographic light-sensitive silver halide materials. The silver halide emulsions for microelectronic mask making according to the present invention are most advantageously sensitized for the green region of the spectrum. The exposure light is preferably chosen so that it radiates light of a wavelength to which the emulsion has been spectrally sensitized.
They may be chemically sensitized by effecting the ripening in the presence of small amounts of sulphur containing compounds such as allyl thiocyanate, allyl thiourea, sodium thiosulphate, etc. The emulsions may also be sensitized by means of reductors for instance tin compounds as described in French Patent Specification 1,146,955 and in Belgian Patent Specification 568,687, imino-amino methane sulphinic acid compounds as described in United Kingdom Patent Specification 789,823 and small amounts of noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium.
The said emulsions may also comprise compounds which sensitize the emulsion by development acceleration for example compounds of the polyoxyalkylene type such as alkylene oxide condensation products as described among others in US. Pats. 2,531,832 and 2,533,990, in United Kingdom Patent Specification 920,637, 940,051, 945,340 and 991,608 and in Belgian Patent Specification 648,710 and the known onium compounds including quaternary ammonium, quaternary phosphonium and ternary sulphonium compounds as well as onium derivatives of amino-N-oxides as described in United Kingdom Patent Specification 1,121,696.
Further the emulsions may comprise stabilizers e.g. heterocyclic nitrogen-containing thioxo compounds such as benzothiazoline-Z-thione and 1-phenyl-2-tetrazoline-5- thione and compounds of the hydroxytriazolopyrimidine type. They can also be stabilized with mercury compounds such as the mercury compounds described in Belgian Patent Specifications 524,121 and 677,337, United Kingdom Patent Specification 1,173,609 and in US. Pat. 3,179,520.
The emulsions may also comprise light-absorbing dyes which are so chosen that they absorb light of the Wavelength to which the material is exposed so that scattering and reflection of light within the photographic material is reduced. For more details regarding these dyes there can be referred to Belgian Patent Specification 699,375 and co-pending United Kingdom Patent Application 58,844/ 68. The dyes are preferably used in such amounts that per micron of emulsion layer thickness a density comprised between 0.05 and 0.20, measured in the spectral region of the exposure light, is obtained.
Any of the hardening agents for hydrophilic colloids may be used in the emulsions according to the present invention such as chromium, aluminium, and zirconium salts, formaldehyde, dialdehydes, hydroxy aldehydes, acrolein, glyoxal, halogen substituted aldehyde acids such as mucochloric acid and mucobromic acid, diketones such as divinyl ketone, compounds carrying one or more vinylsulphonyl groups such as divinyl sulphone, 1,3,5- trivinylsulphonyl benzene, hexahydro-s-triazines carrying vinylcarbonyl, halogenoacetyl and/or acyl groups such as 1,3,S-triacryloyl-hexahydro-1,3,5-triazine, 1,3 diacryloyl 5 acetylhexahydro 1,3,5 triazine, 1,3,5 trichloroacetylhexahydro-1,3,5-triazine, etc.
In order to promote adhesion of the emulsion to glass supports in the preparation of high resolution plate materials, the silicon compounds described in co-pending United Kingdom Patent Application 54,678/68 can be incorporated into the emulsion.
The light-sensitive emulsions may also comprise all other kinds of ingredients such as plasticizers, coating aids, etc.
Though the compounds corresponding to the above general formula have been particularly described for use in Lippmann-emulsions they can also be used in other light-sensitive silver halide emulsions to promote enhanced sharpness. The compounds of the invention are silver halide developing agents and release development inhibiting mercaptans. Thus, they may be used in X-ray and other non-optically sensitized emulsions as well as in orthochromatic, panchromatic and infrared-sensitive emulsions. Further, they may be used in emulsions intended for use in the well known silver complex diffusion transfer process.
They are particularly useful in emulsions intended for colour photography where, during development, on the exposed areas the oxidized aromatic primary amino colour developing agent couples with a colour forming coupler to form a dye image. By the presence of the compound of the invention in the emulsion, the development inhibitor is image-wise released which results in reduced graininess and the pyrocatechol developer locally regenerates the aromatic primary amino colour developing agent from its oxidation products.
The following examples illustrate the present invention.
EXAMPLE 1 A silver bromide emulsion comprising per kg. 72 g. of silver bromide and 93 g. of gelatin was prepared by simultaneous addition of a silver nitrate solution and a potassium bromide solution to a 3% aqueous solution of gelatin. The conditions of precipitation were adjusted so that a Lippmann emulsion with an average grain size of 70 nm. was obtained. Details as to the preparation of Lippmann-emulsions can be found amongst others in P. Glafkides Photographic Chemistry, Vol. I, 1958, Fountain Press, London.
The emulsion was sensitized by addition of 150 mg. per g. of silver halide of a merocyanine dye by means of which a strong spectral sensitization in the region of 520-550 nm. was obtained. Then, an amount of the light-absorbing dye having the following structural formula:
was added so as to obtain, after the emulsion is coated, a density of 0.10 per micron of emulsion layer thickness, measured at 550 nm. (absorption maximum of the lightabsorbing dye used).
The emulsion was divided into 2 portions and to one of these portions compound 5 was added in an amount of 500 mg. per mole of silver halide.
The emulsion portions were coated on glass plates pro rata of 230 ml. per sq. In. so as to obtain after drying a layer thickness of 6 microns. The 2 plate materials A and B were then exposed under identical circumstances by means of monochromatic light, the spectral composition of which corresponds with the absorption region of the light-absorbing dye used, through a test pattern, as normally used for the quantitative evaluation of materials for use in microelectronics mask-making, consisting of lines which are separated by spaces of the samewidth as the lines themselves and with a width varying from 1 to 20 The exposure was of such an intensity so as to limit the density in the transparent areas of the images produced, which correspond with the white lines of the test pattern, to the fog value.
After the exposure the 2 plate materials were reversal processed at 20 C., under completely identical circumstances.
For that purpose the exposed materials were first developed for about 5 min. in the following developing liquid the pH of which was adjusted to 10.5
Hydroquinone 2 Monomethyl-p-aminophenol hemisulphate 4 Potassium bromide 2 Sodium carbonate 40 Sodium sulphite 40 Potassium thiocyanate 5 Water to make 1 litre.
After rinsing for some minutes in water the materials were treated for 5 minutes in a clearing bath of the following composition:
Sodium sulphite g 100 Water to make 1000 ccs.
After rinsing again for some minutes the materials were subjected to an overall exposure in order to render the residual silver bromide developable whereupon they 7 were treated for about 6 minutes in the following developing liquid:
G. Hydroquinone Monomethyl-p-aminophenol hemisulphate 1 Sodium sulphite 40 Sodium carbonate 30 Potassium bromide 0.5
Water to make 1000 ccs.
EXAMPLE 2 Example 1 was repeated with the dilference that materials A and B were processed so as to obtain a negative image by means of a developing liquid of the following composition:
Water ml 800 Monomethyl-p-aminophenol' hemisulphate g 1.5 Sodium sulphite (anhydrous) g 25 Hydroquinone g 6 Sodium carbonate (anhydrous) g 40 Potassium bromide g 1 Water to make 1 litre.
As compared with material A, material B showed improved image-sharpness and less distortions in line-reproduction.
We claim:
1. Photographic silver halide emulsion comprising a compound of the general formula:
8 wherein: R is hydrogen, acyl, haloacyl or acyl carrying a quaternary ammonium group, R, is hydrogen, alkyl, aryl, halogen or alkoxy, and R is an aliphatic, aromatic or heterocyclic group.
2. Photographic silver halide emulsion according to claim 1, wherein in the formula R stands for a l-substituted S-tetrazolyl or 3-triazolyl group or for a 2-benzothiazolyl group.
3. Photographic silver halide emulsion according to claim 1, wherein said emulsion is a Lippmann-emulsion having an average-grain size of less than 100 nm.
4. Photographic silver halide emulsion according to claim 3, wherein the said compound is present in an amount comprised between 20 mg. and 2 g. per mole of silver halide.
5. Photographic silver halide emulsion according to claim 3, wherein the ratio of silver halide to hydrophilic colloid binder in the Lippmann-emulsion is comprised between 1:2 and 4: 1.
6. Photographic emulsion according to claim 3, wherein the said emulsion is a silver bromide emulsion which may comprise silver iodide in an amount of at most 8 mole percent and which has an average grainsize of at most nm.
7. Photographic material comprising a support and an emulsion according to claim 1.
8. Photographic material according to claim 9, wherein the said support is a glass support.
References Cited UNITED STATES PATENTS 3,700,457 10/1972 Youngquist 96-114.1
RONALD H. SMITH, Primary Examiner A. T. SURO PICO, Assistant Examiner US. Cl. X.R.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB5229071A GB1400149A (en) | 1971-11-10 | 1971-11-10 | Photographic silver halide material |
Publications (1)
Publication Number | Publication Date |
---|---|
US3825426A true US3825426A (en) | 1974-07-23 |
Family
ID=10463370
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00303404A Expired - Lifetime US3825426A (en) | 1971-11-10 | 1972-11-03 | Development of exposed photographic silver halide elements |
Country Status (8)
Country | Link |
---|---|
US (1) | US3825426A (en) |
JP (1) | JPS5611937B2 (en) |
BE (1) | BE791112A (en) |
CA (1) | CA995051A (en) |
DE (1) | DE2254358A1 (en) |
FR (1) | FR2159289B1 (en) |
GB (1) | GB1400149A (en) |
SU (1) | SU464135A3 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4254216A (en) * | 1977-09-12 | 1981-03-03 | Konishiroku Photo Industry Co., Ltd. | Color photographic material |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8630183D0 (en) * | 1986-12-17 | 1987-01-28 | Ciba Geigy Ag | Processing method |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3379529A (en) * | 1963-02-28 | 1968-04-23 | Eastman Kodak Co | Photographic inhibitor-releasing developers |
DE1903229C3 (en) * | 1969-01-23 | 1979-08-23 | Agfa-Gevaert Ag, 5090 Leverkusen | Process for the spectral sensitization of particularly fine-grain silver halide emulsions |
-
1971
- 1971-11-10 GB GB5229071A patent/GB1400149A/en not_active Expired
-
1972
- 1972-10-25 JP JP10702772A patent/JPS5611937B2/ja not_active Expired
- 1972-11-02 FR FR7238877A patent/FR2159289B1/fr not_active Expired
- 1972-11-03 US US00303404A patent/US3825426A/en not_active Expired - Lifetime
- 1972-11-07 DE DE2254358A patent/DE2254358A1/en active Granted
- 1972-11-09 CA CA156,114A patent/CA995051A/en not_active Expired
- 1972-11-09 SU SU1846498A patent/SU464135A3/en active
- 1972-11-09 BE BE791112A patent/BE791112A/en not_active IP Right Cessation
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4254216A (en) * | 1977-09-12 | 1981-03-03 | Konishiroku Photo Industry Co., Ltd. | Color photographic material |
US4314011A (en) * | 1977-09-12 | 1982-02-02 | Konishiroku Photo Industry Co., Ltd. | Color photographic material |
Also Published As
Publication number | Publication date |
---|---|
DE2254358A1 (en) | 1973-05-17 |
DE2254358C2 (en) | 1987-04-16 |
SU464135A3 (en) | 1975-03-15 |
CA995051A (en) | 1976-08-17 |
BE791112A (en) | 1973-05-09 |
FR2159289B1 (en) | 1976-06-04 |
FR2159289A1 (en) | 1973-06-22 |
JPS4856129A (en) | 1973-08-07 |
GB1400149A (en) | 1975-07-16 |
JPS5611937B2 (en) | 1981-03-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US3704130A (en) | Photographic fine grain silver halide emulsions | |
JPS59212829A (en) | Aryl hydrazide | |
US4469783A (en) | Silver halide photographic emulsions | |
EP0059144B1 (en) | Silver halide emulsion containing latent image stabilizer and element | |
US3765901A (en) | Spectral sensitization of light-sensitive silver halide emulsions | |
US4335200A (en) | Silver halide photographic materials | |
US3759713A (en) | Merocyanine dye and a corbocyanine dye fogged direct positive silyer halide emulsion supersensitized with a | |
US3266897A (en) | Antifoggant agents for photography | |
US3632340A (en) | Cored direct positive silver halide emulsion developed with polyhydroxybenzene | |
US3869290A (en) | Photographic silver halide elements of the Lippmann-type | |
US3825426A (en) | Development of exposed photographic silver halide elements | |
US3717466A (en) | Fogged direct positive silver halide element containing a selenium compound sensitizer | |
US4467029A (en) | Method for producing a photographic image from a Lippmann type silver halide photographic light-sensitive material | |
US3841877A (en) | Development of exposed photographic silver halide elements | |
US3765900A (en) | Spectrally sensitized silver halide emulsions | |
US3615517A (en) | Direct-positive silver halide emulsion containing halogen conductor and electron acceptor developed with polyhydroxy benzene | |
US4202695A (en) | Photographic Lippmann emulsions | |
US4108661A (en) | Lippmann-emulsions and reversal processing thereof | |
US4065312A (en) | Process for the production of photographic vesicular images in photographic silver halide material | |
JPH0252333A (en) | Improved high contrast dot quality composition and photographic product and use thereof | |
US3652280A (en) | Light-sensitive silver halide emulsion with high resolving power | |
US3847617A (en) | Process of preparing fine-grain silverhalide emulsions | |
US4260674A (en) | Silver salt photographic material for the production of silver and bubble photographic images with 80% transparency | |
US3752673A (en) | Silver halide emulsion containing a merocyanine dye | |
US3671259A (en) | Photographic bleaching and antifogging agents |