US3081170A - Fog reduction in photographic silver halide emulsions - Google Patents
Fog reduction in photographic silver halide emulsions Download PDFInfo
- Publication number
- US3081170A US3081170A US765339A US76533958A US3081170A US 3081170 A US3081170 A US 3081170A US 765339 A US765339 A US 765339A US 76533958 A US76533958 A US 76533958A US 3081170 A US3081170 A US 3081170A
- Authority
- US
- United States
- Prior art keywords
- silver halide
- emulsion
- thione
- hydrogen
- mercaptobenzothiazole
- 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
- 239000000839 emulsion Substances 0.000 title description 55
- -1 silver halide Chemical class 0.000 title description 37
- 229910052709 silver Inorganic materials 0.000 title description 26
- 239000004332 silver Substances 0.000 title description 26
- 150000001875 compounds Chemical class 0.000 description 28
- 229910052739 hydrogen Inorganic materials 0.000 description 20
- 239000001257 hydrogen Substances 0.000 description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 15
- 150000002431 hydrogen Chemical class 0.000 description 14
- 125000003118 aryl group Chemical group 0.000 description 13
- 230000000087 stabilizing effect Effects 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 12
- 125000004429 atom Chemical group 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 230000005070 ripening Effects 0.000 description 8
- 229910052717 sulfur Inorganic materials 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 125000000623 heterocyclic group Chemical group 0.000 description 6
- 125000001424 substituent group Chemical group 0.000 description 6
- 229940054266 2-mercaptobenzothiazole Drugs 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 150000002780 morpholines Chemical class 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 description 4
- 125000001931 aliphatic group Chemical group 0.000 description 4
- 125000003710 aryl alkyl group Chemical group 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 2
- VVJKKWFAADXIJK-UHFFFAOYSA-N Allylamine Chemical compound NCC=C VVJKKWFAADXIJK-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 125000002252 acyl group Chemical group 0.000 description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000012937 correction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 2
- ZILSBZLQGRBMOR-UHFFFAOYSA-N 1,3-benzodioxol-5-ylmethanamine Chemical compound NCC1=CC=C2OCOC2=C1 ZILSBZLQGRBMOR-UHFFFAOYSA-N 0.000 description 1
- AIGNCQCMONAWOL-UHFFFAOYSA-N 1,3-benzoselenazole Chemical compound C1=CC=C2[se]C=NC2=C1 AIGNCQCMONAWOL-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical compound C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
- ODIRBFFBCSTPTO-UHFFFAOYSA-N 1,3-selenazole Chemical compound C1=C[se]C=N1 ODIRBFFBCSTPTO-UHFFFAOYSA-N 0.000 description 1
- JINXYLZMLZNPAR-UHFFFAOYSA-N 1-sulfanylidene-1,3-benzothiazole Chemical compound C1=CC=C2S(=S)C=NC2=C1 JINXYLZMLZNPAR-UHFFFAOYSA-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
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-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
- YGYXYFFFRWOVAE-UHFFFAOYSA-N 3-(morpholin-4-ylmethyl)-1,3-benzothiazole-2-thione Chemical compound S=C1SC2=CC=CC=C2N1CN1CCOCC1 YGYXYFFFRWOVAE-UHFFFAOYSA-N 0.000 description 1
- VVEQSNONASWWMH-UHFFFAOYSA-N 3h-1,3-benzoselenazole-2-thione Chemical compound C1=CC=C2[se]C(S)=NC2=C1 VVEQSNONASWWMH-UHFFFAOYSA-N 0.000 description 1
- CFHLPYGPURTAMI-UHFFFAOYSA-N 4,5-diethyl-3h-1,3-thiazole-2-thione Chemical compound CCC=1N=C(S)SC=1CC CFHLPYGPURTAMI-UHFFFAOYSA-N 0.000 description 1
- NLHAIPFBNQZTMY-UHFFFAOYSA-N 4-methyl-3h-1,3-thiazole-2-thione Chemical compound CC1=CSC(S)=N1 NLHAIPFBNQZTMY-UHFFFAOYSA-N 0.000 description 1
- ZVNPWFOVUDMGRP-UHFFFAOYSA-N 4-methylaminophenol sulfate Chemical compound OS(O)(=O)=O.CNC1=CC=C(O)C=C1.CNC1=CC=C(O)C=C1 ZVNPWFOVUDMGRP-UHFFFAOYSA-N 0.000 description 1
- JAHGNXIJPWTQNB-UHFFFAOYSA-N 5,6-dichloro-3h-1,3-benzothiazole-2-thione Chemical compound ClC1=C(Cl)C=C2SC(S)=NC2=C1 JAHGNXIJPWTQNB-UHFFFAOYSA-N 0.000 description 1
- YPXQSGWOGQPLQO-UHFFFAOYSA-N 5-nitro-1,3-dihydrobenzimidazole-2-thione Chemical compound [O-][N+](=O)C1=CC=C2N=C(S)NC2=C1 YPXQSGWOGQPLQO-UHFFFAOYSA-N 0.000 description 1
- QPOZGXKWWKLJDK-UHFFFAOYSA-N 6-nitro-3h-1,3-benzothiazole-2-thione Chemical compound [O-][N+](=O)C1=CC=C2NC(=S)SC2=C1 QPOZGXKWWKLJDK-UHFFFAOYSA-N 0.000 description 1
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- JZICLIPTNFCEOJ-UHFFFAOYSA-O SC1=NC(C=CC=C2)=C2[S+]1Cl Chemical compound SC1=NC(C=CC=C2)=C2[S+]1Cl JZICLIPTNFCEOJ-UHFFFAOYSA-O 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910021612 Silver iodide Inorganic materials 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical class C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 125000005111 carboxyalkoxy group Chemical group 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 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
- 229920002678 cellulose Polymers 0.000 description 1
- 125000002603 chloroethyl group Chemical group [H]C([*])([H])C([H])([H])Cl 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-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
- 239000000975 dye Substances 0.000 description 1
- VMSUNVQFEYKKMB-UHFFFAOYSA-N ethanamine;methanamine Chemical compound NC.CCN VMSUNVQFEYKKMB-UHFFFAOYSA-N 0.000 description 1
- JUOXYWXXPHUSAI-UHFFFAOYSA-N ethylamino acetate Chemical compound CCNOC(C)=O JUOXYWXXPHUSAI-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- ZLTPDFXIESTBQG-UHFFFAOYSA-N isothiazole Chemical compound C=1C=NSC=1 ZLTPDFXIESTBQG-UHFFFAOYSA-N 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 description 1
- CWMRFSSMSXQUJC-UHFFFAOYSA-N pyrrole-2-thione Chemical class S=C1C=CC=N1 CWMRFSSMSXQUJC-UHFFFAOYSA-N 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- ADZWSOLPGZMUMY-UHFFFAOYSA-M silver bromide Chemical compound [Ag]Br ADZWSOLPGZMUMY-UHFFFAOYSA-M 0.000 description 1
- 229940045105 silver iodide Drugs 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 1
- 229940001482 sodium sulfite Drugs 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 125000001712 tetrahydronaphthyl group Chemical group C1(CCCC2=CC=CC=C12)* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
- G03C1/00—Photosensitive materials
- G03C1/005—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
Definitions
- an object of this invention to produce a light-sensitive emulsion which is fast, stable, has a reduced tendency to fog and has good'contrast.
- a further object of this invention resides in a lightsensitive emulsion which contains a compound which stabilizes the emulsion against fogging and at the same time does not materially reduce thespeed and/ or the contrast of the emulsion.
- N-substituted-3-aminomethylazolethiones when added to a light-sensitive silver halide emulsion, stabilize and inhibit the fogging of the emulsion.
- R and R are hydrogen atoms or alkyl radicals
- acyl radical e.g.,-acetyl, propionyl and the like
- a carboxyalkoxy radical e.g., carboxymethoxy, carboxyethoxy, carboxyprop'oxy
- X represents alkyl, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, chloroethyl, carboxymethyl, allyl; aryl, .e.g., phenyl, naphthyl, tetrahydronaphthyl, aralkyl, e.g., benzyl, phenethyl; X represents hydrogen .or a substituent having the value stated for X; and wherein X and X together represent the atoms necessary to complete a heterocyclic, hydrogenated ring system, e.g., a
- These compounds are prepared by reacting a 2-mercapto-substituted azole of the oxazole, benzoxazole, selenazole, benz-oselenazole, thiazole and benzothiazole series simultaneously with formaldehyde and a primary or secondary amine in the presence of a suitable solvent such as methanol, ethanol, isopropanol and the like.
- a suitable solvent such as methanol, ethanol, isopropanol and the like.
- the antifogging agent of our invention is added to the emulsion just prior to coating it on a suitable support such as glass, paper, or film at a time when the emulsion has nearly attained its maximum sensitivity.
- the antifogging and stabilizing compounds of our invention in a separate layer such as an undercoating layer or in an antiabrasion gelatin surface. Sometimes it is desirable to incorporate the compounds in one or all processing baths or in the preand post-baths.
- the antifoggants of our invention are preferably added to the emulsion in an amount ranging from 0.1 milligram to 20 milligrams per 0.6 mol of silver halide and when used as a coating final, it is preferably added in an amount ranging from 0.5 milligram .to 50 milligrams per 0.6 mol of silver halide.
- the optimum amount to be added depends primarily on the type of emulsion and should be determined also be used in combination with known antifoggants and stabilizers,
- the antifoggants of our invention can also be used in combination with sensitiz'ers such as sulfur, metal and reduction sensitizers as well as with speedincreasing agents and accelerators such as the reaction products of long-chain alcohols and ethylene oxide (see US. Patent 1,970,578) and their derivatives and polyvinyl-pyrrolidone.
- novel antifoggants of our invention may be used with various'types of photographic emulsions, such as non-sensitized orthochromatic,panchromatic and X-ray emulsions, paper emulsions and color emulsions.
- Example I A silver halide emulsion in gelatin containing 2 percent silver iodide and 98 percent silver bromide was prepared in a conventional manner and brought up to its maximum light sensitivity. It was then readied for coating, finals were added such as sensitizing dyes and hardening agents. A 0.1 percent solution of 3-morpholinomethyl benzothiazole-Z-thione prepared according to the method described in British Patent 377,253 was added in varying amounts to .samples of the emulsion as an anti- -foggant and stabilizer. Each emulsion sample contained about 0.6 mol of silver halide. The so prepared emulsion samples were coated on a suitable cellulose ester base and dried. Samples of these film coatings were then exposed in a type IIB sensitometer and developed in a developer of the following composition:
- Example II The procedure followed was identical to Example I, except that in place of 3-morpholinomethyl-benzothiazole- Z-thione' the compound used was 3-piperidinomethyl-benzoxazole-Z-thioiie prepared according to the method described in Berichte, v01. 90, page 2246.
- Example I was repeated except that 4-chl-oro-3 -morpholinomethyl-benzoxazole-2-thione was used in place of 3- morpholinomethyl-benzothiazole-Z-thione. The results obtained were essentially the same as those reported in Example I.
- the compound was prepared as follows:
- Example V Example I was repeated except that 6-nitno-3-piperidinomethyl-benzothiazole-Z-thione was used in place of 3- morpholinomethyl-benzothiazole-Z-thione. The results obtained were very similar to those described in Example I.
- the benzothiazolethione was prepared as follows:
- X and X are selected from the group consisting of hydrogen, alkyl, aryl and aralkyl, X being a substituent other than hydrogen when X is hydrogen, and X represents the atoms necessary to complete a hydrogenated heterocyclic ring system of the piperidine and morpholine series.
- a light-sensitive photographic element comprising a base and a coating of gelatino-silver halide emulsion thereon, said emulsion containing as an antifogging and stabilizing agent, a compound selected from the group having the following formulae:
- R and R are selected irom the group consisting of hydrogen, an aliphatic radical, an aromatic radical; Z represents the atoms necessary to complete a fused-on aromatic ring structure, Y is a member selected from the group consisting of oxygen and sulfur, A is a member selected from the class consisting of and wherein X and X are selected from the group consisting of hydrogen, aliphatic, aryl and aralkyl radicals, X being a substituent other than hydrogen when X is hydrogen, and wherein X represents the atoms necessary to complete a hydrogenated heterocyclic ring system of the piperidine and morpholine series.
- a light-sensitive structure comprising a base, a lens, and a lens.
- N 5HrA and Y Y ⁇ 0 O z o s s o l :2 a N OH2OH: N 5 5 H2N /N H: CH2CH2
- R and R are selected from the group consisting of hydrogen, an aliphatic radical, an aromatic radical
- Z represents the atoms necessary to complete a fused-on aromatic ring structure
- Y is a member selected from the group consisting of oxygen and sulfur
- A is a member selected from the class consisting of and wherein X and X are selected from the group consisting of hydrogen, aliphatic, aryl and aralkyl radicals, X being a substituent other than hydrogen when X is hydrogen, wherein X represents the atoms necessary to complete a hydrogenated heterocyclic ring system of the piperidine and morpholine series.
- a process of forming a photographic silver halide emulsion having a reduced tendency to fog which comprises forming the emulsion, ripening the emulsion and during said ripening adding thereto a compound selected from the group having the following general formulae:
- R and R are selected from the group consisting or hydrogen, an aliphatic radical, an aromatic radical; Z represents the atoms necessary to complete a fused-on aromatic ring structure, Y is a member selected from the group consisting of oxygen and sulfur, A is a member selected from the class consisting of and wherein X and X; are selectedfrorn the group consisting of hydrogen, aliphatic, aryl and ara-lkyl radicals, X being a substituent other than hydrogen when X is hydrogen, and wherein X represents the atoms necessary to complete a hydrogenated heterocyclic ring system of the piperidine and morpholine series.
- a process of forming a light-sensitive photographic element having a reduced tendency to fog which cornprises forming a silver halide emulsion, ripening said emulsion, coating said emulsion on a base and adding to said emulsion just prior to the coating thereof on the base a compound selected frorn the group having the following general formulae:
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Description
United States Patent "ce This invention relates to photographic materials and to methods of preparing them. More particularly, this invention relates to light-sensitive silver halide emulsions containing as a stabilizing and antifogging agent an N- substituted-3-aminomethylazolethione.
It is well known in the photographic art that light-- sensitive emulsions, such as gelatino-silver halide emulsions, have a tendency to fog. Fog is usually caused by a prolonged ripening of the emulsion, by prolonged storage especially at elevated temperatures and humidity,
and by prolonged development. To overcome this undesirable property, it has been the practice in this art to add certain chemical compounds to the emulsions to. increase their stability and to reduce their tendency to fog. However, the stabilizing and antifogging compounds heretofore used in this art have the disadvantage that upon addition to the emulsion they cause a loss of speed and/ or contrast of the emulsion.
It is, accordindgly, an object of this invention to produce a light-sensitive emulsion which is fast, stable, has a reduced tendency to fog and has good'contrast.
A further object of this invention resides in a lightsensitive emulsion which contains a compound which stabilizes the emulsion against fogging and at the same time does not materially reduce thespeed and/ or the contrast of the emulsion.
We have discovered that N-substituted-3-aminomethylazolethiones when added to a light-sensitive silver halide emulsion, stabilize and inhibit the fogging of the emulsion.
The azolethiones, the use of which is contemplated herein, may be represented by the following formulae:
and
wherein R and R are hydrogen atoms or alkyl radicals,
e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl,
amyl, dodecyl and the like; and acyl radical, e.g.,-acetyl, propionyl and the like; a carboxyalkoxy radical, e.g., carboxymethoxy, carboxyethoxy, carboxyprop'oxy, X represents alkyl, e.g., methyl, ethyl, propyl, isopropyl, butyl, isobutyl, amyl, isoamyl, chloroethyl, carboxymethyl, allyl; aryl, .e.g., phenyl, naphthyl, tetrahydronaphthyl, aralkyl, e.g., benzyl, phenethyl; X represents hydrogen .or a substituent having the value stated for X; and wherein X and X together represent the atoms necessary to complete a heterocyclic, hydrogenated ring system, e.g., a p'iperidine, tetrahydroquinoline, morpholine or 3,081,170 Patented Mar, 12, 1963 2 piperazine ring system, Y is an oxygen, selenium or sulfur atom, and Z represents the atoms necessary to complete a fused-0n aromatic ring system such as a benzo or naphtho ring which can be further substituted.
The following specific compounds are examples of compounds belonging to the class of compounds having the general formula given above which we have found suitable for use as stabilizing an antifogging agents:
(llHzN CH2 GH2OH2 v 3-piperidinomethyl-benzoxazole-2rthione HzN N Hz CHr-C 1 V 1, l-bisbenzoxazole-2-thione-3-methylpiperazine N HP H:
3-morpholinomethylbe DzoXazole 2-thione O 3H5 H2 v Cgl15 I 3-diethy1aminomethyl-benzoxazoIe Z-thiOne .CHrCHz CH: CHg-CH2 3-piperidinomethyl-benzothiazole-2-thlone CHzN O CHz GZ 3-morpholinomethy1-benzothlazo1e-2-thione CHzN HzN N-CH:
CHz-CH:
1,4-blsbenzothiazole-2-thione-B-methylpiperazine III OHi-OHH CHzN CH2 CHr-OH: 3-piper1dinomethyl-benzoselenazole-2-thione These compounds are prepared by reacting a 2-mercapto-substituted azole of the oxazole, benzoxazole, selenazole, benz-oselenazole, thiazole and benzothiazole series simultaneously with formaldehyde and a primary or secondary amine in the presence of a suitable solvent such as methanol, ethanol, isopropanol and the like. The preparation of these compounds is described in more detail in US. Patent 2,411,253, British patent 377,253; and Journal of the Chemical Society, 1948, page 1717.
As representatives of azoles used in the reaction the following are mentioned:
4-methyl-2-mercaptothiazole 4-ethyl-2-meroaptothiazole 4-pnopyl-2-mercaptothiazole 4-dodecyl-2-mercaptothlazole 4-buttyl-2-mercaptothi azole 4-phenyl-2-mercaptothiazole 4-p-chlorophenyl-2-mereaptothiazole 4-p-methoxyphenyl-Z-mercaptothiazole 4,5 -propano-2-mercaptothiazole 4,5 -dimethyl-2-mercaptothiazole 4,5 -:diphenyl-2-mercaptothi-azole 4,5 -diethyl-2-mercaptothiazole 5-oarbomethoxy-4-m-ethyl-Z-mercaptothiazole 5-methyl-Z-mercapbobenzothiazole 6-methyl-2-mercaptobenzothiazole 7-methyl-2-mercaptobenzothiazole 6-ter-t.-butyl-2-mercaptobenzothiazole 61phenyl-2-mercaptobenzothiazole 5-hydroxy-Z-mercaptobenzothiazole S-chloro-2-mercaptobenzothiazole S-bmomo-Z-mercaptob enzothiazole 6-chloro 2-mercaptobenzothiazole 6-bromo-2-mercaptobenzothiazole 6-nitro-2-rnercaptobenzothiazole S-amino-2-mercaptobenzothiazole 6-amino-2-mercaptobenzothiazole 6-acetamido-2-mercaptobenzothiazole 6-benzamido-2-mercaptobenzothiazole 6-dimethylamino-2-m-ercaptobenzothiazole 5-carboxyl-2-mercaptob enzothiazole 4,6adimethyl-2-rnercaptobenzothiazole 4-methyl-6-chloro-Z-mercaptobenzothiazole 5,6-dichloro-2-mercaptobenzothiazole 4-carboXy-6-chlono-2-mercaptobenzothiazole 4,6-dimethyl-7-chloro-2-rnercaptobenzothiazole 4,6-dimethyl-5,7-dichloro-3 -mercaptobenzothiazole 4,5-benzo-Z-mercaptobenzothiazole 6,7-benzo-2-mercaptobenzothiazole 2-mercapto-4,5,6,7-dibenzobenzothiazole Z-mercapto-S,6-naphthobenzothiazole 2-mercapto-5,6-benzobenZothi-azole 2-mercapto-4,5-fiuorenyl 1,2 -thiazole 6,7-benzo-2-mercaptobenzo selenazole 2-mercaptobenzoselenazole Z-mercaptos elenazole 2-meroapto-5-methoxybenzoselenazole 2-mercapto-S-methylbenzoselenazole 2-mencapto-6-methoxyquinoline 2-mercapto-6-rnethylquinoline 2-mercaptobenzoxazole 2-rnercapto-51phenylbenzoxazole 2-mencapto-S-methoxybenzoxazole 2-mercapto-S-methylbenzoxazole 2-mercapto-4,S-benzobenzoxazole The following list is representative .of primary and secondary amines, the latter including cyclic amines, which can be condensed with formaldehyde and the mercap toazoles Methylamine Ethylamine fl-Hydroxyethylamine fi-Chlo-roethylamine \Allyl-amine Benzylamine B-P-henylethylamine Ethylenediamine Ethyl amino acetate w-Aminoacetophenone Tetrahydno-fi-naphthylamine Aniline 3,4-methylene-dioxybenzyl-amine ,4 Dirnethylamine Diethylamine Diethanolarnine Dipropylamine Di-n-butylamine -Diisoamylamine Dibenzylamine methyldiethylethylenediamine Methylaniline Piperidine 1 ,2,3 ,4-tetrahydroisoquinoline 6-methoxy-1,2,3,4-tetrahydroisoquinoline Morpholine Piperiazine w-Methy-laminopnopiophenone fi-Acetylethylbenzylamine Benzyl-( 2-cyclohexanonylmethyl -amine 3,4-methylenedioxybenzyl- (2acyclohexanylm ethyl -amine The antifogging agents of our invention may be added to the emulsion at any stage during its process of production. Thus, they may be added as a ripening final or as a coating final. When added as a ripening final, they are added during the ripening or sensitivity increasing stage of the emulsion making process. Such addition may be made before, during or after the addition of the soluble silver salt to the soluble halide in the presence of a suitable colloid, such as gelatin, polyvinyl alcohol, solubilized casein or albumin. When added as a coating final, the antifogging agent of our invention is added to the emulsion just prior to coating it on a suitable support such as glass, paper, or film at a time when the emulsion has nearly attained its maximum sensitivity.
In some instances, it is advantageous to apply the antifogging and stabilizing compounds of our invention in a separate layer such as an undercoating layer or in an antiabrasion gelatin surface. Sometimes it is desirable to incorporate the compounds in one or all processing baths or in the preand post-baths.
When used as a ripening final, the antifoggants of our invention are preferably added to the emulsion in an amount ranging from 0.1 milligram to 20 milligrams per 0.6 mol of silver halide and when used as a coating final, it is preferably added in an amount ranging from 0.5 milligram .to 50 milligrams per 0.6 mol of silver halide. The optimum amount to be added depends primarily on the type of emulsion and should be determined also be used in combination with known antifoggants and stabilizers, The antifoggants of our invention can also be used in combination with sensitiz'ers such as sulfur, metal and reduction sensitizers as well as with speedincreasing agents and accelerators such as the reaction products of long-chain alcohols and ethylene oxide (see US. Patent 1,970,578) and their derivatives and polyvinyl-pyrrolidone.
The novel antifoggants of our invention may be used with various'types of photographic emulsions, such as non-sensitized orthochromatic,panchromatic and X-ray emulsions, paper emulsions and color emulsions.
The following specific examples are [given as an illustration of the manner in which the anti'foggants of our invention can be used. It is to be understood, however, that these examples are given byway of illustration and not by way of limitation.
Example I A silver halide emulsion in gelatin containing 2 percent silver iodide and 98 percent silver bromide was prepared in a conventional manner and brought up to its maximum light sensitivity. It was then readied for coating, finals were added such as sensitizing dyes and hardening agents. A 0.1 percent solution of 3-morpholinomethyl benzothiazole-Z-thione prepared according to the method described in British Patent 377,253 was added in varying amounts to .samples of the emulsion as an anti- -foggant and stabilizer. Each emulsion sample contained about 0.6 mol of silver halide. The so prepared emulsion samples were coated on a suitable cellulose ester base and dried. Samples of these film coatings were then exposed in a type IIB sensitometer and developed in a developer of the following composition:
Grains Metol 1.5 Sodiumsulfite (anhydrous) 45 Sodium bisulfite 1 Hydroquinone 6 Sodium carbonate (monohydrated) .8
Water to make -1 liter.
The developed samples were short-stopped, fixed, washed and dried. The results obtained were as follows:
Fog at 12 Oven Fog Quantity of Compound Used Relative Minute at ti Minute Speed Develop- Development ment Example II The procedure followed was identical to Example I, except that in place of 3-morpholinomethyl-benzothiazole- Z-thione' the compound used was 3-piperidinomethyl-benzoxazole-Z-thioiie prepared according to the method described in Berichte, v01. 90, page 2246.
The procedure followed was identical to Example I, but in place of 3-morpholinomethyl-benzothiazole-2- thione, the compound used was 3-dimethylaminomethyl- 6' benz-oaxazole-2-thione which had been prepared according to the method described in Berichte, vol. 90, page 2246;
The results obtained were as follows:
Example I was repeated except that 4-chl-oro-3 -morpholinomethyl-benzoxazole-2-thione was used in place of 3- morpholinomethyl-benzothiazole-Z-thione. The results obtained were essentially the same as those reported in Example I.
The compound was prepared as follows:
A solution of 4.6 grams of 4-chloro-2mercaptobenzoxaz ole and 2.4 milliliters of morpholine in 10 milliliters of methanol was cooled to about 5 C. After the addition of 3.3 milliliters of formaldehyde (37 percent) to the solution, an instantaneous reaction took place. The reaction mixture was then left standing for 2 hours at room temperature. The product which separated was recrystallized from methanol and melted at -151 C.
Example V Example I was repeated except that 6-nitno-3-piperidinomethyl-benzothiazole-Z-thione was used in place of 3- morpholinomethyl-benzothiazole-Z-thione. The results obtained were very similar to those described in Example I.
The benzothiazolethione was prepared as follows:
A suspension of 6.3 grams of 6-nitro-2-mercaptobenzothiazole in 30 milliliters 'of methanol was added to a solution of 2.5 milliliters of piperidine and 2.7 milliliters of formaldehyde (37 percent) in 10 milliliters of methanol. The reaction mixture was left for 2 hours at room temperature after the exothermic reaction had subsided. The precipitate was recrystallized from ethyl acetate and melted at 169 C.
Our invention is not limited to the detailed description contained herein, but includes all modifications that fall within the scope of the appended claims.
We claim:
1. A lightsensitive silver halide emulsion containing as an antifogging and stabilizing agent a compound selected from the group of those having the'following general chemical formulae:
l CHr-A and Y 0 2:" o=s N CHz-A and /Y Y z: o s s=o :z 0 O N omoHi N wherein X and X are selected from the group consisting of hydrogen, alkyl, aryl and aralkyl, X being a substituent other than hydrogen when X is hydrogen, and X represents the atoms necessary to complete a hydrogenated heterocyclic ring system of the piperidine and morpholine series.
2. A light-sensitive photographic element comprising a base and a coating of gelatino-silver halide emulsion thereon, said emulsion containing as an antifogging and stabilizing agent, a compound selected from the group having the following formulae:
wherein R and R are selected irom the group consisting of hydrogen, an aliphatic radical, an aromatic radical; Z represents the atoms necessary to complete a fused-on aromatic ring structure, Y is a member selected from the group consisting of oxygen and sulfur, A is a member selected from the class consisting of and wherein X and X are selected from the group consisting of hydrogen, aliphatic, aryl and aralkyl radicals, X being a substituent other than hydrogen when X is hydrogen, and wherein X represents the atoms necessary to complete a hydrogenated heterocyclic ring system of the piperidine and morpholine series.
3. A light-sensitive structure comprising a base, a
8 layer of light-sensitive silver halide emulsion thereon, and a separate layer adjacent said first mentioned layer containing as an anti-fogging and stabilizing agent com pound, a compound selected from the group having the following general chemical structures:
R-O It ("3 N Hl-A and Y z: o=s
a N 5HrA and Y Y\ 0 O z: o s s o l :2 a N OH2OH: N 5 5 H2N /N H: CH2CH2 wherein R and R are selected from the group consisting of hydrogen, an aliphatic radical, an aromatic radical; Z represents the atoms necessary to complete a fused-on aromatic ring structure, Y is a member selected from the group consisting of oxygen and sulfur, A is a member selected from the class consisting of and wherein X and X are selected from the group consisting of hydrogen, aliphatic, aryl and aralkyl radicals, X being a substituent other than hydrogen when X is hydrogen, wherein X represents the atoms necessary to complete a hydrogenated heterocyclic ring system of the piperidine and morpholine series.
4. A process of forming a photographic silver halide emulsion having a reduced tendency to fog which comprises forming the emulsion, ripening the emulsion and during said ripening adding thereto a compound selected from the group having the following general formulae:
and
. and
CH2-C a wherein R and R are selected from the group consisting or hydrogen, an aliphatic radical, an aromatic radical; Z represents the atoms necessary to complete a fused-on aromatic ring structure, Y is a member selected from the group consisting of oxygen and sulfur, A is a member selected from the class consisting of and wherein X and X; are selectedfrorn the group consisting of hydrogen, aliphatic, aryl and ara-lkyl radicals, X being a substituent other than hydrogen when X is hydrogen, and wherein X represents the atoms necessary to complete a hydrogenated heterocyclic ring system of the piperidine and morpholine series.
5. A process of forming a light-sensitive photographic element having a reduced tendency to fog which cornprises forming a silver halide emulsion, ripening said emulsion, coating said emulsion on a base and adding to said emulsion just prior to the coating thereof on the base a compound selected frorn the group having the following general formulae:
wherein R and R; are selected from the group consisting 65 10 of: hydrogen, alkyl, acyl and carboxyalkexy; Z represents the atoms necessary to complete a fused-on aromatic ring structure of the benzene and naphthalene se- =ries; Y is a member selected from the group consisting of oxygen and sulfur; A is a member selected from the class consisting of wherein X and X are selected from the group consisting of hydrogen, alkyl, aryl and aralkyl, X being a substituent other than hydrogen when X is hydrogen, and X represents the atoms necessary to complete a hydrogenated heterocyclic ring system of the piperidine and morpholine series.
6. A light-sensitive silver halide emulsion as recited in claim 1, wherein the antifogging and stabilizing compound is 3-morpholinomethyl-benzoth-iazole-2-thione.
7. A light-sensitive silver halide emulsion as recited in claim 1, wherein the antifogging and stabilizing compound is 3-piperidinome-thyl-benzoxazole-2-thione.
8. A light-sensitive halide emulsion as recited in claim 1, wherein the antifogging and stabilizing compound is 3-dimethylaminomethyl-benzoxazole-Z-thione.
9. A light-sensitive silver halide emulsion as recited in claim 1, wherein the antifogging and stabilizing compound is 3-morpholinomethylbenzoxazole-Z-thione.
10. A light-sensitive silver halide emulsion as recited in claim 1, wherein the antifogging and stabilizing compound is 3-diethylaminomethyl-benzoxazole-Z-thione.
11. A light-sensitive silver halide emulsion as recited in claim 1, wherein the antifogging and stabilizing compound is 3-piperidin0methyl-benzothiazole-Z-thione.
12. A light-sensitive silver halide emulsion as recited in claim 1, wherein the antifogging and stabilizing compound is present in the emulsion in the ratio of 0.1 to milligrams per 0.6 mol of silver halide.
13. A light-sensitive silver halide emulsion as recited in claim 1, wherein the anti-fogging and stabilizing compound is present in the emulsion in the ratio of 0.1 to 20 milligrams per 0.6 mol of silver halide.
14. A light-sensitive silver halide emulsion as recited in claim 1, wherein the antifogging and stabilizing compound is present in the emulsion in the ratio of 0.5 to 50 milligrams per 0.6 mol of silver halide.
15. A light-sensitive silver halide emulsion as recited in claim 1, wherein said emulsion is a panchromatic emulsion.
16. A light-sensitive silver halide emulsion as recited in claim 1, containing the reaction product of a long chain alcohol and ethylene oxide as an accelerator.
References Cited in the file of this patent UNITED STATES PATENTS 2,099,374 Schwarz Nov. 16, 1937 2,463,346 Russell Nov. 9, 1948 2,819,965 Murray et al. Jan. 14, 1958 2,870,015 Allen et a1. Jan. 20, 19 59 UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,081,170 March 12, 1963 Emil B. Rauch et al.
It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.
Column 7, lines 55 and 56, column 8, lines 34 and 35, and column 9, lines 12 and 13, for "an aliphatic radical, an aromatic radical;", each occurrence, read alkyl, acyl and carboxyalkoxy; column 7, line 57, column 8, line 36, and column 9, line 14, for "structure,", each occurrence, read structure of the benzene and naphthalene series; column 7, line 58, column 8, line 37, and column 9, line 15, for "sulfur,",each occurrence, read sulfur; column 7, line 70, column 8, line 49, and column 9, line 26, for "aliphatic, aryl and aralkyl radicals,", each occurrence,
read alkyl, aryl and aralkyl, column 7, line 72 and column 9, line 29, strike out "wherein", each occurrence; column 8, line 51, for "wherein" read and Signed and sealed this 24th day of November 1964.
(SEAL) Attest:
ERNEST W, SWIDER EDWARD J. BRENNER Attesting Officer Commissioner of Patents
Claims (1)
1. A LIGHT-SENSITIVE SILVER HALIDE EMULSION CONTAINING AS AN ANTIFOGGING AND STABILIZING AGENT A COMPOUND SELECTED FROM THE GROUP OF THOSE HAVING THE FOLLOWING GENERAL CHEMICAL FORMULAE:
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US765339A US3081170A (en) | 1958-10-06 | 1958-10-06 | Fog reduction in photographic silver halide emulsions |
| DEG28090A DE1182059B (en) | 1958-10-06 | 1959-10-06 | Photographic material containing antifoggants |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US765339A US3081170A (en) | 1958-10-06 | 1958-10-06 | Fog reduction in photographic silver halide emulsions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3081170A true US3081170A (en) | 1963-03-12 |
Family
ID=25073301
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US765339A Expired - Lifetime US3081170A (en) | 1958-10-06 | 1958-10-06 | Fog reduction in photographic silver halide emulsions |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3081170A (en) |
| DE (1) | DE1182059B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3251691A (en) * | 1960-09-23 | 1966-05-17 | Gevaert Photo Prod Nv | Photographic material |
| DE2210369A1 (en) * | 1971-03-04 | 1972-09-28 | Fuji Photo Film Co. Ltd., Ashigara-Kamigun, Kanagawa (Japan) | Process for the production of photographic images |
| DE2263808A1 (en) * | 1971-12-28 | 1973-07-05 | Fuji Photo Film Co Ltd | LIGHT SENSITIVE SILVER HALOGENIDE MATERIAL |
| JPS5036979B1 (en) * | 1971-03-04 | 1975-11-28 | ||
| US4001020A (en) * | 1971-03-04 | 1977-01-04 | Fuji Photo Film Co., Ltd. | Developing a silver ha1ide emulsion in contact with a heterocyclic thione and a polyalkylene oxide |
| JPS5284734A (en) * | 1976-10-04 | 1977-07-14 | Fuji Photo Film Co Ltd | Photographic image formation |
| DE2822320A1 (en) * | 1977-05-23 | 1978-12-07 | Fuji Photo Film Co Ltd | PHOTOGRAPHIC SILVER HALOGENIDE EMULSION |
| US4518781A (en) * | 1980-03-27 | 1985-05-21 | Rhone-Poulenc Agrochimie | Process for the preparation of 3-hydroxymethyl-6-chlorobenzoxazolone |
| US4618574A (en) * | 1985-07-18 | 1986-10-21 | Eastman Kodak Company | High contrast photographic elements exhibiting reduced pepper fog |
| US4634661A (en) * | 1985-07-18 | 1987-01-06 | Eastman Kodak Company | High contrast photographic elements exhibiting stabilized sensitivity |
| US4874866A (en) * | 1983-09-06 | 1989-10-17 | Eastman Kodak Company | Photographically useful chalcogenazoles, chalcogenazolines, and chalcogenazolinium and chalcogenazolium salts |
| US4946962A (en) * | 1986-03-24 | 1990-08-07 | Minnesota Mining And Manufacturing Company | Bis(thiazolinethiones) |
| US4965005A (en) * | 1987-09-17 | 1990-10-23 | Ciba-Geigy Corporation | Aminomethyl derivatives of monothiocarbamates and dithiocarbamates as additives for lubricants |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2099374A (en) * | 1934-04-07 | 1937-11-16 | Gevaert Photo Production N V | Photographic developer and a process of photographic developing |
| US2453346A (en) * | 1945-10-25 | 1948-11-09 | Eastman Kodak Co | Stabilization of processed photographic emulsions to high temperatures and humidities |
| US2819965A (en) * | 1956-02-23 | 1958-01-14 | Eastman Kodak Co | Carboxymethylmercapto compounds as stabilizers for photographic emulsions |
| US2870015A (en) * | 1957-03-08 | 1959-01-20 | Eastman Kodak Co | Stabilized photographic silver halide emulsions |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB522997A (en) * | 1938-09-23 | 1940-07-03 | Kodak Ltd | Improvements in photographic emulsions |
| US2728667A (en) * | 1952-11-08 | 1955-12-27 | Eastman Kodak Co | Molecular compounds of mercury salts with benzothiazoles as fog inhibitors in a silver halide emulsion |
| DE957183C (en) * | 1953-07-01 | 1957-01-31 | Eastman Kodak Co | Stabilized photographic material |
-
1958
- 1958-10-06 US US765339A patent/US3081170A/en not_active Expired - Lifetime
-
1959
- 1959-10-06 DE DEG28090A patent/DE1182059B/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2099374A (en) * | 1934-04-07 | 1937-11-16 | Gevaert Photo Production N V | Photographic developer and a process of photographic developing |
| US2453346A (en) * | 1945-10-25 | 1948-11-09 | Eastman Kodak Co | Stabilization of processed photographic emulsions to high temperatures and humidities |
| US2819965A (en) * | 1956-02-23 | 1958-01-14 | Eastman Kodak Co | Carboxymethylmercapto compounds as stabilizers for photographic emulsions |
| US2870015A (en) * | 1957-03-08 | 1959-01-20 | Eastman Kodak Co | Stabilized photographic silver halide emulsions |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3251691A (en) * | 1960-09-23 | 1966-05-17 | Gevaert Photo Prod Nv | Photographic material |
| DE2210369A1 (en) * | 1971-03-04 | 1972-09-28 | Fuji Photo Film Co. Ltd., Ashigara-Kamigun, Kanagawa (Japan) | Process for the production of photographic images |
| JPS5036979B1 (en) * | 1971-03-04 | 1975-11-28 | ||
| US4001020A (en) * | 1971-03-04 | 1977-01-04 | Fuji Photo Film Co., Ltd. | Developing a silver ha1ide emulsion in contact with a heterocyclic thione and a polyalkylene oxide |
| JPS576092B2 (en) * | 1971-12-28 | 1982-02-03 | ||
| DE2263808A1 (en) * | 1971-12-28 | 1973-07-05 | Fuji Photo Film Co Ltd | LIGHT SENSITIVE SILVER HALOGENIDE MATERIAL |
| JPS4873135A (en) * | 1971-12-28 | 1973-10-02 | ||
| US3895948A (en) * | 1971-12-28 | 1975-07-22 | Fuji Photo Film Co Ltd | Silver halide light-sensitive material containing a heterocyclic thione and a polyalkylene oxide |
| JPS5284734A (en) * | 1976-10-04 | 1977-07-14 | Fuji Photo Film Co Ltd | Photographic image formation |
| DE2822320A1 (en) * | 1977-05-23 | 1978-12-07 | Fuji Photo Film Co Ltd | PHOTOGRAPHIC SILVER HALOGENIDE EMULSION |
| US4518781A (en) * | 1980-03-27 | 1985-05-21 | Rhone-Poulenc Agrochimie | Process for the preparation of 3-hydroxymethyl-6-chlorobenzoxazolone |
| US4874866A (en) * | 1983-09-06 | 1989-10-17 | Eastman Kodak Company | Photographically useful chalcogenazoles, chalcogenazolines, and chalcogenazolinium and chalcogenazolium salts |
| US4618574A (en) * | 1985-07-18 | 1986-10-21 | Eastman Kodak Company | High contrast photographic elements exhibiting reduced pepper fog |
| US4634661A (en) * | 1985-07-18 | 1987-01-06 | Eastman Kodak Company | High contrast photographic elements exhibiting stabilized sensitivity |
| US4946962A (en) * | 1986-03-24 | 1990-08-07 | Minnesota Mining And Manufacturing Company | Bis(thiazolinethiones) |
| US4965005A (en) * | 1987-09-17 | 1990-10-23 | Ciba-Geigy Corporation | Aminomethyl derivatives of monothiocarbamates and dithiocarbamates as additives for lubricants |
Also Published As
| Publication number | Publication date |
|---|---|
| DE1182059B (en) | 1964-11-19 |
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