US3791830A - Silver halide photographic element containing a reaction product of a heterocyclic mercaptan and a chloroformic acid ester as antifog agent - Google Patents

Silver halide photographic element containing a reaction product of a heterocyclic mercaptan and a chloroformic acid ester as antifog agent Download PDF

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Publication number
US3791830A
US3791830A US00362737A US3791830DA US3791830A US 3791830 A US3791830 A US 3791830A US 00362737 A US00362737 A US 00362737A US 3791830D A US3791830D A US 3791830DA US 3791830 A US3791830 A US 3791830A
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United States
Prior art keywords
compound
fog
emulsion
mol
silver halide
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Expired - Lifetime
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US00362737A
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English (en)
Inventor
W Abele
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EIDP Inc
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EI Du Pont de Nemours and Co
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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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D285/00—Heterocyclic compounds containing rings having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by groups C07D275/00 - C07D283/00
    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
    • C07D285/125—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
    • C07D285/135—Nitrogen atoms

Definitions

  • A is a nitrogen-containing heterocyclic radical having 5 or 6 atoms in the heterocyclic ring; Y is S for n l and S or S and NH for n 2; R is any desired substituent such as alkyl, halogen or hydroxyalkyl; Z is S or 80:; and n is l or 2.
  • the subject of the present invention is a photographic material with at least one light-sensitive, silver halide emulsion layer that is stabilized against overdevelopment.
  • stabilizers from the class of the triazaindolizines which are outstandingly suitable for the prevention of fog on storage, give no protection against overdevelopment, because their protective action declines and practically disappears at the end of development, through removal by diffusion and other mechanisms, when it is most needed.
  • Other stabilizers with known effectiveness such as mercury compounds or heterocyclic mercapto compounds are indeed able to reduce the development fog considerably in the normal development and also in the overdevelopment region, but have the great disadvantage that when used in sufficient amounts they reduce the utilizable sensitivity of the photographic emulsion considerably.
  • a fundamental disadvantage of the direct addition to silver halide emulsions of heterocyclic mercapto compounds, that are known to be particularly effective against overdevelopment fog, is that they are completely active starting from the time of addition, that is, also during the casting process, during the entire time of storage of the unprocessed film material and, finally, in the initial stage of photographic development. Therefore, even before the processing, desensitizing effects occur, and during the development itself the inherent sensitivity of the material is not completely utilized. To solve this problem, substitution of the mer capto groups of these compounds by suitable radicals has already been tried, which is supposed to inactivate them until a time when they should become active.
  • the compounds can be added to the light-sensitive emulsion without damage, since the active groups are liberated first during the development process. It is important to know, however, the time at which the reactivation of the protected group takes place because if reactivation takes place too slowly, the overdevelopment fog is not sufficiently hindered; and if it takes place too rapidly, the image build up is impaired. In both instances an optimum sensitivity/fog ratio cannot be achieved.
  • the invention therefore relates to photographic material comprising a film support and at least one lightsensitive silver halide emulsion layer, said emulsion layer being in contact with an antifog agent of the formula given above.
  • Contact between the antifog agent and the emulsion layer may be effected by incorporating the antifog agent in the emulsion or by incorporating the antifog agent in an auxiliary layer that is in contact with the emulsion.
  • Preparation of the new antifog agents is accomplished by reaction of the antifog agents containing mercapto groups with chloroformic acid esters in the presence of acid acceptors and can be represented by the following reactions:
  • antifog agents within the general formula given above are listed in the following table:
  • the potassium salt of l-phenyl--mercaptotetrazole (10.8 g 0.05 mol) is dissolved in 300 ml of acetone and reacted dropwise with stirring at 5 C. with 1 1.5 g (0.05 mol) of p-tolylthioethylene chloroformate in 50 ml of anhydrous acetone.
  • the reaction mixture is stirred for another 5 hours at room temperature and allowed to stand overnight. Subsequently, the mixture is heated to boiling, the precipitated potassium chloride is filtered off and the filtrate is concentrated in vacuo. The oily residue is recrystallized repeatedly from a little ethanol.
  • the potassium salt of l-phenyl-5-mercaptotetrazole (l0.8 g 0.05 mol) is dissolved in 300 ml of acetone and reacted dropwise with stirring at 5 C. with 10.8 g of phenylthioethylene chloroformate (0.05 mol) in 50 ml of anhydrous acetone.
  • the reaction mixture is stirred for another 5 hours at room temperature and allowed to stand overnight. Subsequently, the mixture is heated to boiling, the precipitated potassium bromide (7) is filtered off and the filtrate is concentrated in vacuo. The oily residue is recrystallized repeatedly from a little ethanol.
  • the potassium salt of 1-phenyl-S-mercaptotetrazole 712' 0.0'3'3'hib1' is dissolved in 200 ml of acetone and reacted with stirring at C. with 6.2 gof (0.033 mol) of B-bromoethyl chloroformic acid. The solution is allowed to stand overnight, subsequently filtered and the filtrate is concentrated in vacuo.
  • 2,5-Dimercaptothiodiazole (3.0 g 0.02 mol) is dissolved in 200 ml of acetone and treated with 1.6 g (0.04 mol) of magnesium oxide. To this slurry is added dropwise with stirring at 5 C. a solution of 9.2 g (0.04
  • 2-Amino-5-mercaptothiodiazole (4.0 g 0.03 mol) is dissolved in 250 ml of acetone and treated with 2.4 g (0.06 mol) of magnesium oxide.
  • To this slurry is added dropwise with stirring at 5 C. a solution of 13.9. g (0.06 mol) of p-tolylthioethylene chloroformate in 50 ml of anhydrous acetone. After addition is completed the mixture is stirred at room temperature for another 5 hours and allowed to stand overnight. Subsequently, the slurry is heated to boiling, filtered hot, and the hot acetone solution is concentrated in vacuo. The oily residue is recrystallized repeatedly from ethanol.
  • the antifog agents are added to the light-sensitive emulsions or also to the light-insensitive auxiliary layers, such as interlayers, protective layers and the like. Addition is accomplished most advantageously before casting the emulsions, but it is possible also to add the compounds at another time in the emulsion production.
  • the compounds preferably are added in quantities of 0.05 to 5 mmol based on 1.0 mol of silver halide, whereas in the auxiliary layers they display the best action in quantities of 0.1 to 5 mmol.
  • the optimum quantity at the time depends on the nature of the antifog agent and the emulsion used and can be determined easily from case to case.
  • the compounds described can be dissolved in a suitable solvent and added to the emulsion in this form.
  • Sensitivity Fog Sensitivity Fog
  • the new antifog agents can be used in the most varied kinds of recording materials, for example, in opti- A 22:33: 010 107 042 cally unsensitized materials like X-ray films, but also in B 102 (m9 120 0,11 orthochromatic and panchromatic sensitized recording g v i 2 materials.
  • the light-sensitive emulsions used tabe can contain the customary additives, such as chemical sensitizers, hardeners, wetting agents, and the like.
  • An optically unsensitized, h1gh-sens1t1v1ty silver halide emulsion is produced which contains about 5 persamph cent of gelatin and about 10 percent of silver halide.
  • Sensitivity 2 Sensitivity 1;
  • the silver halide consists of 98 weight per cent of silver A comparison m0 0 120 033 bromide and 2 weight per cent of silver iodide.
  • the emulsion emulsion produced in this way is divided into two parts 8 compound; 125 A and B. Part A contains no additive and serves as a of table comparison sample.
  • To part B, per mol of silver bromide is added a solution of 0.3 mmol of the compound EXAMPL l of the table, dissolved in acetone.
  • a i i g i gg grepared light-sensitive material obtained is evaluated in the mg 0 e a a m Xamp e a e per m0 0 usual way silver bromide, an acetone solut1on of 0.2 mmol of the And, in fact, the samples, in the form of the known compgund, r and cast exposed and test strips, are exposed for 2 sec with two Osram lamps 40 Release as m d h b (Wi 9 2,660 K.) at a distance of 1.2 m in a grey-wedge f t e ts recor e m t e ta 6 were 0 sensitometer with a wedge constant of D 0.15/cm tamed with filters BG 3 (1.8 mm) and BG 38 (1.5 mm), and sample 5 gb: then developed for 25 sec at temperatures of 35 C. and Sensitivity Fog
  • Example 2 To a silver bromide-iodide emulsion prepared according to the data in Example 1 is added, per mol of silver bromide, an acetone solution of 0.4 mmol of the compound 6 of the table, cast and exposed as in Example l and developedfor 3 min and 12 min at 20 C. in the developer given there.
  • Example 2 To a silver bromide-iodide emulsion prepared according to the data in Example 1 is added, per mol of silver bromide, an acetone solution of 0.2 mmol of the compound 7 of the table, cast and exposed as in Example l and developed for 3 min and 12 min at 20 C. in the, developer given there.
  • Example 2 To a silver bromide-iodide emulsion prepared according to the data in Example 1 is added, per mol of silver bromide, an acetone solution of 0.1 mmol of the compound 9 of the table, cast and exposed as in Example 1 and developed for 25 sec at temperatures of 35 C. and 39 C. in the developer given there.
  • Sensitivity Fog Sensitivity Fog A comparison 0.15 128 0.43
  • Example 2 To a silver bromide-iodide emulsion prepared according to the data in Example 1 is added, per mol of silver bromide, an acetone solution of 0.1 mmol of the compound 10 of the table, cast and exposed as in Example 1 and developed for 3 min and 12 min at 20 C. in the developer given there.
  • Example 2 To a silver bromide-iodide emulsion prepared according to the data in Example 1 is added, per mol of silver bromide, an acetone solution of 0.1 mmol of the compound 11 of the table, cast and exposed as in Example l and developed for 3 min and 12 min at 20 C. in the developer given there.
  • Example 2 To a silver bromide-iodide emulsion prepared according to the data in Example 1 is added, per mol of silver bromide, an acetone solution of 0.1 mmol of the compound 12 of the table, cast and exposed as in Example 1 and developed for 25 sec at temperatures of 35 C. and 39 C. in the developer given there.
  • Sensitivity Fog Sensitivity Fog A comparison 100' 0.18 107 0.42
  • Example 2 To a silver bromide-iodide emulsion prepared according to the data in Example 1 is added, per mol of silver bromide, an acetone solution of 0.2 mmol of the compound 13 of the table, cast and exposed as in Example 1 and developed for 3 min and 12 min at 20 C. in the developer given there.
  • Example 2 To a silver bromide-iodide emulsion prepared according to the data in Example 1 is added, per mol of silver bromide, an acetone solution of 0.2 mmol of the compound 14 of the table, cast and exposed as in Example 1 and developed for 3 min and 12minat 20 C. in the developer given there.
  • Example 2 To a silver bromide-iodide emulsion prepared according to the data in Example 1 is added, per mol of silver bromide, and acetone solution of 0.1 mmol of the compound 15 of the table, cast and exposed as in Example 1 and developed for 3 min and 12 min at C. in the developer given there.
  • Example 2 To a silver bromide-iodide emulsion prepared according to the data in Example 1 is added, per mol of silver bromide, an acetone solution of 0.1 mmol of the compound 16 of the table, cast and exposed as in Example 1 and developed for 3 min and 12 min at 20 C. in the developer given there.
  • a silver bromide-iodide emulsion prepared according to Example 1 is divided into 5 parts. Whereas, part A is cast on a polyester base unchanged as a comparison, the parts B, C, D and E are treated with acetone solutions of the following additives:
  • the exposed test strips were developed for 3 min and 12 min at 20 C. with the developer mentioned in Example 1, subsequently fixed in a customary fixing bath, washed and dried.
  • the advance achieved with the invention consists in that the overdevelopment fog can be reduced without the appearance of a loss in sensitivity. Beyond this, as a result of the better functional controllability of the reactivation process in the compounds of the invention,
  • Photographic material comprising a film support and at least one light-sensitive silver halide emulsion layer,'containing an antifog agent or being in contact with an auxiliary layer containing an anti-fog agent, said antifog agent having the general formula:
  • Photographic material according to claim 1 wherein said antifog agent is contained in said auxiliary layer in contact with said light-sensitive silver halide emulsion layer.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US00362737A 1970-12-16 1973-05-22 Silver halide photographic element containing a reaction product of a heterocyclic mercaptan and a chloroformic acid ester as antifog agent Expired - Lifetime US3791830A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE2061972A DE2061972C3 (de) 1970-12-16 1970-12-16 Photographisches Aufzeichnungsmaterial

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US (1) US3791830A (da)
JP (1) JPS559696B1 (da)
BE (1) BE776719A (da)
DE (1) DE2061972C3 (da)
GB (1) GB1357037A (da)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4772537A (en) * 1985-09-18 1988-09-20 Fuji Photo Film Co., Ltd. Silver halide photographic materials containing a photographic reagent precursor
US5358843A (en) * 1993-08-20 1994-10-25 Minnesota Mining And Manufacturing Company Photothermographic elements containing silyl blocking groups
US5439790A (en) * 1994-06-24 1995-08-08 Minnesota Mining And Manufacturing Company Phthalimide blocked post-processing stabilizers for photothermography
US5478721A (en) * 1995-01-31 1995-12-26 Eastman Kodak Company Photographic elements containing emulsion stabilizers
US6020210A (en) * 1988-12-28 2000-02-01 Miltenvi Biotech Gmbh Methods and materials for high gradient magnetic separation of biological materials
US6280922B1 (en) 1998-12-30 2001-08-28 Eastman Kodak Company High chloride silver halide elements containing activated precursors to thiolic stabilizers
US6280913B1 (en) 2000-06-13 2001-08-28 Eastman Kodak Company Photographic element comprising an ion exchanged photographically useful compound
US20050123867A1 (en) * 2003-12-04 2005-06-09 Eastman Kodak Company Silver halide elements containing activated precursors to thiocyanato stabilizers
EP2107122A1 (en) 2008-03-31 2009-10-07 FUJIFILM Corporation Protease detection material, set of protease detection materials, and method for measuring protease
WO2024079043A1 (en) 2022-10-10 2024-04-18 Bachem Holding Ag Method of manufacturing a peptide with a lysine derivative
WO2025078040A1 (en) 2023-10-09 2025-04-17 Bachem Holding Ag Lysine salt and method of manufacturing a lysine derivative

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2394198A (en) * 1944-10-17 1946-02-05 Gen Anilline & Film Corp Stabilized silver halide emulsions
US3364028A (en) * 1963-04-27 1968-01-16 Agfa Ag Photographic material containing yellow fog-preventing agents

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2394198A (en) * 1944-10-17 1946-02-05 Gen Anilline & Film Corp Stabilized silver halide emulsions
US3364028A (en) * 1963-04-27 1968-01-16 Agfa Ag Photographic material containing yellow fog-preventing agents
US3365294A (en) * 1963-04-27 1968-01-23 Agfa Ag Photographic material containing yellow fog-preventing agents

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4772537A (en) * 1985-09-18 1988-09-20 Fuji Photo Film Co., Ltd. Silver halide photographic materials containing a photographic reagent precursor
US6020210A (en) * 1988-12-28 2000-02-01 Miltenvi Biotech Gmbh Methods and materials for high gradient magnetic separation of biological materials
US6417011B1 (en) * 1988-12-28 2002-07-09 Miltenyi Biotec Gmbh Methods and materials for improved high gradient magnetic separation of biological materials
US5358843A (en) * 1993-08-20 1994-10-25 Minnesota Mining And Manufacturing Company Photothermographic elements containing silyl blocking groups
US5439790A (en) * 1994-06-24 1995-08-08 Minnesota Mining And Manufacturing Company Phthalimide blocked post-processing stabilizers for photothermography
US5478721A (en) * 1995-01-31 1995-12-26 Eastman Kodak Company Photographic elements containing emulsion stabilizers
US6280922B1 (en) 1998-12-30 2001-08-28 Eastman Kodak Company High chloride silver halide elements containing activated precursors to thiolic stabilizers
US6280913B1 (en) 2000-06-13 2001-08-28 Eastman Kodak Company Photographic element comprising an ion exchanged photographically useful compound
US20050123867A1 (en) * 2003-12-04 2005-06-09 Eastman Kodak Company Silver halide elements containing activated precursors to thiocyanato stabilizers
EP2107122A1 (en) 2008-03-31 2009-10-07 FUJIFILM Corporation Protease detection material, set of protease detection materials, and method for measuring protease
WO2024079043A1 (en) 2022-10-10 2024-04-18 Bachem Holding Ag Method of manufacturing a peptide with a lysine derivative
WO2025078040A1 (en) 2023-10-09 2025-04-17 Bachem Holding Ag Lysine salt and method of manufacturing a lysine derivative

Also Published As

Publication number Publication date
GB1357037A (en) 1974-06-19
JPS559696B1 (da) 1980-03-11
DE2061972B2 (de) 1975-01-16
DE2061972C3 (de) 1975-09-11
BE776719A (fr) 1972-06-15
DE2061972A1 (de) 1972-07-06

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