US3764339A - Silver halide emulsions stabilized with n-(1,3,4-thiadiazol-2-yl)-dithiocarbamic acid esters - Google Patents

Silver halide emulsions stabilized with n-(1,3,4-thiadiazol-2-yl)-dithiocarbamic acid esters Download PDF

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Publication number
US3764339A
US3764339A US00178845A US3764339DA US3764339A US 3764339 A US3764339 A US 3764339A US 00178845 A US00178845 A US 00178845A US 3764339D A US3764339D A US 3764339DA US 3764339 A US3764339 A US 3764339A
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United States
Prior art keywords
silver halide
thiadiazol
dithiocarbamic acid
acid esters
emulsions
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Expired - Lifetime
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US00178845A
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English (en)
Inventor
W Himmelmann
Koenig A Von
W Saleck
F Moll
D Ruecker
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • 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
    • 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

  • This invention relates to a photographic material comprising at least one silver halide emulsion layer whose stability is improved by the addition of N-(l,3,4-thiadiazol-2-yl)-dithiocarbamic acid esters.
  • Fog depends both upon the nature of the emulsion and the conditions of development. For a given emulsion it increases with the degree of development. It is common practice to make accelerated tests of the stability of photographic emulsions by storage at increased temperature or humidity, or both. It is desirable to have emulsions as stable as possible under the condition of high temperature, which may occur in tropical climates. Fog usually appears over the whole area of the light-sensitive layer, but when severe is quite frequently non-uniform.
  • arylthio preferably phenylthio
  • alkoxyalkoxy the aryl radicals can contain further substituents, for example one or more halogen atoms and 1 to 3 alkyl groups or 1 to 3 alkoxy groups;
  • R stands for hydrogen or an alkyl, alkenyl or alkinyl radical of up to 4 carbon atoms preferably alkyl of up to 3 carbon atoms;
  • R represents (1) a saturated or unsaturated linear, branched or cyclic aliphatic group, with preferably 1 to 8 carbon atoms, which can be substituted, for example by halogen such as fluorine, chlorine or bromine; by alkoxy or alkylthio with preferably up to 5 carbon atoms; or by aryloxy or arylthio, preferably phenoxy or phenylthio,
  • aryl such as a group of the phenyl or naphthyl series, or
  • aralkyl such as benzyl or phenylethyl whose aryl rings can be substituted with one or more alkoxy groups, alkyl groups, or halogen, for example fluorine, chlorine or bromine, the alkyl and alkoxy groups containing 1 to 3 carbon atoms.
  • This intermediate product is then alkylated with an alkyl or aryl halide of the general formula:
  • dimethyl sulfoxide alcohols, water, ethers such as tetrahydrofuran and dioxan.
  • ethers such as tetrahydrofuran and dioxan.
  • reaction temperatures can be varied within a relatively wide range, although in most instances the reaction is carried out at a temperature of from C. to 100 C.
  • To prepare the compounds it is best to mix equimolar quantities of the Z-amino-l,3,4-thiadiazole, carbon disulfide and alkali metal hydroxide at a temperature from 0 to C., followed by addition of an equivalent quantity of an alkylating agent after 30 minutes. After the exothermic reaction has abated, the reaction product is worked up in the usual way.
  • the resulting N-(S-trifluoromethyl-1,3,4-thiadiazol-2-yl)-dithiocarbamic acid benzyl ester melts at 224 C
  • the N-(1,3,4-thiadiazol-2-yl)-dithiocarbamic acid esters used in accordance with the invention have the advantage over a number of conventional stabilizers in that they do not contain any free mercapto groups.
  • the photographic properties such as sensitivity, gradation and clarity are excellently stabilised by the compounds used according to the invention and they cause no fogging or adverse effect upon grain.
  • N-(1,3,4-thiadiazol-2-y1)-dithiocarbamic acid esters used according to the present invention can be added either to silver halide layers or to other water-permeable layers for example to intermediate layers, protective layers or to the baryta-coatings which contact the silver halide layers.
  • these compounds are added to lightsensitive silver halide emulsions, this can be done at any stage during preparation of the emulsion. They are preferably added before after-ripening. The quantity added can be varied within wide limits. Quantities of from 0.001 to 5 g. per mol of silver halide have generally proved to be adequate. Particularly good results are obtained when the emulsion contains 1 to 50 mg. of the stabilizer per mol of silver halide.
  • suitable solvents include lower alcohols, such as methanol, ethanol or propanol, tetrahydrofuran, acetone and dimethyl formamide.
  • the usual silver halide emulsions are suitable for the present invention.
  • the silver halide may be silver chloride, silver bromide or a mixture thereof, which may additionally contain a small amount of silver iodide of up to 10 mol percent.
  • Gelatin is preferably used as binder for the photographic layer. It can, however, be replaced, either wholly or in part, by other natural or synthetic binders.
  • suitable natural binders include alginic acid and its derivatives, such as its salts, esters, or amides; cellulose derivatives such as carboxymethyl cellulose and alkyl celluloses such as hydroxyethyl cellulose; starch or its derivatives such as its ethers or esters; and carrageenates.
  • Polyvinyl alcohol, partially hydrolysed vinyl acetate, polyvinyl pyrrolidone and the like are examples of suitable synthetic binders.
  • the emulsions can also be chemically sensitized, for example by the addition during chemical ripening of sulphur-containing compounds, for example allyl isothiocyanate, allyl thiourea, and sodium thiosulfate.
  • Reducing agents can also be used as chemical sensitisers, for example the tin compounds described in Belgian patent specification No. 493,464 or 568,687, polyamines such as diethylene triamine, or aminomethyl sulphinic acid derivatives, for example those of the kind described in Belgian patent specification No. 547,323.
  • Suitable chemical sensitisers include noble metals or compounds of noble metals, such as gold, platinum, palladium, iridium, ruthenium or rhodium. This method of chemical sensitisation is described in the article by R. Koslowsky in Z. Wiss. Phot. 46, 65-72 (1951).
  • polyalkylene oxide derivatives for example with polyethylene oxide having a molecular weight of from 1000 to 20,000, and also with condensation products of alkylene oxides and aliphatic alcohols, glycols, cyclic dehydration products of hexitols, with alkyl-substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
  • the condensation products have molecular weights of at least 700, and preferably of more than 1000.
  • these sensitisers can of course be used in combination with one another, as described in Belgian patent specification No. 537,278 and in British patent specification No. 727,982.
  • the emulsions can also be optically sensitized, for example with the conventional polymethine dyes such as neutrocyanines, basic or acid carbocyanines, thiocyanines, hemicyanines, styryl dyes, or oxonols.
  • Sensitisers of this kind are described in the work by F. M. Hamer The Cyanine Dyes and Related Compounds (1964).
  • the emulsions can contain known stabilisers, for example homopolar or saltlike compounds of mercury with groups containing aromatic or heterocyclic rings, such as mercapto triazoles, simple mercury salts, sulphonium mercury double salts, and other mercury compounds.
  • suitable stabilisers include azaindenes, preferably tetraor penta-azaindenes, especially those substituted by hydroxy or amino groups. Compounds of this kind are described in the article by Birr in Z. Wiss. Phot., 47, 2-58 (1952).
  • Other suitable stabilisers include inter alia heterocyclic mercapto compounds, for example phenyl mercapto tetrazole, quaternary benzthiazole derivatives, or benzotriazole.
  • the emulsions can be hardened in the usual way, for example with formaldehyde or halogen-substituted aldehydes containing a carboxyl group, such as mucobromic acid, diketones, methane sulphonic acid esters, and dialdehydes.
  • formaldehyde or halogen-substituted aldehydes containing a carboxyl group such as mucobromic acid, diketones, methane sulphonic acid esters, and dialdehydes.
  • the emulsions can also contain colour couplers in dissolved or dispersed form.
  • the stabilizers which we have described may be used in various kinds of photographic emulsions. In addition to being useful in X-ray and other non-optically sensitized emulsions they may also be used in ortho-chromatic, panchromatic and infrared-sensitive emulsions. They may also be used for emulsions suitable for use in the silver salt diffusion process for color-photography and for photographic materials for the silver dye bleach process.
  • EXAMPLE 1 A highly sensitive silver bromide/iodide emulsion containing 6 mol percent of silver iodide is prepared in the usual way, the silver nitrate solution being run at intervals into a solution containing gelatin, potassium bromide and potassium iodide. The emulsion is then flocculated in known manner with ammonium sulfate and freed from the usual salts. The flocculate is redispersed in warm water, and the required quantity of sulfur-containing ripening gelatin is added, followed by ripening in the presence of gold (I) thiocyanate complexes and sodium thiosulfate up to optimum sensitivity.
  • gold (I) thiocyanate complexes and sodium thiosulfate up to optimum sensitivity.
  • the emulsion Before the emulsion is heated to the ripening temperature, it is divided into 22 portions.
  • the first portion is ripened in the absence of any other additives, whilst the compounds mentioned in the following Table 2 are individually added to the other portions.
  • EXAMPLE 2 A highly sensitive silver bromide/iodide emulsion containing 5 mol percent of silver iodide is prepared in the usual way, silver nitrate solution being run into a solution containing gelatin,potassium iodide and potassium bromide. The emulsion is flocculated in known manner with ammonium sulfate and freed from soluble salts by washing. The flocculate is redispersed in warm water, and the required quantity of sulfur-containing ripening gelatin is added, followed by ripening to optimum sensitivity in the presence of gold (I) -thiocyanate complexes and sodium thiosulfate. V
  • hyde based in each instance on 1 kg. of emulsion, are then added to the emulsions.
  • the emulsion is then divided into 19 portions. One portion is left without any additives, whilst the other portions contain the compounds mentioned in the table below. 7
  • the emulsions are cast on to a support of cellulose acetate, and are dried and then exposed and developed as already described. Some of the samples are stored for 3 days at60 C. and then developed for 16 minutes at 20 C.
  • a light-sensitive photographic silver halide emulsion which contains in an amount that inhibits fogging, an N-(1,3,4-thiadiazol-2-yl)-dithiocarbamic acid ester of the formula:
  • R represents trifiuoromethyl or alkylthio with up to 5 carbon atoms.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)
US00178845A 1970-09-09 1971-09-08 Silver halide emulsions stabilized with n-(1,3,4-thiadiazol-2-yl)-dithiocarbamic acid esters Expired - Lifetime US3764339A (en)

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Application Number Priority Date Filing Date Title
DE19702044622 DE2044622A1 (de) 1970-09-09 1970-09-09 Photographisches Material mit ver besserten Eigenschaften

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US (1) US3764339A (enrdf_load_stackoverflow)
BE (1) BE772323A (enrdf_load_stackoverflow)
CA (1) CA962504A (enrdf_load_stackoverflow)
CH (1) CH568585A5 (enrdf_load_stackoverflow)
DE (1) DE2044622A1 (enrdf_load_stackoverflow)
FR (1) FR2107498A5 (enrdf_load_stackoverflow)
GB (1) GB1323227A (enrdf_load_stackoverflow)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3910791A (en) * 1973-01-30 1975-10-07 Agfa Gevaert Ag Silver halide photographic material containing a 2-propynylthio derivative as stabilizer
US3982947A (en) * 1974-03-14 1976-09-28 Agfa-Gevaert, N.V. Fog-inhibitors for silver halide photography silver halide photographic material containing an iodo benzene compound as antifoggant
US4115122A (en) * 1975-12-09 1978-09-19 Fuji Photo Film Co., Ltd. Internal latent image silver halide emulsion containing a heterocyclic quaternary salt having a propargyl or a butyryl containing substituent
US4378426A (en) * 1981-11-12 1983-03-29 Eastman Kodak Company Photographic speed increasing and latent image stabilizing compounds, silver halide emulsions, and photographic elements

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3272640D1 (en) * 1982-01-22 1986-09-18 Basf Ag Thiadiazole derivatives, process for their preparation, and their use in combatting unwanted plant growth
EP0084673B1 (de) * 1982-01-22 1986-04-02 BASF Aktiengesellschaft Aminothiadiazole, Verfahren zu ihrer Herstellung und ihre Verwendung zur Bekämpfung unerwünschten Pflanzenwuchses

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3910791A (en) * 1973-01-30 1975-10-07 Agfa Gevaert Ag Silver halide photographic material containing a 2-propynylthio derivative as stabilizer
US3982947A (en) * 1974-03-14 1976-09-28 Agfa-Gevaert, N.V. Fog-inhibitors for silver halide photography silver halide photographic material containing an iodo benzene compound as antifoggant
US4115122A (en) * 1975-12-09 1978-09-19 Fuji Photo Film Co., Ltd. Internal latent image silver halide emulsion containing a heterocyclic quaternary salt having a propargyl or a butyryl containing substituent
US4378426A (en) * 1981-11-12 1983-03-29 Eastman Kodak Company Photographic speed increasing and latent image stabilizing compounds, silver halide emulsions, and photographic elements
US4451557A (en) * 1981-11-12 1984-05-29 Eastman Kodak Company Photographic speed increasing and latent image stabilizing compounds, silver halide emulsions, and photographic elements

Also Published As

Publication number Publication date
DE2044622A1 (de) 1972-03-23
CA962504A (en) 1975-02-11
GB1323227A (en) 1973-07-11
FR2107498A5 (enrdf_load_stackoverflow) 1972-05-05
BE772323A (fr) 1972-03-08
CH568585A5 (enrdf_load_stackoverflow) 1975-10-31

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