US3692527A - Silver halide emulsion containing a mercapto pyrimidine derivative antifoggant - Google Patents

Silver halide emulsion containing a mercapto pyrimidine derivative antifoggant Download PDF

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Publication number
US3692527A
US3692527A US95401A US3692527DA US3692527A US 3692527 A US3692527 A US 3692527A US 95401 A US95401 A US 95401A US 3692527D A US3692527D A US 3692527DA US 3692527 A US3692527 A US 3692527A
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US
United States
Prior art keywords
silver halide
compound
mercapto
acid
emulsions
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
Application number
US95401A
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English (en)
Inventor
Anita Von Konig
Hans-Joachim Kabbe
Helmut Mader
Rigobert Otto
Helmut Reuss
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Agfa Gevaert AG
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Agfa Gevaert AG
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • 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

  • the invention relates to a photographic material comprising at least one silver halide emulsion layer whose stability in storage and development has been improved by means of the addition of pyrimidine derivatives.
  • Additional fogging may also occur during development itself, due to the use of contaminated or very much used developers or if development is carried on for too long or at extremely high temperatures.
  • the formation of fog during storage can be delayed by storing the photographic material at low temperature and at relatively low humidity.
  • photographic materials often have to be stored and developed under adverse conditions, e.g. in the tropics where both high relative humidity and high temperatures prevail.
  • the tendency of the photographic silver halide emulsions to fog can be suppressed by the addition of so-called stabilizers or antifoggants.
  • stabilizers or antifoggants are, for example, heterocyclic mercapto compounds or organic mercury compounds.
  • Another object of the invention is the preparation of photographic emulsions which are stabilized with these agents.
  • a photographic material having at least one silver halide emulsion layer stabilized with a ice pyrimidine derivative which contains, as stabilizer, a 2- mercapto-4-keto-3,4-dihydropyrirnidine derivative having at least one carboxy or sulfo group of the following formula:
  • R represents hydrogen, a saturated or olefinically unsaturated aliphatic group having preferably up to 12 carbon atoms or aryl, preferably a ring of the phenyl series, and
  • ring members required for completing a condensed carbocyclic ring of the benzene series, the cyclopentene series or the cyclohexene series, or a condensed heterocyclic ring selected from the following group: pyridine, tetrahydropyridine, pyrimidine, pyrrole, furan, thiophene, oxazole, isooxazole, imidazole or pyrazole.
  • the condensed carbocyclic or heterocyclic ring may carry further substituents, e.g.
  • the compounds to be used according to the invention may be prepared by methods which are known in principle.
  • the pyrimidine ring may be obtained by reacting an amine with an ortho-alkoxycarbonylisothiocyanate or by reacting an isothiocyanate with an orthoaminocarboxylic acid derivative.
  • the 4-mercapto group in 2,4-dimercaptopyrimidine derivatives may be replaced by the 4-keto group.
  • the carboxyl groups present in the end products may also be introduced as their derivatives such as esters, amides or nitriles from which they are liberated by saponification.
  • Compound 5 The method employed is the same as in Example 4 but using 18 g. of the sodium salt of p-a-minobenzoic acid. Yield of p-[3-(2-mercapto-3,4-dihydro-4-keto-quinazolinyl)]-benzoic acid: 19 g. v(62%), M.P. 342 C.
  • Compound 7 The method employed is the same as in Example 4 but using 15.3 g. of the sodium salt of fi-aminocaproic acid. Yield of 6- 3- Z-mercapto-3,4-dihydro-4-keto-quinazolinyl)]-caproic acid: 20 g. (70%), M.P. 210 C.
  • Compound 8 The method employed is the same as in Example 4 but using w-amino-decan carboxylic acid. Yield of w-[3-(2- mercapto 3,4 dihydro-4-keto-quinazo1inyl)J-decancarboxylic acid: (51%), M.P. 132 C.
  • Compound 9 The method employed is the same as in Example 5, but using 18 g. of the sodium salt of anthranilic acid. Yield of o-[3-(2-mercapto 3,4 dihydro-4-keto-quinazolinyl) benzoic acid: 23 g. (77%), M.P. 133 C.
  • the stabilizers according to the invention are advantageously added to the light-sensitive silver halide emulsions after chemical ripening although they may, of course, also be added to other photographic layers.
  • concentration of the stabilizers in the emulsion may vary within wide limits. It depends on the nature of the emulsion and the effect required. The required effects are generally obtained with quantities of 1 mg. to 1 g. per mol of silver halide.
  • the quantities used for black and white emulsions are preferably 100 to 500 mg. per mol of silver halide and the quantities used for emulsions which contain color couplers are preferably 5 to 100 mg. of stabilizer per mol of silver halide.
  • the optimum quantity to be added to any given emulsion can easily be determined by the usual tests.
  • the stabilizers according to the invention may be used in any silver halide emulsions.
  • Suitable silver halides are silver chloride, silver bromide or mixtures thereof, optionally with a small silver iodide content of up to mols percent.
  • the silver halides may be dispersed in the usual hydrophilic compounds, for example carboxymethyl-cellulose, alkyl cellulose, hydroxyethylcellulose, starch or its derivatives, carrageenates, polyvinyl alcohol, polyvinylpyrrolidone, alginic acid and its salts, esters or amides and preferably gelatin.
  • the emulsions may be chemically sensitized in the usual manner, for example with salts of noble metals such as ruthenium, rhodium, palladium, iridium or platinum. They may also be sensitized with gold salts as described in the article by R. Koslowsky, Z. Wiss. Phot. 46, 65-72 1951).
  • noble metals such as ruthenium, rhodium, palladium, iridium or platinum.
  • gold salts as described in the article by R. Koslowsky, Z. Wiss. Phot. 46, 65-72 1951).
  • the emulsions may also be chemically sensitized, e.g. by the addition of compounds which contain sulfur during chemical ripening, for example allylisothiocyanate, allyl thiourea, sodium thiosulfate or the like.
  • Reducing agents e.g. the tin compounds described in Belgian Pats. Nos. 493,464 and 568,687, or polyamines such as diethylene triamine or aminomethylsulfinic acid derivatives, e.g. those mentioned in Belgian Pat. No. 547,323, may also be used as chemical sensitizers.
  • the emulsions may also be sensitized with polyalkylene oxide derivatives, e.g. with polyethylene oxide having a molecular weight of between 1000 and 20,000, with condensation products of alkylene oxides and aliphatic alcohols or glycols or cyclic dehydration products of hexitols, or with alkyl substituted phenols, aliphatic carboxylic acids, aliphatic amines, aliphatic diamines and amides.
  • the condensation products have a molecular weight of at least 700 and preferably more than 1000.
  • These sensitizers may, of course, also be combined in order to achieve special effects, as described in Belgian Pat. No. 537,278 and in British Pat. No. 727,982.
  • the emulsions may also be optically sensitized, e.g. with the usual polymethine dyes such as neutrocyanines, basic or acid carbocyanines, rhodacyanines, hemicyanines, styryl dyes, oxonoles and the like. Sensitizers of this type have been described in the work by F. M. Hamer The Cyanine Dyes and related Compounds (1964).
  • the emulsions may be hardened in the usual manner, for example With formaldehyde or halosubstituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.
  • formaldehyde or halosubstituted aldehydes which contain a carboxyl group, such as mucobromic acid, diketones, methanesulfonic acid esters, dialdehydes and the like.
  • the silver halide emulsions according to the invention may contain other stabilizers in addition, preferably tetraor penta-azaindenes and especially those which are substituted with hydroxyl or amino groups. Compounds of this type have been described in the article by Birr in Zeitschrift fiirtician Photographic, volume 47, 1952, page 2 to 28.
  • the emulsions may also contain heterocyclic mercapto compounds such as mercapto tetrazoles or mercury compounds as stabilizers.
  • the pyrimidine stabilizers to be used according to the invention are especially advantageous in their effect in silver halide emulsions which contain color couplers.
  • the presence of the color couplers often severely reduces the effect of known stabilizers so that in the case of such emulsions it is especially difiicult to achieve satisfactory stability in storage or sufiicient freedom frem fogging if development is carried out for a long time or at high temperatures.
  • the formation of color fog is practically completely suppressed by the pyrimidine derivatives described here.
  • These stabilizers are especially effective in the rapid processing of color photographic materials, in which development is carried out at elevated temperatures.
  • the pyrimidine derivatives used according to the invention have much less effect on the sensitivity of the photographic emulsions used than the known heterocyclic mercapto compounds used for this purpose. Even the sensitivity of the most highly sensitive silver halide emulsions is not substantially reduced by the present stabilizers.
  • a red sensitized photographic silver bromide emulsion which contains g. of gelatine and 0.4 mol of silver bromide.
  • the emulsion in addition contains 50 ml. of a 1% methanolic solution of 4-hydroxy-6- methyl-1,3,3a,7-tetraazaindene, 30 ml. of a 10% aqueous saponin solution and 15 ml. of a 0.5% aqueous chrome acetate solution.
  • Compound 1 20 Compound 2 50 Compound 3 50 Compound 4 50 Compound 5 50 Compound 6 20
  • the control sample does not contain any additional stabilizer.
  • the 7 samples are applied to a layer support of celluose triacetate in a thickness of about 45,14.
  • the pH of the casting solution is adjusted to 6.7.
  • the film After drying, the film is exposed in a conventional sensitometer behind a stepless grey Wedge and the samples are processed separately in two different developers.
  • the development times are 15 minutes for developer 1 and 8, 12 and 16 minutes for developer 2.
  • Hardening bath (4 minutes): 0.32 g. of sodium hydroxide; 0.5 g. of sodium hexametaphosphate; 9.04 g. of soda; 20 ml. of Formalin; water up to l 1.
  • the densitometric determination shows that all the 7 samples have practically the same sensitivity.
  • the fog values are summarized in the following table:
  • Fog values after thte following develop- An emulsion is prepared in the same way as in Example 1 but it is green sensitized, and instead of the cyan coupler it contains, per kg, 300 ml. of a 2.5% solution of the following magenta coupler in aqueous NaOH solution:
  • the emulsion is divided into 4 parts, and the following compounds, in each case in the form of a 0.1% solution in methanol, are added to three of these parts:
  • EXAMPLE 3 An unwashed silver chlorobromide gelatine emulsion (20 mol percent of AgBr) which contains 0.18 mol of silver halide per litre is applied to a layer support of baryta paper in a known manner after the addition of 20 ml. of a 10% aqueous saponin solution and 2 ml. of a 30% aqueous Formalin solution, and dried. The amount of silver applied is 1.5 to 1.6 g./m.
  • the emulsion mentioned above is divided into several parts before being casting.
  • the stabilizers are added to these parts in the form of a 1% ⁇ solution in dimethylformamide.
  • the quantities added are shown in the table here inafter.
  • the samples were developed fresh and after 48 hours storage in a heating cupboard at C. and 40% relative humidity, using a developer of the following composition:
  • a washed silver bromide gelatine emulsion containing 0.16 mol of silver bromide per litre is applied to a support of baryta-coated paper in a known manner after the addition of the casting additives mentioned in Example 1 and dried.
  • the amount of silver applied is 1.7 to 1.8 g./m.
  • the emulsion indicated above is divided into several parts, and the stabilizers are added as indicated in Example 3.
  • the papers are processed as in Example 3 and the following results are obtained:
  • a light-sensitive photographic material having at least one silver halide emulsion layer containing therein 9 an antifogging concentration of a mercapto substituted pyrimidine derivative of the following formula:
  • R hydrogen, a saturated or olefinically unsaturated aliphatic group or aryl
  • Z1 the ring members required for completing a condensed benzene, cyclopentene or cyclohexene ring or a heterocyclic ring selected from the following group pyridine, tetrahydropyridine, pyrimidine, pyrrol'e, furan, thiophene, oxazole, isooxazole, imidazole or pyrazole ring; R or Z contains at least one carboxyl or sulfo group.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Physics & Mathematics (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen And Oxygen Or Sulfur-Condensed Heterocyclic Ring Systems (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US95401A 1969-12-13 1970-12-04 Silver halide emulsion containing a mercapto pyrimidine derivative antifoggant Expired - Lifetime US3692527A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE1962605A DE1962605C2 (de) 1969-12-13 1969-12-13 Photographisches Aufzeichnungsmaterial

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US3692527A true US3692527A (en) 1972-09-19

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US95401A Expired - Lifetime US3692527A (en) 1969-12-13 1970-12-04 Silver halide emulsion containing a mercapto pyrimidine derivative antifoggant

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US (1) US3692527A (cg-RX-API-DMAC7.html)
JP (1) JPS4944896B1 (cg-RX-API-DMAC7.html)
BE (1) BE760188A (cg-RX-API-DMAC7.html)
CA (1) CA952758A (cg-RX-API-DMAC7.html)
CH (1) CH557551A (cg-RX-API-DMAC7.html)
DE (1) DE1962605C2 (cg-RX-API-DMAC7.html)
FR (1) FR2073677A5 (cg-RX-API-DMAC7.html)
GB (1) GB1308166A (cg-RX-API-DMAC7.html)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3892576A (en) * 1970-02-24 1975-07-01 Agfa Gevaert Nv Photographic water-insoluble compounds having a hydrophobic diffusion-fast substituent
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
US3910791A (en) * 1973-01-30 1975-10-07 Agfa Gevaert Ag Silver halide photographic material containing a 2-propynylthio derivative as stabilizer
US4021248A (en) * 1974-09-03 1977-05-03 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
FR2344050A1 (fr) * 1976-03-09 1977-10-07 Agfa Gevaert Ag Technique d'introduction d'additifs photographiques dans des emulsions d'un sel d'argent
US4430426A (en) 1982-06-04 1984-02-07 Minnesota Mining And Manufacturing Company Stabilization of silver halide emulsions
EP0691578A2 (en) 1994-03-22 1996-01-10 Agfa-Gevaert N.V. Imaging element and method for making a printing plate according to the silver salt diffusion transfer process
EP0698822A2 (en) 1994-08-22 1996-02-28 Agfa-Gevaert N.V. Lithographic printing plate precursor with a flexible support and method for making a lithographic printing plate therewith
EP0791858A1 (en) 1996-02-26 1997-08-27 Agfa-Gevaert N.V. A method for making by phototypesetting a lithographic printing plate according to the silver salt diffusion transfer process
US5747497A (en) * 1993-05-12 1998-05-05 E. I. Du Pont De Nemours And Company Fungicidal fused bicyclic pyrimidinones
US6255311B1 (en) * 1998-01-14 2001-07-03 E. I. Du Pont De Nemours And Company Fungicidal fused bicyclic pyrimidinones

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6079348A (ja) * 1983-10-06 1985-05-07 Fuji Photo Film Co Ltd ハロゲン化銀写真感光材料
EP0465728A1 (en) * 1990-07-09 1992-01-15 Agfa-Gevaert N.V. Stabilization of tabular grains by pyrimidine derivatives

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE543978A (cg-RX-API-DMAC7.html) * 1955-01-03

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3892576A (en) * 1970-02-24 1975-07-01 Agfa Gevaert Nv Photographic water-insoluble compounds having a hydrophobic diffusion-fast substituent
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
US3910791A (en) * 1973-01-30 1975-10-07 Agfa Gevaert Ag Silver halide photographic material containing a 2-propynylthio derivative as stabilizer
US4021248A (en) * 1974-09-03 1977-05-03 Fuji Photo Film Co., Ltd. Color photographic light-sensitive material
FR2344050A1 (fr) * 1976-03-09 1977-10-07 Agfa Gevaert Ag Technique d'introduction d'additifs photographiques dans des emulsions d'un sel d'argent
US4430426A (en) 1982-06-04 1984-02-07 Minnesota Mining And Manufacturing Company Stabilization of silver halide emulsions
US5747497A (en) * 1993-05-12 1998-05-05 E. I. Du Pont De Nemours And Company Fungicidal fused bicyclic pyrimidinones
EP0691578A2 (en) 1994-03-22 1996-01-10 Agfa-Gevaert N.V. Imaging element and method for making a printing plate according to the silver salt diffusion transfer process
EP0698822A2 (en) 1994-08-22 1996-02-28 Agfa-Gevaert N.V. Lithographic printing plate precursor with a flexible support and method for making a lithographic printing plate therewith
EP0791858A1 (en) 1996-02-26 1997-08-27 Agfa-Gevaert N.V. A method for making by phototypesetting a lithographic printing plate according to the silver salt diffusion transfer process
US6255311B1 (en) * 1998-01-14 2001-07-03 E. I. Du Pont De Nemours And Company Fungicidal fused bicyclic pyrimidinones

Also Published As

Publication number Publication date
CH557551A (de) 1974-12-31
JPS4944896B1 (cg-RX-API-DMAC7.html) 1974-11-30
DE1962605C2 (de) 1983-09-08
BE760188A (nl) 1971-06-11
CA952758A (en) 1974-08-13
GB1308166A (en) 1973-02-21
DE1962605A1 (de) 1971-07-15
FR2073677A5 (cg-RX-API-DMAC7.html) 1971-10-01

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