US3615500A - Silver halide emulsions which contain color couplers - Google Patents

Silver halide emulsions which contain color couplers Download PDF

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Publication number
US3615500A
US3615500A US852073A US3615500DA US3615500A US 3615500 A US3615500 A US 3615500A US 852073 A US852073 A US 852073A US 3615500D A US3615500D A US 3615500DA US 3615500 A US3615500 A US 3615500A
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United States
Prior art keywords
sample
silver halide
emulsion
tosyl
photographic material
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Expired - Lifetime
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US852073A
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English (en)
Inventor
Harald Huckstadt
Erwin Ranz
Herbert Grabhofer
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • 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
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/043—Polyalkylene oxides; Polyalkylene sulfides; Polyalkylene selenides; Polyalkylene tellurides

Definitions

  • the invention relates to a process for increasing the sensitivity of photographic silver halide emulsions which contain color couplers as well as to color photographic silver halide emulsions with improved sensitivity.
  • water-soluble quaternization products of a, w-bis-(thiomorpholinyl)-alkanes with bifunctional polyalkylene oxide derivatives are excellently suitable for use as development accelerators or chemical sensitizers for silver halide emulsions which contain color couplers.
  • VI LL wherein represents a 2 to 6
  • y 2 to 10 preferably 2 to 5, x any anion, e.g. halide, perchlorate, benzene sulfonate or the like.
  • the substances according to the invention are prepared by quaternizing a bis-(thiomorpholinyl)-alkane, for example with the bis-tosylate of a polyalkylene oxide of desired chain length.
  • The-method of preparation will be described in the following with reference to compound 1]:
  • the substances according to the invention may be added to the photographic emulsion at any stage of its preparation before, during or after chemical ripening. They may also be added to the casting solution immediately before casting. The quantity added depends on the desired effect and can easily be determined by the expert by the usual tests. Quantities of 0.1 to 10 g. per mol of silver halide will normally be sufficient.
  • the emulsions can also be optically sensitized with cyanine dyes such as basic or acid carbocyanines, cyanine dyes of the betaine type, rhodacyanine or merocyanine dyes, styryl or oxonol dyes. Suitable sensitizers are described by F. M. Hamer The Cyanine Dyes and related Compounds. lnterscience Publishers, (1964).
  • cyanine dyes such as basic or acid carbocyanines, cyanine dyes of the betaine type, rhodacyanine or merocyanine dyes, styryl or oxonol dyes.
  • Suitable sensitizers are described by F. M. Hamer The Cyanine Dyes and related Compounds. lnterscience Publishers, (1964).
  • the emulsions may also contain chemical sensitizers, e.g. reducing agents such as stannous salts, polyamines such as diethyltriamine or aminomethane sulfinic acids or derivatives thereof such as described in Belgian patent specification No. 547,323 or sulfur compounds as described in U.S. Pat. No 1,574,944, for example allyl thiocyanate, allylthiourea, sodiumsulfate and the like.
  • Suitable chemical sensitizers are also salts of noble metals such as ruthenium, rhodium, palladium, iridium, platinum or gold, as described in the article by R. Koslowsky, Z, wiss.phot. 46, 65 72 (I959).
  • polyalkylene oxides especially polyethylene oxide having an average molecular weight of 1,000 to 20,000 and derivatives thereof, such as condensation products of alkylene oxides with aliphatic alcohols, glycols cyclic dehydration products of hexitoles, alkyl substituted phenols, aliphatic carboxylic acids, aliphatic amines, diamines or amides.
  • the said condensation products have preferably a molecular weight of above 1,000. It is also possible to apply combinations of several chemical sensitizers. 1
  • Particular suitable for the emulsion of the present invention are chemical sensitizers of the thiomorpholine series such as described in French Pat. No. 1,506,230.
  • the emulsions according to the invention may additionally contain the usual stabilizers, e.g. homopolar or salt-type compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts, and other mercury compounds.
  • stabilizers which may be used include azaindenes, especially tetraazaindenes or pentaazaindenes, in particular those substituted with hydroxyl or amino groups. Compounds of this type have been described in the article by Birr, Z. wiss.phot. 47, 2-58 1952).
  • Other suitable stabilizers include heterocyclic mercapto compounds, e.g. l-phenyl-5-mercapto-tetrazole, quaternary benzthiazole derivatives and benztriazoles.
  • the emulsions may be hardened in the usual manner, for example, with formaldehyde or halogen-substituted aldehydes that contain a carboxyl group, e.g. mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
  • formaldehyde or halogen-substituted aldehydes that contain a carboxyl group, e.g. mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
  • the substances described may also be added to the developer, although they are less effective when used in this way. Amounts of l to 20 g. per. 1. of the aqueous developing composition have proved sufficient.
  • EXAMPLE 1 A mixed emulsion composed of 90 percent of a silver iodobromide gelatine emulsion and percent of a silver iodochlorobromide gelatine emulsion, which mixed emulsion has been ripened to optimum sensitivity in known manner with gold compounds and sulfur compounds is sensitized by the addition of 45 mg. of the following sensitizing dye per kg. of emulsion:
  • emulsion g. of l-(3'-sulfo-4-phenoxy)-phenyl-3-heptadecylpyrazolone as magenta coupler, 250 mg. of l,3,3a,7-tetraaza4-hydroxy-6-methylindene as stabilizer, ml: ofa 5 percent aqueous solution of saponin as wetting agent, 2,5 ml. of a 30 percent aqueous solution of formaldehyde as hardener.
  • the emulsion is divided into 10 parts and the following substances per kg. of emulsion are added to the individual parts:
  • Sample A Comparison sample without additive.
  • Sample B 300 mg. of ofSubstance 1.
  • Sample C 300 mg. of Substance 111.
  • Sample D 1 g. ofSubstance IV.
  • Sample E 300 mg. of Substance V.
  • Sample F 300 mg. of Substance VI.
  • Sample G 300 mg. ofSubstance VII.
  • Sample H 300 mg. of Substance VII of British Pat. specification No. 1,145,186 of the following formula:
  • Color development 7 minutes Short stop bath 5 minutes washing 5 minutes Bleaching bath 5 minutes 5 Washing 5 minutes Fixing bath 5 minutes Washing 10 minutes
  • the color developer has the following composition:
  • the other treatment baths had the following composition:
  • EXAMPLE 2 To the emulsion described in example 1 are added an optical sensitizer for the red region of the spectrum (40 mg./kg.) of the formula:
  • the other additives are the same as those given in example 1.
  • the emulsion is divided into 1 1 parts and the following substances per kg. of emulsion are added to the individual parts:
  • Sample A Comparison sample without additive.
  • Sample C 300 mg. of Substance 111.
  • Sample 1-1 300 mg. of Substance V111.
  • Sample K as sample I of Example 1.
  • 3' denote a difference ofone shutter stop.
  • Sample A Comparison sample without additive.
  • Sample C l g. ofSubstance 111.
  • Sample 1-1 300 mg. of Substance V111.
  • the individual layers are optically sensitized as described in examples 1 and 2 (the blue sensitive top layer emulsion in this case does not contain an optical sensitizer) and the following color couplers are added:
  • top layer consists of the nonsensitized emulsion of example 3 which contains 20 g. of yellow coupler 3-stearylaminobenzoyl- 3',5'-dicarboxyacetanilide and the other additives of example 1.
  • the above multilayer material is used as comparison sample (Sample A).
  • a second multilayer material (Sample B) was made in the same way but in addition contains 500 mg. of compound 11 per kg. of emulsion in each emulsion layer.
  • Samples A and B are exposed to white light behind a grey step wedge and developed for 8 minutes in a developer of the following composition:
  • the samples are furthermore processed as described in examples l to 3.
  • An increase by 3" corresponds to a sensitivity increase of one shutter stop.
  • EXAMPLE illustrates the comparative ineffectiveness of the substances according to the invention in a silver chloride emulsion which does not contain a color coupler.
  • the following casting additives 5 ml. of a 1 percent aqueous solution of --phenyl-5-mercaptotetrazole as stabilizer,
  • Sample A Comparison sample without additive.
  • This casting solution is applied onto a baryta coated paper support, exposed behind a grey step wedge and developed at C. for 1 minute in a developer of the following composition:
  • a difference ol'3.0 corresponds to a sensitivity difference ofone shutter stop.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US852073A 1968-09-06 1969-08-21 Silver halide emulsions which contain color couplers Expired - Lifetime US3615500A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19681797263 DE1797263A1 (de) 1968-09-06 1968-09-06 Verfahren zur Steigerung der Empfindlichkeit photographischer,farbkupplerhaltiger Halogensilberemulsionen

Publications (1)

Publication Number Publication Date
US3615500A true US3615500A (en) 1971-10-26

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US852073A Expired - Lifetime US3615500A (en) 1968-09-06 1969-08-21 Silver halide emulsions which contain color couplers

Country Status (6)

Country Link
US (1) US3615500A (de)
BE (1) BE738260A (de)
CH (1) CH543104A (de)
DE (1) DE1797263A1 (de)
FR (1) FR2017532A1 (de)
GB (1) GB1272328A (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5604084A (en) * 1994-11-18 1997-02-18 Imation Corp. Chemical sensitisation of silver halide emulsions

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5604084A (en) * 1994-11-18 1997-02-18 Imation Corp. Chemical sensitisation of silver halide emulsions

Also Published As

Publication number Publication date
BE738260A (de) 1970-03-02
CH543104A (de) 1973-10-15
GB1272328A (en) 1972-04-26
FR2017532A1 (de) 1970-05-22
DE1797263A1 (de) 1971-08-05

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