US3778279A - Sensitisation of photographic silver halide layers for the silver dye beach process - Google Patents

Sensitisation of photographic silver halide layers for the silver dye beach process Download PDF

Info

Publication number
US3778279A
US3778279A US00162665A US3778279DA US3778279A US 3778279 A US3778279 A US 3778279A US 00162665 A US00162665 A US 00162665A US 3778279D A US3778279D A US 3778279DA US 3778279 A US3778279 A US 3778279A
Authority
US
United States
Prior art keywords
silver
dye
silver halide
photographic
sensitisation
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
US00162665A
Other languages
English (en)
Inventor
J Goete
E Boeckly
O Riester
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agfa Gevaert AG
Original Assignee
Agfa Gevaert AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Agfa Gevaert AG filed Critical Agfa Gevaert AG
Application granted granted Critical
Publication of US3778279A publication Critical patent/US3778279A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • 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
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/22—Methine and polymethine dyes with an even number of CH groups
    • 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
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials

Definitions

  • This invention relates to spectrally sensitized silver halide emulsions for color photographic materials for the silver dye bleach process, which contains merocyanine sensitizers.
  • One of the serious disadvantages of the silver dye bleach process is that the sensitivity of the photographic layers is very substantially reduced by the fact that they are already colored before exposure. This is shown most markedly if the material is subjected to a complementary sensitisation of the kind which is usual for color photographic layers, in which the blue-sensitive layer is colored yellow, the green-sensitive layer is colored magenta and the red-sensitive layer cyan. In such a case, the sensitisation maximum coincides with the absorption maximum. of the image dye and the sensitivity of these layers is very considerably reduced.
  • One of the great difficulties of this process therefore lies in the production of sufliciently sensitive layers and multi-layered products for the production of color photographic images by the silver dye bleach process. 7
  • Sensitizers for silver dye bleach materials must satisfy numerousrequirements above those which must be met for other conventional materials.
  • the sensitizers must not deleteriously affect the stability of the silver halide emulsions, in particular the storage stability and stability under tropical conditions.
  • the support for example paper, or the layer-formng substance, e.g. gelatine, should not appear to be colored by the sensitizer after the photographic processing.
  • the sensitizing dyes must be adsorbed 3,778,279 Patented Dec. 11,
  • Merocyanines have also been described for use in the silver dye bleach process. These are neutral molecules which have no affinity for the binder. Merocyanines are completely different in their constitution from the abovementioned betaine cyanines.
  • The: betaine cyanines have an electron deficiency distributed over the whole methine chain and thus carry a positive charge. This charge is compensated by acid groups with a negative charge which are attached to the molecule.
  • the molecule accordingly has a betaine structure which can be caused to undergo structural changes by the addition of other organic or inorganic substances.
  • Merocyanines by contrast, do not carry a charge which is externally apparent.
  • merocyanines are largely inert not only towards the azo dyes of the photographic layers for the silver dye bleach process but also towards other additives, especially stabilisers, mordants such as biguanides or guanides used in the normal quantities, Wetting agents,
  • additives for influencing the viscosity properties of azo dyes in gelatine and/or photographic emulsions various types of hardeners such as chrome alum or formaldehyde, and plasticisers such as glycerol.
  • silver halide emulsion layers spectral contain an azo dye, which sensitizers which have a sufiiciently high i (I)
  • R (1) a saturated or olefinically unsaturated aliphatic group preferably containing up to 5 carbon atoms, e.g. methyl, ethyl, propyl, butyl or allyl, (2) aryl, particularly a group of the phenyl or naphthyl series, e.g. aor fl-naphthyl, or (3) cycloalkyl, e.g.
  • Y sulfur or selenium
  • Z a biltunctional, straight-chain or branched chain, saturated or unsaturated, aliphatic group containing preferably 2-6 carbon atoms and more particularly 3 or 4 carbon atoms, the aliphatic group may contain further substituents, e.g. hydroxyl, alkoxy or halogen such as chlorine or bromine;
  • R' sulfo, sulfato, carboxyl or sulfonamide, in particular acyl-substituted sulfonamide, preferably sulfonamide groups which are substituted with an acyl radical which is derived from an aliphatic carboxylic acid which contains up to 5 carbon atoms; the above mentioned acid radicals may also be present in the neutralized form, e.g. as alkali metal salts, ammonium salts, etc.;
  • R" (1) hydrogen, (2) alkyl preferably containing up to 5 carbon atoms which may be substituted, e.g. with phenyl or (3) aryl and in particular phenyl; R" preferably is a hydrogen atom;
  • R' (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group preferably containing up to 40 5 carbon atoms such as methyl, ethyl or allyl, these alkyl radicals being substituted if desired, e.g. with phenyl or (3) aryl, preferably phenyl, or (4) cycloalkyl; the above-mentioned radicals may contain further substituents, e.g. alkyl or alkoxy preferably containing up to 5 carbon atoms, halogen such as chlorine or bromine, carboxyl.
  • H-SOINE (17) f Se o i 02Hs-NH-JJ-NH N ('JH;-CH CH; H, bH-Cl CH -S0:Na (18) propene sultone, chloropropane sultone or 1-ch1oro-2- s o t hydroxy-El-propane sulfonic acid:
  • sensitizer 5 omggocm 32 g. of Z-methyl-G-aminobenzothiazole and 350 cc. of (20) benzene are heated to about 60 C., 25 g. of cyclohexyl Y O X I R-NH-ii-NH CH: CzHgO-CH- Acetonltrll :Ha)
  • the compounds of Formula II are obtained by the addition of isocyanates or isothiocyanates to the molecules of amino-substituted azoles in accordance with the equation given below, followed by quaternisation with a suitable quaternising agent, e.g. with propane sultone,
  • Quaternisation is carried out by boiling 14 g. of the above mentioned base with 7 g. of propane sultone in cc. of anisole for 40 minutes.
  • the quaternized product is then precipitated by the addition of acetone, 16.5 -g. of a quaternary salt of the following formula being obtained:
  • the merocyanines for use according to the invention are particularly advantageous for sensitizing to green (500-600 nm.) highly sensitive iodide-containing silver bromide emulsions which contain magenta azo dyes. They are preferably added to the emulsion either individually or as mixtures in quantities of 20-600 mg. per mol of silver halide, preferably 70-450 mg. per mol of silver halide.
  • the sensitizing dyes of the present invention are distinguished from the known merocyanines, e.g. those mentioned in US. Pat. No. 3,401,404 by the fact that when used in the presence of azo dyes they result in strikingly steep sensitization curves, in particular a steep decay towards the long-wave region of the green part of the visible spectrum. This property results not only in a still greater improvement in the color separation and true color reproduction (with respect to the original) but also in increased darkroom safety so that processing is considerably facilitated.
  • the silver halide emulsion layers according to the invention which contain azo dyes have excellent stability on storage even under tropical conditions, and to digestion.
  • the present merocyanines are are superior to known merocyanines for example those described in US. patent specification No. 3,520,693 in that their sensitizing effect is substantially greater and in that they can be washed out more readily, discoloring of the washed layers being completely avoided.
  • the azo dyes used for the silver halide layers accord ing to the invention may suitably be those azo dyes already known for the silver dye bleach process, especially those which contain phenolic hydroxyl and/or sulfonic acid groups.
  • Dye bleaching 15 minutes in a bath of Quinoline ml 50 Sodium hypophosphite g 5 Potassium iodide g 10 Cone. sulfuric acid ml- 75 Water up to 1000 ml.
  • chlorine, bromine, nitrile stituent aryl group may be substituted with an alkyl group containing up to 5 carbon atoms;
  • X oxygen or sulfur
  • Y sulfur or selenium
  • Z a bifunctional straight or branched saturated or unsaturated aliphatic chain
  • R' sulfo, sulfato, carboxyl
  • R"- hydrogen, alkyl or aryl
  • R"' (1) hydrogen, (2) a saturated or olefinically unsaturated aliphatic group having up to 5 carbon atoms, or (3) an aryl group or a cycloalkyl; the substituent groups may be substituted by alkoxy or alkylthio groups containing up to bromine, carboxyl and the substitutent aryl group may be substituted with an alkyl group containing up to 5 carbon atoms.
  • R represents 'a saturated or olefinically 'unsaturated aliphaticgroups having up to 5 carbon atoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Thiazole And Isothizaole Compounds (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
US00162665A 1970-07-18 1971-07-14 Sensitisation of photographic silver halide layers for the silver dye beach process Expired - Lifetime US3778279A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702035727 DE2035727A1 (de) 1970-07-18 1970-07-18 Sensibihsierung photographischer Halo gensilberschichten fur das Silberfarbbleich verfahren

Publications (1)

Publication Number Publication Date
US3778279A true US3778279A (en) 1973-12-11

Family

ID=5777169

Family Applications (1)

Application Number Title Priority Date Filing Date
US00162665A Expired - Lifetime US3778279A (en) 1970-07-18 1971-07-14 Sensitisation of photographic silver halide layers for the silver dye beach process

Country Status (6)

Country Link
US (1) US3778279A (enrdf_load_stackoverflow)
BE (1) BE769399A (enrdf_load_stackoverflow)
CH (1) CH581336A5 (enrdf_load_stackoverflow)
DE (1) DE2035727A1 (enrdf_load_stackoverflow)
FR (1) FR2103039A5 (enrdf_load_stackoverflow)
GB (1) GB1316212A (enrdf_load_stackoverflow)

Also Published As

Publication number Publication date
DE2035727A1 (de) 1972-02-03
FR2103039A5 (enrdf_load_stackoverflow) 1972-04-07
GB1316212A (en) 1973-05-09
CH581336A5 (enrdf_load_stackoverflow) 1976-10-29
BE769399A (nl) 1972-01-03

Similar Documents

Publication Publication Date Title
US3705896A (en) Pyrazolo(3,2-c)-s-triazoles and process for the manufacture thereof
US3617293A (en) Photographic supersensitized silver halide emulsions
US3666480A (en) Spectrally sensitized silver halide photographic emulsion
US3615632A (en) Supersensitized photographic silver halide light-sensitive elements
US2933390A (en) Supersensitization of photographic silver halide emulsions
US3984246A (en) Antihalation and filter dyes for photographic materials
US3734738A (en) Silver halide emulsions containing reactive quaternary salts nucleating agents
US3769024A (en) Light-sensitive silver halide photographic material with sensitizing dye combination
US3810761A (en) Dyes for photography
US3765901A (en) Spectral sensitization of light-sensitive silver halide emulsions
US3687678A (en) Spectrally sensitized silver halide photographic material sensitized with xanthylium dyes and acid mercapto compounds
JP2557252B2 (ja) ハロゲン化銀写真感光材料
US2158882A (en) Photographic emulsion
US3288610A (en) Optically sensitized photographic silver halide emulsions
JPS5946646A (ja) ハロゲン化銀写真感光材料
US3778279A (en) Sensitisation of photographic silver halide layers for the silver dye beach process
US3424586A (en) Silver halide emulsions sensitized with cyanine dyes containing a hydroxypropyl sulfonic acid radical
US3702767A (en) Spectrally sensitized light sensitive material
US3681080A (en) Silver halide photographic emulsion
US3401404A (en) Merocyanine dye-sensitized photographic materials comprising silver halide emulsion layers containing azo-dyes
US4179294A (en) Silver halide light-sensitive element containing dye
US3592657A (en) Optically sensitized silver halide light-sensitive material
US3173791A (en) Supersensitized photographic silver halide emulsions
US3094418A (en) Silver halide meulsions containing cationic oxonol and benzylidene dyes
US2206076A (en) Photographic emulsion