US3401404A - Merocyanine dye-sensitized photographic materials comprising silver halide emulsion layers containing azo-dyes - Google Patents

Merocyanine dye-sensitized photographic materials comprising silver halide emulsion layers containing azo-dyes Download PDF

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US3401404A
US3401404A US428205A US42820565A US3401404A US 3401404 A US3401404 A US 3401404A US 428205 A US428205 A US 428205A US 42820565 A US42820565 A US 42820565A US 3401404 A US3401404 A US 3401404A
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dye
silver
dyes
silver halide
azo
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Seidel Bernhard
Riester Oskar
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Agfa Gevaert AG
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Agfa Gevaert AG
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    • 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
    • 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
    • C09B23/107—The polymethine chain containing an even number of >CH- groups four >CH- groups
    • 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
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02—Disazo dyes
    • C09B35/021—Disazo dyes characterised by two coupling components of the same type
    • C09B35/023—Disazo dyes characterised by two coupling components of the same type in which the coupling component is a hydroxy or polyhydroxy compound
    • 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
    • C09B35/00—Disazo and polyazo dyes of the type A<-D->B prepared by diazotising and coupling
    • C09B35/02—Disazo dyes
    • C09B35/039—Disazo dyes characterised by the tetrazo component
    • C09B35/08—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl
    • C09B35/10—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl from two coupling components of the same type
    • C09B35/16—Disazo dyes characterised by the tetrazo component the tetrazo component being a derivative of biphenyl from two coupling components of the same type from hydroxy-amines
    • 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 a merocyanine dye-sensitized photographic element comprising at least one silver halide emulsion layer uniformly dyed with an azo-dye for use in the silver dye bleach process.
  • Colored photographic images can be prepared by the silver dye bleach process in which a negative or a positive silver image is obtained, depending on the processing, by exposure and subsequent development of uniformly colored photographic layers.
  • the azo-dye is bleached, generally in a strongly acidic bleach bath, in accordance with the silver image.
  • dye image of the original is obtained.
  • the dye image has a gradation opposite to the gradation of the silver image.
  • the dyes generally employed are azo dyes, both water-soluble dyes and insoluble pigments.
  • One of the great disadvantages of the silver dye bleach process is that the sensitivity of the dyed photographic layers is very considerably reduced. This occurs in particular if the layers are sensitized in such a way, as is generally the case, that the blue-sensitive layer is dyed yellow, the green-sensitive layer magenta and the red-sensitive layer cyan. The reason for this is that the sensitization maxima coincide with the absorption maxima of the dyes. With respect to the sensitivity of the light-sensitive layers, the silver dye bleach process is inferior to other color photographic processes. Accordingly, one of the great difiiculties of the silver dye bleach process is the preparation of sufficiently sensitive layers. 4
  • sensitizers which are to be used in materials for the silver dye bleach process have to satisfy several requirements. In addition to good sensitizing properties the sensitizer must not deleteriously effect the stability of the emulsions, particularly in storage and under tropical conditions. Furthermore the sensitizing dyes have to be sufliciently soluble in the processing baths, so that the dye is readily washed out and no coloring of the support, for example paper,- or the binding agent of the layer, for example gelatin, occurs.
  • the sensitizer must adhere sufficiently firmly to the silver halide grains as not to be displaced by the azo-dyes, because otherwi-se the sensitizing action is decreased in the presence of vazo-dyes.
  • sensitizing dyes for silver halide emulsion layers to be used in the silver dye bleach process.
  • Another object is to provide photographic materials comprising at least one lightsensitive silver halide emulsion layer optically sensitized and containing an azo-dye.
  • merocyanine dyes are outstanding in their optically sensitizing properties for silver halide emulsion layers which contain uniformly distributed azo-dyes and which are to be used in the silver dye bleach process.
  • the merocyanines of the present invention are characterized by two 5- or 6-membered heterocyclic rings which contain nitrogen as a ring member and which are linked together by way of 2 or 4 methine groups.
  • Merocyanines of this type are generally known as zero-, dior tetramethine merocyanines.
  • X represents the ring members necessary to complete a 5- or 6-membered heterocyclic ring, preferably of the following groups: thiazole, benzthiazole, napthothiazole, oxazole, benzoxazole, naphthoxazole, selenazole, benzselenazole, naphthoselenazole, benzirnidazole, indoline, pyrrolidine, tetrazole, thiodiazole;
  • Y hydrogen or alkyl preferably lower alkyl having up to 3 carbon atoms, such as methyl or ethyl;
  • Z the ring members necessary for completing a S-membered heterocyclic ring preferably such as thiazole oxazole, selenazole, imidazole or pyrazole;
  • R alkyl preferably lower alkyl having up to 5 carbon atoms in particular methyl or ethyl, whereby the alkyl groups can be substituted by carboxy, sulfo, hydroxy or chlorine;
  • R' alkyl preferably alkyl up to 5 carbon atoms such as methyl or ethyl, olefinically unsaturated alkyl, preferably up to 5 carbon atoms such as allyl, cyeloalkyl such as cyclohexyl, or aryl preferably phenyl;
  • n 0 or 1.
  • heterocyclic or aromatic rings can be substituted, for example, with alkyl preferably lower alkyl of up to 5 carbon atoms, alkoxy having up to 5 carbon atoms, hydroxy or halogen preferably chlorine.
  • the merocyanine dyes of the present invention are outstanding in their optically sensitizing action' for silver halide emulsion layers containing an azo-dye. Furthermore they are superior to betain cyanines since the color images obtained by the process of the invention show very clear white portions of the images without any color stain.
  • the above merocyanines are substantially inert both to the azo-dyes in the photographic layers for the silver dye bleach process and to other additives, in particular stabilizers, mordants such as biguanides or guanides, wetting agents, agents for influencing the viscosity of azo-dyes in gelatin and/or photographic emulsions, hardening agents such as chrome alum, paraformaldehyde, or plasticizers such as glycerol.
  • the merocyanine dyes of the invention are preferably incorporated in the washed, finished silver halide emulsions before the azo-dyes are added and should be uniformly distributed throughout the emulsion.
  • the silver halides of the emulsions comprise silver Example 1 500 g. of a silver bromide emulsion of average sensitivity are sensitized with mg. of a dyestufi of the formula dissolved in methanol.
  • the preparation of the sensitizer is described in- French patent specification No. 1,133,324.
  • chloride, silver bromide or silver chlorobromide which of a yellow dyestulf of the formula SOSH: may contain a small amount of silver iodide, preferably as described in British patent specification No. 766,020,
  • the type of silver halide emulsions that can be sensitized with the merocyanines of the present invention include any of those prepared with hydrophilic colloids that are known to be satisfactory for dispersing silver halides.
  • These colloids include preferably gelatin which can be used in admixture with other hydrophilic colloids such as albumin, alginic acids and derivatives thereof, hydrophilic synthetic resins such as polyvinyl alcohol, polyvinyl pyrrolidone and the like.
  • the concentration of the merocyanine dye and the light-sensitive emulsion can vary widely from about 5 to about 100 mg. per liter of emulsion.
  • the suitable and most economical concentration for any given emulsion will be apparent to those skilled in the art upon making the tests customarily used in the art of emulsion making.
  • a silver halide emulsion sensitized with a merocyanine of the present invention the following procedure is satisfactory: The desired quantity of the sensitizing dye is dissolved in a suitable solvent and a volume of this solution containing the desired amount of the dye is slowly added to the silver halide emulsion. Thereafter, the azo-dye is added preferably from a solution in a suitable solvent. With most of the merocyanine dyes of the present invention 10-30 mgs. of sensitizing dye per liter of emulsion are suflicient to produce the maximum sensitizing effect.
  • the photographic emulsions may be coated on any of the photographic supports including paper, cellulose esters such as cellulose acetate or nitrate, polystyrene, polyesters in particular of polyethylene terephthalate, poly carbonates, preferably of bis-hydroxy phenyl alkanes, and the like.
  • Photographic silver halide emulsions containing the merocyanines of the invention can also contain such additives as chemical sensitizers, for instance, sulfo sensitizers, nobel metal compounds such as gold or palladium compounds, stabilizers such as benzotriazole compounds, heterocyclic mercapto compounds, mercury compounds or azaindenes; hardeners such as glyoxal, formaldehyde, acrolein or the like.
  • chemical sensitizers for instance, sulfo sensitizers, nobel metal compounds such as gold or palladium compounds, stabilizers such as benzotriazole compounds, heterocyclic mercapto compounds, mercury compounds or azaindenes
  • hardeners such as glyoxal, formaldehyde, acrolein or the like.
  • Azo-dyes which can advantageously be used in combination with the merocyanines of the invention comprise the customarily employed dyes which are known to be satisfactory for the silver d-ye bleach process.
  • Preferred Example 1 is added to the emulsion.
  • the emulsion is then mordanted with 2 g. of diphenyl-4-4-dibiguanide, as described in French patent specification No. 864,332 to increase the resistance to diffusion of the dye, and applied onto a baryta-coated paper.
  • the resulting layer contains p-Methyl aminophenol g 1 Sodium sulfite anhydrous g 13 Hydroquinone g 3 Sodium carbonate (anhydrous) g 26 Potassium bromide g 1 Water ml 1000 (2) Rinsing for 1 minute.
  • Tetrasodium ethylenediaminetetraacetate g 26 Sodium carbonate (anhydrous) g 24
  • Ferric chloride g 15 Sodium sulfite (anhydrous) g 13
  • Sodium thiosulfate g 200 Water ml 500 6 Final rinsing for minutes. (prepared according to German Patent No. 883,025) and with 300 ml. of a 1% aqueous solution of the mordanted azo-dye referred to in Example 1.
  • the processing is performed as described in Example 1.
  • the sensitized sample is more sensitive by 1.1 logarithmic units than the unsensitized emulsion.
  • Two direct-positive color wedges are formed which are measured behind a blue filter.
  • the difference in the sensitivity is 1.7 logarithmic units.
  • the paper support is unstained.
  • Example 2 After melting with a small amount of 4-hydroxy-6- methyl-1,3,3a,7-tetraazainden as a stabilizer, 500 g. of a highly sensitive silver iodobromide emulsion is sensitized 10 to green light by adding 15 mg. of the sensitizing dye of the formula Example 5
  • the procedure is the same as in Example 2, except that the dye used in that example is replaced by 15 mg. of the sensitizer of the formula the preparation of which is described in Belgian patent o0 specification 648,068.
  • the usual additives are then incorporated, followed by the addition of 200 ml. of a 1% which y e P p in accordance wi h Bri i h Pataqueous solution of the magenta azo dye of the formula ents Nos. 426,718 and 428,360.
  • Example 2 which is prepared in accordance with German patent The material is processed as described in Example 2. specification No. 1,039,840. To improve its fastness to The sensitized sample has a sensitivity higher by 1.2 difiusion, a solution of 0.75 g. of bis-[3-anisidyl-4-bigualogarithmic units than that of the unsensitized sample. nide] is added, and the emulsion is applied onto a support Example 6 of cellulose triacetate as described in Example 1.
  • a sample 40 is exposed in ra sensitometer behind a step wedge and yel- The Pfh r h me as In Example 2, except that low filter, and is then processed as describedinExample 1 the Sehslhlef used In that example 15 replaced y 15 and compared with a standard sample which is not senof the y of the formula sitized by sensitometric measurement behind a green filter the difference in the sensitivity of the two samples CH3 is found to be 1.7 logarithmic units.
  • (1:113 N I the sensitizer used in-Example. 2 is replaced by 15 mg. of a sensitizing dye of the formula H v which may be prepared as described in British Patent No. C" l i 428,360. Contrary to Example 2, no mordant is used.
  • I The material is processed as described in Example 1.
  • the sensitized sample has a sensitivity of 0.73 logarithmic 0: 2 units greater than the unsensitized sample.
  • Example 7 brr N I JHQ v If the sensitizer referred to in Example 2 is'replaced by I After exposure, processing and evaluation as in Ex- .5 mg-Of the dye ample2, the difiF erence in sensitivity between the sensitized and unsensitized layers is 0.9 logarithmic units. 1 CHCH (IIH;
  • Example 8 If the sensitizer mentioned in Example 2 is replaced by 15 mg. of the compound of the formula which may be prepared according to J. Am. Chem. Soc. 73, 5332 (1951 and if the procedure described in Example 2 is followed, there is an increase in the sensitivity of the sensitized sample of 0.82 logarithmic units as compared with an identical unsensitized emulsion.
  • Example 9 The procedure is the same as in Example 2, except that the emulsion has a high silver content and, to obtain a suitable -value, is diluted with such a quantity of gelatin, that, after exposure and development, there is still sufiicient silver left to bleach the azo-dye completely.
  • a sensitizing dye of the formula HaO-Q-SOz-NH H 8 Example The procedure is the same as in Example 9, except that the sensitizer dye has the formula 50:13: A simple is exposed and processed as described above. The sensitized sample is 1.4 logarithmic u-nits more sensitive than an unsensitized comparison sample.
  • the sensitizing dye is prepared as follows:
  • Example 11 15 mg. of the sensitizing dye of the formula which is prepared by a method analogous to that described in J. Am. Chem. Soc. 73, 5337 (1951) Merodicarbocyanine are added to 500 ml. of a highly sensitive silver bromide emulsion containing 50 mg. of 1-phenyl-5- mercapto tetrazole as a stabilizer. After the addition of hardening agents such as 0.4 g. of chrome alum and 0.3 g. of paraformaldehyde, and wetting agents such as 20 ml. of a 5% solution of saponin the emulsion is mixed with 250 ml. of an aqeuous gelatin solution containing 1% of the cyan dye of the formula I I )11 NH-SOz-GCH:
  • reaction solution is taken up in acetone and the 2 (phenylacetamino-ethylide-ne)-intermediate product which crystallizes out, is suction-filtered. Yield: 22.2 g. M.P. 286 C.
  • the dye is made resistant to diffusion 'by adding 0.5 g. of bis-(3-anisidyl-4-biguanide) in a 1% aqueous gelatin solution, and applied onto a baryta-coated paper base.
  • the dried layer contains 1.5 g. of silver per square meter as silver halide.
  • an otherwise iden- Example 12 solution an acidic thiosulfate both containing for instance 200 g. of sodium thiosulfate and The procedure ls the Same as m Examp 1e except that 20 g. of potassium metabisulfite per liter of solution, will the azo dye is replaced by the following cyan dye:
  • Example 11 which is itself highly resistant to diffusion and, for this generally be used as a fixer. Combined bleaching and reason, does not require mordanting.
  • This compound is fixing baths are also very useful, however, and an exprepared in accordance with Example 1 of German Pat- 15 ample of such a composition comprising an Fe(III)-come t N 1,041,355, The comparison s d i n f m plex of ethylene diamine tetraacetic acid is described in which the mordant, bis-(3-anisidyl-4-biguanide), has also Example 1. been omitted. The samples are processed as described in We claim: Example 11.
  • a lightensitive photographic element comprising colored wedges obtained the en iti ed a le i m re at least one supported light-sensitive silver-dye-bleach itiv by 1,87 logaritmic it silver halide emulsion layer which contains a silver-dye-
  • differences in sensitivity are given blfiach 3Z0 dye and is sensitized y a sensitizing amount in logarthmic units wherein a difference of sensitivty of of a merocyanine y of the formula 0.3 log. units correspond to a difference by a factor of 2 and 1.0 log. units correspond to a difference by a factor Y of 10.
  • both of X represents the ring members necessary to complete a which can be combined in one composition.
  • tetralole, benlthialole, indoline! PY befllimiddeveloper and dye bleach bath other steps such as fixing azole, thiadiazole or benzoxazole g;
  • n Y stands for hydrogen or alkyl having up to 3 carbon
  • developer compositions those containing for instance atoms
  • Z stands for the ring members necessary for completing other systems especially those containing l phenyl pyra rhodanine, thiohydamoi or Pyrazolone ring;
  • R stands for alkyl having up to 5 carbon atoms, carboxy-
  • R stands for alkyl having up to 5 carbon atoms, carboxy-
  • substituted alkyl in which the alkyl has up to 5 carbon azo dye bleaching baths may contain 40 atoms, sulfa-substituted alkyl having up to 5 carbon fr 10 to 80 f thiouwa, 20 to 30 ghof an alkali atoms, hydroxy-substituted alkyl having up to 5 carbon halide and 10 to 20 g. of a mineral acid per liter such atoms or chloro'substimted alkyl having P to 5 as described in U.S. Patent No. 2,217,544.
  • Silver bleach baths for use in the process 3,053,655 9/ 1962 Dreyfuss et a1 96-99 of the process of the invention may, e.g., consist of copper 3,157,507 ll/ 1964 Bruengger et al 9699 chloride (10 to 50 g.) and potassium bromide (10-100 g.) together with hydrochloric acid (5 to 20 ml. per liter of TRAVIS BROWN, Primary Examiner- UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 ,401 ,404 September 10 I968 Bernhard Seidel et a1 It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US428205A 1964-02-13 1965-01-26 Merocyanine dye-sensitized photographic materials comprising silver halide emulsion layers containing azo-dyes Expired - Lifetime US3401404A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEA0045221 1964-02-13
DEA47431A DE1213240B (de) 1964-02-13 1964-10-24 Lichtempfindliches photographisches Material mit mindestens einer Azofarbstoff enthaltenden optisch sensibilisierten Halogensilber-Emulsions-schicht fuer das Silberfarbbleichverfahren

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BE (1) BE659657A (en])
CH (1) CH451702A (en])
DE (1) DE1213240B (en])
FR (1) FR1428104A (en])
GB (1) GB1078227A (en])

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3520693A (en) * 1966-07-16 1970-07-14 Agfa Gevaert Ag Merocyanine dye-sensitized photographic materials comprising silver halide emulsion layers containing azo-dyes
US3658521A (en) * 1969-10-03 1972-04-25 Eastman Kodak Co 1-aminopyridinium dyes as sensitizers in electrophotographic layers
US3860583A (en) * 1970-12-09 1975-01-14 Bayer Ag Indolenine dyestuffs
US3904613A (en) * 1970-12-09 1975-09-09 Bayer Ag Hemicyanine dyestuffs
US5136045A (en) * 1989-09-22 1992-08-04 Sumitomo Chemical Company, Limited Pyrazole containing methine compounds

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1239017A (en]) * 1968-02-22 1971-07-14

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2612448A (en) * 1948-04-02 1952-09-30 Gaspar Photographic elements containing azo dyes and process using them
US3053655A (en) * 1950-01-06 1962-09-11 Minnesota Mining & Mfg Photographic material and process
US3157507A (en) * 1958-12-04 1964-11-17 Ciba Ltd Optical sensitization of photographic materials suitable for the silver-dyebleachingprocess

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2612448A (en) * 1948-04-02 1952-09-30 Gaspar Photographic elements containing azo dyes and process using them
US3053655A (en) * 1950-01-06 1962-09-11 Minnesota Mining & Mfg Photographic material and process
US3157507A (en) * 1958-12-04 1964-11-17 Ciba Ltd Optical sensitization of photographic materials suitable for the silver-dyebleachingprocess

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3520693A (en) * 1966-07-16 1970-07-14 Agfa Gevaert Ag Merocyanine dye-sensitized photographic materials comprising silver halide emulsion layers containing azo-dyes
US3658521A (en) * 1969-10-03 1972-04-25 Eastman Kodak Co 1-aminopyridinium dyes as sensitizers in electrophotographic layers
US3860583A (en) * 1970-12-09 1975-01-14 Bayer Ag Indolenine dyestuffs
US3904613A (en) * 1970-12-09 1975-09-09 Bayer Ag Hemicyanine dyestuffs
US5136045A (en) * 1989-09-22 1992-08-04 Sumitomo Chemical Company, Limited Pyrazole containing methine compounds

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CH451702A (de) 1968-05-15
BE659657A (en]) 1965-08-12
FR1428104A (fr) 1966-02-11
DE1213240B (de) 1966-03-24
GB1078227A (en) 1967-08-09

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