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
  • C09B23/0075—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of an heterocyclic ring
• • 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
  • C09B23/0066—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain being part of a carbocyclic ring,(e.g. benzene, naphtalene, cyclohexene, cyclobutenene-quadratic acid)
• • 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
  • G03C1/26—Polymethine chain forming part of a heterocyclic ring
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0622—Heterocyclic compounds
  • G03G5/0644—Heterocyclic compounds containing two or more hetero rings
  • G03G5/0661—Heterocyclic compounds containing two or more hetero rings in different ring systems, each system containing at least one hetero ring
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0664—Dyes
  • G03G5/0666—Dyes containing a methine or polymethine group
  • G03G5/0668—Dyes containing a methine or polymethine group containing only one methine or polymethine group
  • G03G5/067—Dyes containing a methine or polymethine group containing only one methine or polymethine group containing hetero rings
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03G—ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
  • G03G5/00—Recording-members for original recording by exposure, e.g. to light, to heat or to electrons; Manufacture thereof; Selection of materials therefor
  • G03G5/02—Charge-receiving layers
  • G03G5/04—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor
  • G03G5/06—Photoconductive layers; Charge-generation layers or charge-transporting layers; Additives therefor; Binders therefor characterised by the photoconductive material being organic
  • G03G5/0664—Dyes
  • G03G5/0666—Dyes containing a methine or polymethine group
  • G03G5/0672—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups
  • G03G5/0674—Dyes containing a methine or polymethine group containing two or more methine or polymethine groups containing hetero rings

Definitions

• the present invention relates to light-sensitive photographic materials which are spectrally sensitized with new types of sensitizing dyes, and more particularly to materials of this type which contain silver halide emulsion layers.
• the adsorption on the silver halide should be of such a strength that the sensitizing effect is disturbed very little by other necessary additives such as wetting agents and emulsifiers, stabilizers, color couplers, dyes which can be bleached or white toners.
• the sensitization should be reliable even under extreme conditions such as conditions of high temperature and moisture and the sensitizing dyes should not increase the basic fogging as is occasionally the case with basic cyanine dyes.
• the sensitizing dyes are also required to have certain sensitization properties such as suflicient intensity or sensitization in the sensitization range and above all a very steep drop in sensitization in the transition to light of longer wavelengths. For these reasons, there is considerable interest in finding new sensitization dyes which do not have the preceding disadvantages.
• Y is an aliphatic hydrocarbon radical required for completing a S-membered or 6-membered ring, e.g.
• R and R are (1) hydrogen (2) saturated or unsaturated aliphatic hydrocarbon groups which preferably.
• R and R may represent a heterocyclic ring together with nitrogen atom, e.g. a pyrrolidine, piperidine, hexamethyleneimine, morpholine, thiomorpholine, piperazine, phenomorpholine or tetrahydroquinoline ring;
• R is hydrogen or saturated or unsaturated aliphatic hydrocarbon groups, preferably having up to 6 C atoms, for example methyl, ethyl, propyl or butyl; or aryl, especially phenyl;
• R, R and R are (1) hydrogen (2) saturated or olefinically unsaturated aliphatic hydrocarbon groups preferably having up to 6 C atoms which may be substituted, e.g. with phenyl, hydroxyl or carboxyl, (3) cycloalkyl, example cyclohexyl, or (4) aryl, especially phenyl; and can be the same or different;
• R is hydrogen, alkyl, alkoxy or alkylthio preferably having up to 3 C atoms, for example methyl, methoxy or methylthio; or aryl, for example phenyl;
• R is (l) saturated or unsaturated aliphatic hydrocarbon groups preferably having up to 6 C atoms, which groups may be substituted, e.g. with phenyl, hydroxyl, halogen, amino, carboxyl, sulfo, sulfonyl amino, sulfamyl, carbonamido, carbamyl, carbalkoxy, sulfate or thiosulfate (2) cycloalkyl such as cyclohexyl or (3) aryl, especially phenyl;
• X and Z may be identical or different and may represent --O, -S, -NR or CONR p and q are identical or different and represent 0 or 1;
• Anion is any anion, e.g. a halide, such as chloride, bromide or iodide, perchlorate, sulfate, methylsulfate, ptoluenesulfonate and the like; the anion is not present in cases where R contains an acid group in the anionic form so that a betaine is present;
• a halide such as chloride, bromide or iodide, perchlorate, sulfate, methylsulfate, ptoluenesulfonate and the like
• Q a radical required for completing a heterocyclic group comprising a S-membered or 6-membered heterocyclic ring;
• the heterocyclic group may contain a condensed -benzene or naphthalene ring and other substituents;
• thiazole series e.g. thiazole, 4- methylthiazole, S-methylthiazole, 4,5-dimethy1thiazole, 4- phenylthiazole, S-phenylthiazole, 4,5 diphenylthiazole, benzothiazole, 4 chlorobenzothiazole, 5 .chlorobenzothiazole, 6 chlorobenzothiazole, 7 chlorobenzothiazole, 6 bromobenzothiazole, 5 iodobenzothiazole, 6 iodobenzothiazole, 4 methylbenzothiazole, 5 methylbenzothiazole, 6 methylbenzothiazole, 5,6 dimethylbenzothiazole, 4 phenylbenzothiazole, 5-phenylbenzothiazole, 6 phenylbenzothiazole, S-hydroxybenzothiazole, 6 hydroxybenzothiazole, 4 methoxybenzothiazole, S-methoxy
• oxazole 4- methyloxazole, 4 phenyloxazole, 4,5-diphenyloxazole, benzoxazole, 5 chlorobenzoxazole, 6-chlorobenzoxazole, 5,6 dimethylbenzoxazole, 5 phenylbenzoxazole, S-hydroxybenzoxazole, 5 methoxybenzoxazole, 5 ethoxybenzoxazole, 6 dialkylaminobenzoxazole, 5 carboxybenzoxazole, 5 sulfonbenzoxazole, 5 sulfonamidobenzoxazole, 5 B carboxyvinylbenzoxazole, naphtho[1,2-d] oxazole, naphtho[2,1-d]oxazole or naphtho[2,3-d]oxazole); those of the imidazole series including benzimidazoles-and naphthimidazoles (e.g. P methylimidazole,
• quinoline 3 methylquinoline, 5 methylquinoline, 7 methylquinoline, 8 methylquinoline, 6 chloroquinoline, 8-chlo1'oquinoline, 6 methoxyquinoline, 6 ethoxyquinoline, 6- hydroxyquinoline, 8 hydroxyquinoline or 5 oX'o-5,6,7,8 tetrahydroquinoline); those of the isoquinoline series (e.g. isoquinoline or 3,4 dihydroisoquinoline); and those of the pyrroline, tetrahydropyridine, thiadiazole, oxadiazole, pyrimidine, triazine'or benzothiazine series.
• isoquinoline series e.g. isoquinoline or 3,4 dihydroisoquinoline
• pyrroline tetrahydropyridine, thiadiazole, oxadiazole, pyrimidine, triazine'or benzothiazine series.
• heterocyclic groups may in addition be substituted by any other substituents, e.g. by additional alkyl groups which preferably have up to 3 C atoms, e.g. methyl or ethyl, or halogen such as chlorine or bromine, hydroxyl, alkoxy, preferably with up to 3 C atoms such as methoxy or ethoxy, hydroxyalkyl, alkylthio, aryl such as phenyl, or aralkyl such as benzyl, amino, substituted amino and the like.
• additional alkyl groups which preferably have up to 3 C atoms, e.g. methyl or ethyl, or halogen such as chlorine or bromine, hydroxyl, alkoxy, preferably with up to 3 C atoms such as methoxy or ethoxy, hydroxyalkyl, alkylthio, aryl such as phenyl, or aralkyl such as benzyl, amino, substituted amino and the like
• the starting materials for the preparation of the dyes according to the invention are l-aminocyclohexenone-3 or 1-aminocyclopentenone-3 represented by the following formulae:
• 1-aminocyclohexenone-3 and l-aminocyclopentenone-3 can easily be prepared by the condensation of dihydroresorcinols or cyclopentadiones with amines.
• 1-pyrrolidino-cyclohexenone-3 ene compounds for example with N-ethylrhodanine.
• the multi-nuclear dyes are obtained by again quaternizing the resulting hemioxonoles and reacting the resulting compounds with ketomethylene compounds or with 2-methylquaternary salts of heterocyclic bases.
• Dye 1 1.6 g. of pyrrolidino-cyclohexenone-3 and 1 ml. of dimethylsulfate are heated in an oil bath to 100 C. the reaction temperature rising to 120 C. Without isolating the quaternary salt, the reaction mixture is heated on a steam bath for 5 minutes with 1.6 g. of N-ethylrhodanine in 15 ml. of ethanol with the addition of 2 ml. of triethylamine, the dye partly precipitating in the process. The mixture is cooled and the dye is isolated by suction filtration and recrystallized twice, each time from 40 ml. of ethanol with the addition of active charcoal. Yield 1.4 g., M.P. 179 C. to 180 C.
• Dye 28 3.2 g. of Dye 3 and 4.2 g. of ethyl p-toluenesulfonate are heated on an oil bath to 130 C. for 20 minutes. The mixture is cooled and heated on a steam bath for minutes with 3.4 g. Z-methyl-3-ethyl-benzothiazolium-p-toluene sulfonate in 20 ml. of ethanol with the addition of 2 ml. of triethylamine. The mixture is cooled, the dye is precipitated in the form of an oil with ether, the solution is decanted and the residue is triturated with potassium iodide solution. The dye is isolated by suction filtration and recrystallized from methanol. 3.8 g., M.P. 199 C. to 201 C.
• Dye 31 3.2 g. of Dye 3 are quaternized by the method described for Dye 28 and heated on a steam 'bath for 10 minutes with 1.6 g. of N-ethylrhodanine in 20 ml. of alcohol and 2 ml. of triethylamine. The dye crystallizes on cooling. After recrystallization from 100 ml. of chloroform, 3.7 g. of the dye which has a melting point of 279 to 281 C. are obtained.
• the sensitizing dyes according to the invention may be used in any silver halide emulsions.
• Suitable silver halides are silver chloride, silver bromide or mixtures of these salts, optionally with a small silver iodide content of up to 10 mols percent.
• the silver halides may be dispersed in the usual hydrophilic compounds, for example, carboxymethylcellulose, polyvinyl alcohol, polyvinyl pyrrolidone, alginic acid and its salts, esters or amides or preferably in gelatin.
• hydrophilic compounds for example, carboxymethylcellulose, polyvinyl alcohol, polyvinyl pyrrolidone, alginic acid and its salts, esters or amides or preferably in gelatin.
• the sensitizing dyes to be used according to the present invention are advantageously added to the photographic emulsion after chemical ripening and before casting.
• the methods used for this are generally known in the art.
• the sensitizing dyes are generally incorporated in the emulsion in the form of solutions.
• the solvents must, of course, be compatible with gelatin and must not have any adverse elfect on the photographic properties of the emulsion. Water, methanol, ethanol, acetone or mixtures of these substances are generally used as solvents.
• the quantity of sensitizing dye added may vary within wide limits, e.g. between 10 and 1000 mg./mol of silver halide, and the amount used is preferably between 30 and 300 mg./ mol of silver halide.
• the concentration of the dye may be adjusted to the individual requirements depending on the nature of the emulsion, and the sensitizing eifect required. The most suitable concentration for any given emulsion can easily be determined by the usual tests employed in photography.
• the emulsions may also be chemically sensitized, e.g. by the addition of compounds which contain sulfur at the stage of chemical ripening, for example compounds such as allylisothiocyanate, allylthiourea or sodium thiosulfate.
• Reducing agents e.g. the tin compound described in Belgian Patents 493,464 and 568,687 or polyamines such as diethylenetriamine or aminomethylsulfinic acid derivatives, e.g. as described in British patent specification 789,823, may also be used as chemical sensitizers.
• Noble metals and noble metal compounds e.g. gold, platinum, palladium, iridium, ruthenium or rhodium are also suitable for use as chemical sensitizers. This method 14 of chemical sensitization has been described in the article by R. Koslowsky, Z. Wiss. Phot. 46, 65-72 (1951).
• 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, or with condensation products of alkylene oxide and aliphatic alcohols, 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.
• the emulsions may also contain other spectral sensitizers in addition, e.g. the usual polymethine dyes such as merocyanines, 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 "Ihe Cyanine Dyes and Related Compounds," (1964).
• the emulsions according to the invention may contain the usual stabilizers e.g. homopolar or salt-like compounds of mercury which have aromatic or heterocyclic rings such as mercapto triazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
• stabilizers e.g. homopolar or salt-like compounds of mercury which have aromatic or heterocyclic rings such as mercapto triazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
• Azaindenes are also suitable stabilizers, especially tetraand penta-azaindenes and in particular those which are substituted with hydroxyl or amino groups. Compounds of this type have been described in the article by Birr. Z. Wiss. Phot. 47, 2-5 8 (1952).
• Other suitable stabilizers are e.g. heterocyclic mercapto compounds such as phenylmercaptotetrazole, quaternary benzothiazole derivatives, benzotriazole and the like.
• the emulsions may be hardened in the usual manner, for example with formaldehyde or halosubstituted aldehydes which contain a carboxyl group, e.g. mucobromic acid, diketones, methanesulfonic acid esters or dialdehydes.
• formaldehyde or halosubstituted aldehydes which contain a carboxyl group, e.g. mucobromic acid, diketones, methanesulfonic acid esters or dialdehydes.
• the emulsions according to the present invention may be used for various photographic recording materials, in printing materials, in film used for reproduction photography, in X-ray films, in materials which are suitable for the silver salt diffusion process, in color photographic materials or in photographic materials for the silver dye bleaching process.
• the sensitizers used according to the present invention are also suitable for the spectral sensitization of electrophotographic layers, especially layers which contain photoconductive zinc oxide distributed in an insulating binder.
• Example 30 mg. of each of the sensitizing dyes mentioned in the following table are added to a silver chlorobromide emulsion containing 29.5 g. of silver per kg.
• the emulsion is in each case cast on a baryta paper support in the usual manner and dried.
• the light sensitive layer thus formed is exposed behind a grey step wedge V2 steps) for 10 seconds and then developed for 2 minutes in a developer of the following composition:
• R is hydrogen or alkyl, alkoxy or alkylthio having up to Fresh 355, 3 3 C atoms or aryl;
• Dye sample cupboard R is (1) a saturated or unsaturated aliphatic hydrocarbon group having up to 6 C atoms, which may be sub- 83352223335313: 3 stituted with carboxyl or sulfo; (2) cycloalkyl or (3) g mp dy g g aryl; m 24 X and Z may be identical or ditferent and represent 0, S 5:13 3; NR or co-NR 5 7 27 28 p and q may be identical or different and represent 0 or 1; Dy 26 27 Anion is an anion and can be the anion of an acid group What is claimed is: 25 1.
• a photographic silver halide emulsion which con- Q 15 fi f reqgmed gomplgtmg i g g tains an eflFective amount of a sensitizing dye of the disputedg ere or r lowmg formula: References Cited R! 'Y Ri R I!

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• General Physics & Mathematics (AREA)
• Organic Chemistry (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Plural Heterocyclic Compounds (AREA)

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Cited By (3)

• 1970
  • 1970-04-10 DE DE19702017206 patent/DE2017206A1/de active Pending
• 1971
  • 1971-03-30 US US00129580A patent/US3796580A/en not_active Expired - Lifetime
  • 1971-04-07 BE BE765403A patent/BE765403A/nl unknown
  • 1971-04-09 FR FR7112795A patent/FR2089508A5/fr not_active Expired
  • 1971-04-19 GB GB2631771*A patent/GB1333136A/en not_active Expired

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