Classifications

• • 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
• • 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
  • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
  • G03C1/18—Methine and polymethine dyes with an odd number of CH groups with three CH groups

Definitions

• alkyl is a residue of the formula --C,,H,,,- n being a whole number from I to 4, and in which an acid group B, or B, may have a betainelike structure
• R, and R arc dissimilar aromatic ring systems which contain at most two sixmembered rings and are fused on in the manner indicated by the valency lines
• Betainelike structures result when at least one of the residues B, or B represents a sulfatoalkyl or an alkulsulfonic acid residue, or when B, and B each represents an alkylcarboxylic acid residue.
• the betainelike structure there is no anion Y because the anion is already present in the molecule of the sensitizer itself, that is to say is linked by a homopolar bond with the N-aikyl group of the sensitizer. This is also referred to as a zwitterion or an inner salt.
• the sensitizer does not have a betainelike structure, and the anion Y neutralizes the positive charge of the actual sensitizer molecule.
• A represents a hydrogen atom or an alkyl group containing one to four carbon atoms
• R represents an alkyl group containing one to four carbon atoms or an alkylcarboxylic acid residue containing one to five carbon atoms
• 8. represents a sulfatoalkyl residue containing one to four carbon atoms or an alkylsulfonic acid residue in which alkyl is a residue of the formula -C,,H,,,- and n is a whole number from 1 to 4, preferably from 1 to 3
• B represents an alkyl group containing one to four carbon atoms
• R, and R represent dissimilar aromatic ring systems which contain at most two six-membered rings and are fusedon in the manner indicated by the valency lines
• Y represents an anion and HF! or 2.
• a preferred photographic material contains a sensitizer not having a betainelike structure, corresponding to the formula in whichA, B B R,, R, and Y have the meanings defined above.
• the residue A in the formulas (l) to (III) is in the so-called meso-position of the trimethine chain of the molecule; it is either a hydrogen atom or a methyl, propyl, butyl or especially an ethyl group.
• residues B, and B are residues of the formulas (IV) --alkylene-H, (V) alkyleneCOOl-ll, (VI) alkyleneOSG l-l or (VII) alkylene-SO H,
• alkylene stands for an alkylene group containing one to four carbonatoms.
• residues may be mentioned; methyl, ethyl, propyl, isobutyl groups, acetic acid residues, propionic acid residues, valeric acid residues, sulfatomethyl, sulfatoethyl, propylsult'onic acid or butylsulfonic acid residues.
• residues R, and R- in the formulas (I) to (Ill) represent ring systems fused on as indicated by the valency lines, which must always be different from each other, have an aromatic character and contain at most two six-membered rings.
• R, and R may be different from each other insofar as the type of the ring systems, the kind and number of the substituents in the same ring system or the positions of identical substituents in the same ring system are concerned.
• R, and R may represent the complements, for example, to the following residues: benzene or naphthalene residues, tetrahydronaphthalene residues or heterocyclic residues, for example coumarone, thionaphthene or benzoar-pyrane residues. All these residues may, of course, carry a wide variety of substituents, for example halogen atoms, alkyl, aryl or heterocyclic residues, and these .alkyl or aryl residues or heterocyclic residues may be bound to the ring system directly or through ahetero atom, for example and oxygen or a sulfur atom. Therefore, R, and R may also be, for example diphenyl, furylbenzene or thienylbenzene residues.
• X X X and X each represents a hydrogen or halogen atom, or an alkyl or alkoxy group each containing one to three carbon atoms, and the substituent pair X,/X must differ from the substituent pair X /X as to kind or position, and A, B B and Y have the above meanings.
• the residues X and X are preferably in the 6- or 7-position or 6- or 7'-position, and the residues X and X, are in the 5- are especially valuable; in this formula A, B B X X X X and Y Q have the above meanings and the substituent pair X IX is different from the substituent pair X /X
• the residue Y in the formulas (l) to (Ill) and (Vlll) to (Xll) represents one of the anions conventionally used in the chemistry of the cyanine dyestuffs, which as is known have a minor importance for the sensitizing effect (cf. F. M. Hamer, The Cyanine Dyes and Related Compounds, chapter 10, page 296).
• sensitizers containing preferred anions correspond to the formula (Xlll) ⁇ /s ⁇ /s R.
• Suitable representatives of the red sensitizers according to formula (I) are, for example, the compounds shown in the following table in which there are listed in Column I the formula number Column ll the absorption maximum in mm, measured in ethanol Column lll the sensitizing maximum, measured in an exposed and developed silver halide gelatine emulsion Remarks:
• the compound No. 13* in the table contains a benzene ring fused on in the 4',5-position instead of the residue X,,.
• the compounds Nos. 32 to 35 have additionally an l-l C residue in the 7-position.
• the compound No. 5 8" has additionally an H C residue in the 7 '-position.
• the compound No. contains a benzene ring fused on in the 6,7'-position.
• the cyanine dyes to be used according to this invention as red sensitizers in photographic material for the silver dye bleaching process are in part known or can be manufactured by known methods, for example as described in the book of F. M. Hamer The Cyanine Dyes and Related Compounds, chapters V and VII [lnterscience Publishers, New York, 1964]. Further manufacturing processes have been described, inter alia, in German Pat. No. 917,330 and 929,080, French, Pat. No. 1,166,246, Belgian Pat. No. 571,034 and in US. Pat. No. 2,503,776.
• a quaternary cycloammonium salt of the formula (XVa) S is condensed with a compound of the formula (XVII) photosensitive silver halide layer already contains a dye which absorbs exposinglight and thereby reduces the effective sensitivity of the layer.
• the sensitizing of such dyed layers is rendered especially difficult by the fact that the dyes incorporated with the layer not only reduce the sensitivity by ab sorption but also have a strong desensitizing effect on the emulsion.
• sensitizers of the formula (I) are those which are capable of forming the .l-band; they are distinguished by a very characteristic sensitivity bond with a steep drop towards the longer wavelengths and have, compared with the absorption maximum in an alcoholic solution, a sensitizing maximum displaced bathochromically by 70 to nm.
• This formation of a polymerization band, the so-called J-band, referred to as a sensitization of the second order is technically valuable not only insofar as the location of the sensitizing maximum is concerned but also because of the relative sensitivities attained in this manner.
• the red sensitizers to be used according to this invention in photographic material for the silver dye bleaching process have already been used as sensitizers in gelatine emulsions containing color couplers. These gelatine emulsions containing color couplers are used in the manufacture of color photographs based on the principle of chromogenic development. In such layers these sensitizers are distinguished by the fact that their sensitizing effect is not, or at most only very slightly, affected by the presence of the color coupler. Nevertheless, the fact that such sensitizers can also be used in layers containing azo dye for the silver dye bleaching process successfully was unexpected and surprising.
• azo dyes are generally more substantive in dyeing than the colorless components used as couplers; this is especially true of polyazo dyes (to which practically all cyanazo dyes belong) which diminish the sensitizing capacity of the previously used sen- 'sitizers. Therefore, it should have been expected that in the layers containing an azo dye for use in the silver dye bleaching :process an adequate sensitizing efi'ect of the sensitizer upon the silver halide would not be achieved or would even be totally inhibited. That is to say, it was to be expected that the azo dye could displace the sensitizers adsorbed on the silver halide or that the dye would form an inactive compound with athe sensitizer. Therefore, the extremely high increase in sen- ;sitivity achieved with the use of the sensitizers according to :this invention in the presence of azo dyes, especially polyazo dyes, was entirely unexpected,
• the high sensitivity obtainable by the sensitizers to be used according to this invention is also found in layers containing; azo dyes that are fixed by precipitation with basic precipitants, for example biguanides; this is surprising because it is known that these basic precipitants (biguanides) act as descnsitizers so that it should have been expected that their presence in the emulsion would have an unfavorable effect on the sensitivity.
• basic precipitants for example biguanides
• the present sensitizers can be used independently of the kind of silver halide concerned. Apart from gelatine, other colloids can be used as layer formers. Furthermore, the present sensitizers can be used not only in multilayer materialsbut also, for example, in mixed grain emulsions.
• the emulsions may further contain casting assistants of all kinds, for example wetting agents, hardeners and/or stabilizers.
• red sensitizers of formula (I) with a layer containing ableachable cyanazo dye.
• EXAMPLE 1 Equal parts of a silver bromide-iodide emulsion containing 5 3 g. of silver and 70 g. of gelatine per 1 kg. of emulsion are mixed at 40 C. with different ethanolic solutions of sensitizers so that a sensitizer concentration of 170 mg. per mol of silver results.
• emulsion F is prepared which contains a so-called symmetrical sensitizer which differs from the sensitizers of this invention.
• Emulsion F Sensitizer of the formula
• the solutions A to F are cast on a transparent film base so that the coating contains 3 g. of silver per 111.
• the castings are subjected to sensitometric exposure behind a grey wedge and a yellow filter and then developed as follows:
• the sensitizers used according to this invention in emulsions A to E produce a higher sensitivity and displace the sensitivity maximum towards longer wavelengths than does the symmetrical control sensitizer incorporated in emulsion F.
• a sensitization with a maximum of 600 nm. or higher is generally required, and preferably it is within the range from 640 to 700 nm.
• EXAMPLE 2 Equal parts of a silver bromide-iodide emulsion of medium sensitivity, containing 21 g. of silver and g. of gelatine per 1 kg. of emulsion, are mixed at 40 C. with different ethanolic solutions of sensitizers so that a sensitizing concentration of I50 mg. per mol of silver results.
• Emulsion sensitizer of the fonnula A according to the invention (2) 8 according to the invention (6) C according to the invention D for comparison (XVI)
• conventional additives e.g. stabilizers, wetting agents, softening agents and hardeners, as well as an aqueous solution of the cyan dye of the formula (XVIII) in an amount such that a dye concentration i usllsstef s s esu ts;
• the solutions A to D are cast over a white opaque base to is used in a concentration of 3.6 g. per I kg. of emulsion. produce a coating containing 1.9 g. of silver per m..
• the sensitizers of the formulas (6), (l) and (l I) produce The coated material is subjected to spectral exposure under similarly improved relative sensitivities and sensitization mux a spectrosensitometer and developed as described under l and ima shifted towards longer waves as shown in example 3. 2 in example 1.
• the sensitization maxima thus achieved are as 5 follows: EXAMPLE 5 Sensitization maximum The procedure is as described in example 2, except that the Emulsion in nm.
• sensitizers are used in a concentration of 150 mg. of A according to the invention 640 Sensltwer per mol of sllver: B according to the invention 630 C lccoldinfl invention Emulsion Sensitizer of fonnula D for comparison 7 600 g B (2)
• the sensitization maxima that can be obtained with the senc (7) sitizers according to this invention are found at higher 3 238 wavelengths than can be obtained with the sensitizer 'used for comparison.
• the emulsion is cast as described in example 2, and then The amounts of sensitizer have been chosen so that a maxspectrally exposed and developed as described in example 1. m s itivit is chieved, The following sensitization maxima are found:
• the sensitizers to be A 1.90 630 3.47 used according to this invention display a distinct shift of the B 139 640 sensitization maximum.
• c 1.11 650 2.74 D for comparison '2. 15 600 3.76 EXAMPLE 6 The procedure is as described in example 1, except that a concentration of 200 mg. of sensitizer per mol of silver is used A comparison of th m I H A C Wlth D reveals a and a coating containing 1.6 g. of silver per m.
• Emulsion sensitizer of formula EXAMPLE 4 A As The procedure is as described in example 3, except that in- B 60 stead of the cyan dye of the formula (XVIII) the dye of the C formul w H D Xx (XIX) 01
• emulsion D is prepared which contains a so-called symmetrical sensitizer that is different from the sen-' 004m OH sitizers to be used according to this invention.
• Color development 1 Spectrum sensitivity relative sensitivity lEmulsion maximum in nm. log E D 645 Mil A comparison of emulsions A to C with D reveals a distinct gain in sensitivity 1 and a shift of the sensitization maximum towards longer waves in the case of the sensitizers to be used according to the invention as against the sensitizer compared.
• EXAMPLE 7 The procedure is as described in example I, except that a concentration of 200 mg. of sensitizer per mol of silver is used and a coating containing 1.6 g. of silver per m. is produced with the following sensitizers:
• Emulsion Sensitizer of formula G 65 H XXI for comparison The image dye used is the dye of the formula (XVlll) in an amount such that a dye concentration of 19.5 g. per 1 kg. of emulsion results.
• EXAMPLE 8 The procedure is as described in example 2, except that a concentration of 200 mg. of sensitizer per mol of silver is used and a coating is produced, which contains 1.5 g. of silver per m with the following sensitizers:
• Emulsion sensitizer of formula XX for comparison The image dye used is the dye of the formula (XVll) in an A comparison of emulsions A to G with H reveals a distinct gain in sensitivity and, in some cases, a shift of the sensitization'maximum towards longer waves in the case of the sensitizers to be used according to this invention as against the sensitizer compared.
• EXAMPLE 9 The procedure is as described in example 2, except that a concentration of 200 mg. of sensitizer per mol of silver is used and a coating containing 1.5 g. of silver per m is produced with the following sensitizers:
• Emulsion Sensitizer of formula A B B 20 C 35 D 43 F 62 G 65 H XXI for comparison The results are listed in the following table:
• EXAMPLE 10 The procedure is as described in example 2, except that a concentration of 200 mg. of sensitizer per mol of silver is used and a coating containing 1.5 g. of silver per m? is produced with the following sensitizers:
• emulsion D contains a so- ;called symmetrical sensitizer that is different from the senamount such that a dye concentration of 2.6 g. per 1 kg. of sitizers to be used according to this invention and corresponds lemulsion results.
• a photographic material as claimed in claim 5, which contains a red sensitizer of the formula A comparison of emulsions A to C with D reveals a distinct gain in sensitivity and a shift of the sensitization maximum towards longer waves in the case of the sensitizers to be used according to the invention as against the sensitizer compared.
• a photographic material as claimed in claim 1, which contams the red Sensmzer ofthe formula contains a red sensitizer of the formula 5 Q Re i c-olhi-cn o R4 Y CA1- ⁇ N f s v l B5 a a a a m

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

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Citations (4)

• 1968
  • 1968-08-26 CH CH1277168A patent/CH506098A/de not_active IP Right Cessation
• 1969
  • 1969-07-30 DE DE1938823A patent/DE1938823C3/de not_active Expired
  • 1969-08-19 CA CA059,881A patent/CA942567A/en not_active Expired
  • 1969-08-21 US US852075A patent/US3635716A/en not_active Expired - Lifetime
  • 1969-08-25 BE BE737911D patent/BE737911A/xx not_active IP Right Cessation
  • 1969-08-25 FR FR6929047A patent/FR2016387A1/fr active Pending
  • 1969-08-25 NL NL6912938.A patent/NL164397C/xx not_active IP Right Cessation
  • 1969-08-26 GB GB1257268D patent/GB1257268A/en not_active Expired

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