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
  • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
  • C09B23/06—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups three >CH- groups, e.g. carbocyanines
• • 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
• • 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

• A represents a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms
• B each represents an alkyl residue containing 1 to 4 carbon atoms, an alkylcarboxylic acid residue containing 1 to 5 carbon atoms, a sulphatoalkyl residue containing 1 to 4 carbon atoms or an alkylsulphonic acid residue
• alkyl represents a residue of formulaC,,H and n represents an integer having a value of l to 4, it also being possible for an acid group B, or B to be present as a betainelike structure
• R each represents an aromatic ring system containing at most two six-membered rings and fused-on in the manner indicated by the valency lines
• Y represents an anion
• Z represents an anion
• . represents a sulphur or selenium atom and m is l in the case of a betainelike molecular structure and is 2 in the case of a nonbetainelike molecular structure.
• Betainelike structures results if at least one of the residues B, and B represents a sulphatoalkyl residue or an alkylsulphonic acid residue or if B and B each represents an alkylcarboxylic acid residue.
• the anion Y is absent since the anion is already present in the molecule of the sensitizer itself, that is to say is bonded to the N-alkyl residue of the sensitizer by a homopolar bond.
• zwitter ions or internal salts may be mentioned.
• the sensitizers are of a nonbetainelike structure and the anion Y neutralizes the positive charge of the actual sensitizer molecule.
• the dyestuffs are basic cyanine dyestuffs. If only one of the residues B, and B represents an alkyl residue and the other represents an alkylsulphonic acid residue or sulphatoalkyl residue, the dyestuffs are neutral cyanine dyestuffs. Acid cyanine dyestuffs are .present if B, and B represent acid groups, that is to say carboxylic acid-alkyl, alkylsuphonic acid or sulphatoalkyl groups.
• a photographic material for the silver dyestuff bleaching process which contains a red-sensitizer of formula li zif fl [5555 1] owl-( drm 1 5 wherein A represents a hydrogen atom or an alkyl group conwherein A, B 8,, R,, R,,, Z, p and Y have the meanings given above, is preferred.
• the residue A in formulas (l) to (III) is in the so-called mesoposition of the trimethine chain of the molecule.
• A is either a hydrogen atom or a methyl, propyl, butyl or especially an ethyl residue.
• residues B, and B in formula (I) are residues of formulas (IV) alkylene-H, (V) -alkylene-COOH, (Vl) -alkylene-O-SO H or (Vll) alkyleneSO H, wherein alkylene represents an alkylene residue containing 1 to 4 carbon atoms.
• residues may be mentioned by way of examples: methyl, ethyl, propyl, isobutyl, acetic acid, propionic acid, valeric acid, sulphatomethyl, sulphatoethyl, propylsulphonic acid or butylsulphonic acid residues.
• residues R, and R in formulas (l) to (I11) and (VIII) represent ring systems which are fusedon in the manner indicated by the valency lines, which may be different from one another or identical.
• the residues R, and R must exhibit an aromatic character and may contain at most two six-membered rings.
• R, and R may here represent the completion of, for example, the following residues: benzene or naphthalene residues tetrahydronaphthalene residues or heterocyclic residues, for example, coumarone, thianaphthene or benzo-a-pyrane residues. All these residues can, of course, possessthe most diverse substituents, such as, for example halogen atoms, al-
• Alkyl, aryl or heterocyclic residues are, for example, also diphenyl,'furylbenzene or thienylbenzene residues.
• Red-Sensitizers of formula have proved very successful in the present use, in which formula R and R each represents a benzene or naphthalene residue which is fused-on in the manner indicated by the valency lines and is optionally substituted by halogen atoms or alkyl or alkoxy groups which each contain 1 to 3 carbon atoms, and A, B B Y, Z and p have the meanings given above.
• Sensitizers those of formula are again preferred, wherein X X X and X each represents a hydrogen or halogen atom or an alkyl or alkoxy group each containing 1 to 3 carbon atoms, and A, B B Y, Z and p have the meanings given above.
• the residues X, and X are respectively in the 6- or 7-position or in the 6- or 7'-position and the residues X and X, are respectively in the 5 and 5-position.
• red-sensitizers of formula wherein x,, X x x,,, A, B B, and Y, z and p have the meanings given above are of especial interest.
• red-Sensitizers for example, the cyanine dyestuffs of Table l below, wherein the symbols represent the following:
• Ill Sensitization maximum measured in an exposed and developed gelatine-silver halide emulsion.
• Page 15 Compound No. 55 additionally possesses an H C group in the 7-position.
• Page l5 Compound No. 56 possesses a fused-on benzene ring in the 6,7position.
• the cyanine dyestuffs which according to the invention are 45 to be used as red-sensitizers in photographic material for the silver color bleaching process are in part known or can be manufactured according to known methods which are for example, described in the book by F. M. Hamer The Cyanine (XVIII) Dyes and Related Compounds, chapters V and VI (Interscience Publishers New York 1964). Further manufacturing RI processes are, inter alia, also described in German Patent Nos. 917,330 and 929,080, French Pat. No. 1,166,246, Belgian Pat. No. 571,034 and US. Pat. No. 2,503,776.
• a suitable method for the manufacture of the sensitizers of formula (I) for example, comprises condensing a quaternary cyclammonium salt of formula or condensing a compound of formula (XVII) S with a compound of formula (XIX) S e wherein A, B B R,, R Y and n have the meanings given above.
• r Red-sensitizers of formula (1) which contain acid groups (XVb) e which do not participate in a betainelike structure may be present as free acids or as salts, especially as alkali salts such R1 I 043113 as, for example, sodium or potassium salts.
• red-sensitizers of formula (l) which are capable of forming the J-bands. They are distinguished by a very characteristic sensitization band with a steep drop towards the longer wavelengths and show a sensitization maximum which is bathochromically displaced by 70 to 120 nm. relative to the absorption maximum in alcoholic solution.
• This formation of a polymerization band, the socalled J-band, described as a second-order sensitization, is technically valuable not only as regards the position of the sensitization maximum but also as a result of the relative sensitivities thereby achieved.
• the red-sensitizers to be used according to the invention in photographic material for the silver dyestuff bleaching process have already been used as sensitizers in gelatine emulsions containing color coupling agents. These gelatine emulsions containing color coupling agents were used for the production of colored photographic images according to the chromogenic development principle. In such layers these sensitizers were distinguished by the fact that their sensitizing effect was unchanged, or at most slightly changed, by the presence of the color coupling agent. Nevertheless the fact that such sensitizers can also be successfully used in layers containing azo dyestuff for the silver dyestuff bleaching process was unforeseeable and surprising.
• azo dyestuffs are in general more substantive in dyeing than is the case for the colorless components used as coupling agents.
• polyazo dyestuffs which includes substantially all cyanazo dyestuffs which reduce the sensitizing effect of the hitherto usual sensitizers. lt was, therefore, to be expected that in the case of the layers of a silver dyestuff bleaching material containing azo dyestuffs an adequate sensitizing effect of the sensitizer on the silver halide would not be achieved or that such an effect would be entirely prevented.
• azo dyestuffs are desensitizers and reduce the sensitivity achievable by ordinary cyanine sensitizers.
• red-sensitizers used in accordance with the invention are also achieved in layers with azo dyestuffs which are fixed by precipitation with basic precipitants, such as, for example biguanides.
• basic precipitants such as, for example biguanides.
• the present sensitizers can be employed independently of the nature of the silver halide used. Alongside gelatine, other colloids can also be used as layer-forming agents.
• the present sensitizers can furthermore not only be used in multilayer material but can, for example, also be employed in mixed grain emulsions.
• the emulsions can furthermore contain casting additives of various kinds, for example wetting agents, hardeners or stabilizers.
• red-sensitizers of formula (I) are used in a layer containing a bluish-green bleachable azo dyestuff.
• EXAMPLE 1 Various ethanolic solutions of sensitize'rs are added, in each case to equal parts of a silver bromide-iodide emulsion containing 53 g. of silver and g. of gelatine per 1 kg. of emulsion, at 40 C., so that a sensitizer concentration of 220 mg./mol of silver results.
• Emulsion Sensitizer of Fon'nula A B C (3) D 5 E
• emulsions F and G are additionally manufactured, containing so-called symmetrical sensitizers which differ from the sensitizers according to the invention:
• Solutions A to G are cast on a transparent film substrate with a silver application of 3 g./m.
• the cast layers are exposed sensitometrically behind a grey wedge with a yellow filter, and thereafter the material is developed as follows:
• the unexposed cast films A to E are also spectrally exposed to light in a spectrosensitometer.
• the material is processed as previously indicated under items 1 and 2, that is to say only a black and white development is carried out.
• the sensitizers used according to the invention in emulsions A to E produce a higher sensitivity and result in a sensitization maximum which is displaced to longer wavelengths than the sensitizers in emulsions F and G employed for comparison.
• sensitization with a maximum of 600 nm. and above is generally required, preferably at 640 to 700 nm.
• the sensitizers used according to the invention is emulsions A to D produce a higher sensitivity and result in a sensitization maximum which is displaced to longer wavelengths than the sensitizers in emulsion E employed for comparison purposes.
• Emulsion sensitizers of Formula for comparison purposes, emulsion D is additionally manufactured, containing a so-called symmetrical sensitizer of formula (XX) which differs from the sensitizers according to the 4G
• XX symmetrical sensitizer of formula
• sensitizers used according to the invention in emulsions A to C produce a higher sensitivity and result in a sensitization maximum which is displaced to longer wavelengths than the sensitizers in emulsion D employed for comparison purposes.
• EXAMPLE 4 The procedure in Example 2 is adopted.
• the compound of formula (6) is used as a sensitizer according to the invention in emulsion A.
• emulsion B is manufactured, containing the so-called symmetrical sensitizer of formula (XX).
• the compound of formula is used as the bluish-green image dyestuff. The results are summarized in the table below.
• the sensitizer used according to the invention in emulsion A produces a higher sensitivity and results in a sensitization maximum which is displaced to longer wavelengths than the symmetrical sensitizer of emulsion B.
• EXAMPLE 5 Various ethanol solutions of sensitizers are added in each case to equal parts of a silver bromide-iodide emulsion containing 53 g. of silver and 70 g. of gelatine per 1 kg. of emulsion, at 40 C., so that a sensitizer concentration of I60 mg./mol of silver results:
• emulsions F and G are additionally manufactured, containing so-called symmetrical sensitizers which differ from the sensitizers according to the invention.
• Emulsion F Sensitizer of formula (XX)
• Emulsion G Sensitizer of formula (XXI)
• an aqueous solution of the bluish-green dyestuff of formula (XXII) is added to emulsions A to G in addition to the usual additives, for example stabilizer, wetting agent, plasticizer and hardener, in an amount which results in a dyestuff concentration of 13 g./kg. of emulsion.
• Solutions A to G are cast on a transparent film substrate, applying 3 g./m. of silver. These cast films are exposed and processed as indicated in Example I.
• sensitization with a maximum of 600 nm. and above is generally required, preferably at 640 to 700 nm.
• Emulsion Sensitizer of Formula A (66) B (68) C (70) D (71)
• emulsion E is also manufactured, containing a so-called symmetrical sensitizer of formula (XX), which differs from the sensitizers according to the invention.
• an aqueous solution of the bluish-green dyestuff of formula (XXII) is added to emulsions A to E in addition to the usual additives, for example stabilizers, wetting agents, plasticizers and hardeners, in an amount which results in a dyestuff concentration of 4 g./kg. of emulsion.
• Solutions A to E are cast on an opaque-white substrate, applying l.8 g./m. of silver. The exposure and processing of these cast films takes place as indicated in Example 5.
• the exposure and processing of these cast films takes place as indicated in Example 5.
• the sensitizers used according to the invention in emulsions A to D produce a higher sensitivity and result in a sensitization maximum which is displaced to longer wavelengths than the sensitizer in emulsion E employed for comparison.
• EXAMPLE 7 The procedure described in Example 6 is adopted.
• the compound of formula (68) is used as the sensitizer according to the invention.
• emulsion B is manufactured, containing the so-called symmetrical sensitizer of formula (XX).
• the compound of formula (XXIII) is used as the bluish-green image dyestuff. The results are summarized in the table below.
• EXAMPLE 8 The procedure described in Example 6 is adopted. The fol lowing are used as sensitizers according to the invention.
• for comparison, emulsions F and G are additionally manufactured, containing so-called symmetrical sensitizers which differ from the sensitizers according to the invention.
• Emulsion F Sensitizer of formula (XX)
• Emulsion G Sensitizer of formula (XXI)
• the compound of formula (XXIV) is used as the bluishgreen image dyestuff.
• emulsions K and L are additionally'manufactured, containing so-called symmetrical sensitizers which differ from the sensitizers according to the invention.
• Emulsion K Sensitizer of formula (XXV)
• the sensitizers used according to the invention in emulsions A to J produce a higher sensitivity, and in part result in a sensitization maximum which is displaced to longer wavelengths than the sensitizers of emulsions K and L employed for comparison.
• EXAMPLE 10 The procedure described in Example 1 is adopted. The following are used as sensitizers.
• the dyestuff of 1 formula (XXIII) is used as the image dyestuff, and in particular so as to result in a dyestuff concentration of 24 g./kg. of emulsion.
• sensitizers employed according to the invention in emulsions A to K produce a higher sensitivity and in part result in a sensitization maximum which is displaced to longer wavelengths than the sensitizer of emulsion L employed for comparison.
• EXAMPLE 1 1 The procedure described in Example 2 is adopted. The following are used as sensitizers according to the invention.
• Emulsion Sensitizer of Formula A (16) B (39) C (40) D (45) E (5 I) F (53) G (55) H (56) l .I (83) K (85) L (XXV) for comparison The results are summarized in the table below.
• the sensitizers employed according to the invention in emulsion A to K produce a higher sensitivity and in part result in a sensitization maximum which is displaced to longer wavelengths than the sensitizer of emulsion L employed for comparison.
• EXAMPLE 12 The procedure described in Example 2 is adopted. The following are used as sensitizers.
• the sensitizers used according to the invention in emulsions A to I produce a higher sensitivity and in part result in a sensitization maximum which is displaced to longer wavelengths than the sensitizers of the emulsions K and L employed for comparison.
• Photographic material for the silver dyestuff bleaching process which in at least one red-sensitive silver halide emulsion layer contains a bleachable azo dyestuff as the image dyestuff, wherein this layer contains a red-sensitizer characterized by an absorption maximum above about 554 nm. and a sensitization maximum above about 625 nm.
• A is a hydrogen atom or an alkyl group containing 1 to 4 carbon atoms
• B, and B each is a member selected from the group consisting of an alkyl radical containing 1 to 4 carbon atoms, an alkylcarboxylic acid radical containing 1 to 5 carbon atoms, a sulfatoalkyl radical containing 1 to 4 carbon atoms and an alkylsulfonic acid radical, wherein alkyl is a radical of the formula -C, H and n is an integer of at most 4, provided that each of B and B is not simultaneously an acid group, R and R, each is an aromatic ring system containing at most two six-membered rings which is fused-on in the manner indicated by the valency lines; Y is an anion and Z is a sulfur or selenium atom.
• Photographic material as claimed in claim 1 in which A is ethyl.
• B is an ethyl, methylcarboxylic or ethylcarboxylic acid radical and B is ethyl.
• Photographic material as claimed in claim 1 which con- 8. Photographic material as claimed in claim 1, which contains a red-sensitizer of formal; W
• Photographic material as claimed in claim 1 which conatoms' tains a red-sensitizer of formula 5.
• Photographicmaterial as claimed in claim 4, which con- 1 5 tains a red-sensitizer of formula Q/ X N I CIIgCHgCHzSOa 02m 6.
• Photographic material as claimed in claim 5. in which 10.
• Photographic material as claimed in claim 1 which con- 7.

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Citations (7)

• 1968
  • 1968-08-26 CH CH1277268A patent/CH517322A/de not_active IP Right Cessation
• 1969
  • 1969-07-30 DE DE1938768A patent/DE1938768C3/de not_active Expired
  • 1969-08-19 CA CA059,882A patent/CA942568A/en not_active Expired
  • 1969-08-21 US US852083A patent/US3647466A/en not_active Expired - Lifetime
  • 1969-08-25 FR FR6929048A patent/FR2017033A1/fr active Pending
  • 1969-08-25 BE BE737912D patent/BE737912A/xx not_active IP Right Cessation
  • 1969-08-25 NL NLAANVRAGE6912939,A patent/NL169233C/nl not_active IP Right Cessation
  • 1969-08-26 GB GB42477/69A patent/GB1237614A/en not_active Expired

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