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
  • G03C5/00—Photographic processes or agents therefor; Regeneration of such processing agents
  • G03C5/26—Processes using silver-salt-containing photosensitive materials or agents therefor
  • G03C5/29—Development processes or agents therefor
  • G03C5/305—Additives other than developers
• • 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
  • G03C1/34—Fog-inhibitors; Stabilisers; Agents inhibiting latent image regression
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/156—Precursor compound
  • Y10S430/158—Development inhibitor releaser, DIR

Definitions

• ABSTRACT A method is described of developing an exposed photographic silver halide material in an alkaline medium in the presence of a 2,3- or 2,5dihydroxyphenylbenzotriazole. Upon development, development inhibiting benzotriazole compounds are released at the site of exposure. The method is particularly suitable for the development of photographic colour elements to reduce the contrast and for the development of emulsions of the Lippmann-type to reduce distortions of closely adjacent image details, to promote imagesharpness and to reduce yellow staining upon reversal processing.
• the dihydroxyphenyl nucleus may be further substituted and carry any of the known substituents used in hydroquinone and pyrocatechol type developers, e.g.
• the benzo triazole group may also carry further substituents e.g. halogen, alkyl, nitro, amino, sulpho, acylamino, etc. and may carry a fused-on benzene nucleus. Further, the dihydroxyphenyl group may be linked either to the 1- position or the 2-position of the benzotriazole.
• the 2,3 or 2,5+dihydroxyphenylbenzotriazoles may also be used in a chemically masked form, particularly when added to the photographic material, as is known to be done for dihydroxybenzene developing agents (cfr. US. Pat. No. 3,246,988 of Ralph F. Porter and Thomas E. Gompf issued Apr. 19, 1966 and Belgian Pat. No. 734,140 filed June 6, 1969 by Gevaert- Agfa N.V.)e.g. in the form of derivatives of these dihydroxyphenylbenzotriazoles in which at least one of thehydroxyl groups has been esterified to form a hydrolyzable acyloxy, halocyloxy or acyloxy group with quaternary ammonium substituent.
• dihydroxybenzene developing agents cfr. US. Pat. No. 3,246,988 of Ralph F. Porter and Thomas E. Gompf issued Apr. 19, 1966 and Belgian Pat. No. 734,140 filed June 6, 1969 by Gevaert- Agfa N.
• the present invention provides a method of producing a photographic image, which comprises developing an exposed photographic material comprising a support and a silver halide emulsion layer in an alkaline medium in the presence of a 2,3 or 2,5-dihydroxyphenyl-benzotriazole compound.
• the concentration of the compounds of the invention in the emulsion is dependent on the characteristics of the emulsion and is therefore best determined by trial. 1n most cases, the optimum concentration in the emulsion is between about 50 mg and 5 g, preferably between about 200 mg and 2 g per mole of silver halide.
• Photographic silver halide emulsions useful in the present invention comprise any of the ordinarily employed silver halide emulsions e.g. silver chloride, silver chlorobromide, silver chlorobromoiodide, silver bro mide, and silver bromoiodide emulsions.
• Any of the conventionally employed'water-permeable hydrophilic colloids can be employed in the silver halide emulsions and the other water-permeable layers contiguous thereto.
• Typical water-permeable colloids include gelatin, albumin, polyvinyl alcohols, agar agar, sodium alginate, hydrolysed cellulose esters, hydrophilic polyvinyl copolymers, etc.
• the emulsions may be coated on a wide variety of photographic emulsion supports.
• Typical supports include cellulose ester film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film and related films of resinous materials as well as paper and glass.
• the light-sensitive emulsions to which the development inhibitor releasing compounds of the invention are added may be sensitized chemically as well as spectrally.
• the emulsions may be sensitized chemically by any of the accepted procedures. They may be digested with naturally active gelatin or in the presence of small amounts of sulphur-containing compounds such as allyl thiocyanate, allyl thiourea, sodium thiosulphate, etc.
• the emulsions may also be sensitized by means of reductors, e.g. tin compounds as described in British Pat. No. 789,823 filed Apr. 29, 1955 by Gevaert Photo- Producten N.V., polyamines e.g. diethyltriamine, and small amounts of noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium as described by R. Koslowsky, Z.Wiss.Phot. 46, 67-72 1951
• the emulsions may also be sensitized chemically by the combined use of these chemical sensitizers.
• Emulsions stabilizers or antifoggants may be added to the silver halide emulsion e.g. aliphatic, aromatic and heterocyclic mercapto compounds preferably comprising sulpho groups or carboxyl groups, mercury compounds as those described in Belgian Pat. No. 524,121 filed Nov. 7, 1953 by Kodak Ltd., Belgian Pat No. 677,337 filed Mar. 4, 1966 by Gevaert-Agfa N.V., Belgian Pat. No. 707,386 filed Dec. 1, 1967 by Gevaert- Agfa N.V. and Belgian Pat. No. 709,195 filed Jan. 11, 1968 by Gevaert-Agfa N.V., in British Pat. No.
• the emulsions may further comprise the known speed-increasing alkylene oxide compounds and onium compounds.
• the alkylene oxide compounds include alkylene oxide condensation products or polymers as described in US Pat. No. 1,970,578 of Conrad Schoeller and Max Wittner issued Aug. 21, 1934, US. Pat.
• the onium compounds may be of the ammonium, phosphonium and sulphonium type, e.g. trialkyl sul phonium salts, tetra-alkylammonium salts, alkyl pyridinium and alkyl quinolinium salts, bisalkylene pyridinium salts, quaternary ammonium and phosph'onium polyoxyalkylene salts, etc.
• the compounds of the invention may be used in various kinds of photographic emulsions. In addition to being useful in Xray and other non-optically sensitized emulsions, they may also be used in orthochromatic, panchromatic and infrared-sensitive emulsions. They may be used in emulsions intended for colour photography, e.g. emulsions containing colour forming couplers or emulsions to be developed by solutions containing couplers.
• They may be used in emulsions intended for use in the well-known diffusion transfer process, which utilize the undeveloped silver halide in the non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver halide emulsion layer.
• the compounds of the invention are particularly useful in emulsions intended for colour photography where during development, at the exposed areas, the oxidized aromatic primary amino colour developing agent couples with a colour forming component to form a dye image.
• the development inhibitor is image-wise released, which results in reduced graininess and the hydroquinone developer locally regenerates the aromatic primary amino colour develop ing agent from its oxidation products.
• the compounds of the invention were further found to be particularly suitable for use in silver halide emul sions of the Lippmann-type having an average silver halide grain-size of less than 100 nm as used c. g. for the preparation of masks in the production of microelec tronic integrated circuits.
• These Lippmann emulsions should have a high resolving power and acutance and allow a correct reproduction of the dimensions of the image.
• By means of the compounds of the invention it was found possible, both on reversal and negative processing, to reduce or eliminate the distortions of image details which often arise by mutual influence of closely adjacent image details and to promote the: imagesharpness. Moreover, these compounds were found to reduce the yellow staining often encountered with reversal processing of the Lippmann-matcrial.
• the concentration of the compounds of the invention is best determined by trial. Generally, the most suitable concentration is between 20 mg and 2 g, preferably between 100 mg and 1 g per mole of silver halide.
• drawings are made on highly enlarged scale of the various successive masks necessary to produce one integrated circuit whereupon the drawings are reduced if necessary in successive steps, and reproduced on a photographic plate or film material forming thereby the mask ready for use.
• various photographic and chemical steps photo-etching of lacquered plates
• the images of the masks thus produced are transferred to the surface on which the integrated circuit is to be made, in order to produce the required circuit elements.
• the exposed photographic elements can be subjected to negative processing or to reversal processing.
• the photographic Lippmann-materials used in electronic mask making comprise a silver halide emulsion layer, the thickness of which is generally comprised between 3 and 8 microns, and the average grain size of which is generally less than nm.
• the ratio of silver halide to colloid binder in the Lippmarm-emulsion is preferably at least 1:2 and. at most 4:1.
• TheILippmann-emulsions may be prepared according to methods well known in the art and described in the literature, see -e.g. P. Glatkids Photographic Chemistry," vol. l, 1958, pages 365-368 Meesl- James The Theory of the Photographic Process, 1966, p. 36 and National Physical Laboratory, Notes on Applied Science No. 20 Small scale preparation of Fine-Grain (Colloidal) photographic emulsions B. H. Crawford, London, 1960. They may also be prepared according to the. technique described in French Pat. No, 2,092,505 filed Mar. 25, 1971 by Agfa- Gevaert NV.
• the Lippmann-emulsions may comprise any of the silver halides referred to above but it is favoured to use silver bromide emulsions, which may have an iodide content of at most 8 mole percent.
• the Lippmann-emulsions may further comprise any of the emulsion addenda referred to hereinbefore, e.g. chemical and spectral sensitizers, speed-increasing addenda of the oxyalkyleneand onium type, stabilizers, and antifoggants.
• emulsion addenda e.g. chemical and spectral sensitizers, speed-increasing addenda of the oxyalkyleneand onium type, stabilizers, and antifoggants.
• the Lippmann-emulsions for microelectronic mask making are most advantageously sensitized for the green region of the spectrum.
• the exposure light is preferably chosen so that it has a wavelength, to which the emulsion has been spectrally sensitized.
• the emulsions may further comprise light-absorbing dyes, which are chosen so that they absorb light of the wavelength, to which the material is exposedso that scattering and reflection of light within the photographic material is reduced.
• light-absorbing dyes which are chosen so that they absorb light of the wavelength, to which the material is exposedso that scattering and reflection of light within the photographic material is reduced.
• these dyes there can be referred to Belgian Pat. No. 699,375 filed June 1, 1967 by Eastman Kodak Co. and Belgian Pat. No. 742,954 filed Dec. 11, 1969 by Gevaert-Agfa NV.
• the dyes are preferably used in such amounts that per micron of emulsion layer thickness a density comprised between 0.05 and 0.20, measured in the'spectral region of the exposure light, is obtained.
• Lippmann-emulsions comprising the compounds of invention e.g.'chromium, aluminium and zirconium salts, formaldehyde, dialdehydes, hy-
• the l es cetyl and/or acyl groups such as l,3,5-triacryloylhgi en for the speed, gradation and maximum density exahydro l ,3,5 triazi e, 1,3 di l l 5 are relative values; a value of 100 is given to the sample etylhexahydro-l ,3,5triazine, l,3,5tri chloroacdeveloped in developer Table Deve- Speed Grad- D,,,,,,, Fog side absorption loper ation blue green red blue green etylhexahydrol ,3,5 -triazi ne, etc.
• Example I The sensitometric effects of 2.-(2,5 -dihydroxyphenyl) benzotriazole when used in the colour develop;
• a photographic material comprising a film support and a silver bromoiodide emulsion (2.3 mole percent iodide), which comprises as cyan forming colour coupler the compound of the structure:
• a silver bromide emulsion comprising per kg 72 g of silver bromide and 93 g of gelatin was prepared by simultaneous addition of a silver nitrate solution and a potassium bromidesolution to a 3 percent aqueous solution of gelatin. Theconditions of precipitation were adjusted so that a Lippmann-ernulsion with an average grain-size of nm was obtained. Details as to the preparation of Lippmann emulsions can be found amongst, others in P. Glafkides Photographic chemistry," Vol. I, 1958, Fountain Press, London.
• the emulsion was sensitized by addition of 150 mg per g of silver halide of a merocyanine dye by means of which a strong spectral sensitization in the regionof 520-550 nm was obtained. Then. an amount of the light-absorbing dye having the following structural formula:
• the emulsion was divided into 2 portions and to one of these portions 2--(2,5 -dihydroxyphenyl)benzotriazole was added in an amount of 500 mg per mole of silver halide.
• the emulsion portions were coated on glass plates pro rata of 230 ml per sq.m so as to obtain after drying a layer thickness of 6 microns.
• the 2 plate materials A and B were then exposed under identical circumstances by means of monochromatic light, the spectral composition of which corresponds with the absorption region of the light-absorbing dye used, through a test pattern, as normally used for the quantitative evaluation of materials for use in microelectronics maskmaking, consisting of lines which are separated by spaces of the same width as the lines themselves and with a width varying from 1 to 20 microns.
• the exposure was of such an intensity so as to limit the density in the transparent areas of the images produced, which correspond with the white lines of the test pattern, to the fog value.
• a method of producing a photographic image which comprises developing an image-wise exposed photographic material having a support bearing a silver halide emulsion layer, in an alkaline medium in the presence of a 2,3- or '2,5dihydroxyphenylbenzotriazole.
• emulsion layer is a Lippmann emulsion the average grain-size of which is less than nm.
• Lippmann emulsion is a silver bromide emulsion, which may have a silver iodide content of at most 8 mole percent.
• a photographic material comprising a support bearing a silver halide emulsion layer, there being incorporated in a water-permeable layer on the emulsion side of the support a 2,3- or 2,5-dihydroxyphenylbenzotriazole.
• a photographic material according to claim 13, wherein the Lippmann emulsion is a silver bromide emulsion, which may have a silver iodide content of at most 8 mole percent.
• a photographic material according to claim 15, wherein the ratio of silver halide to hydrophilic colloid birztder in the Lippmann emulsion is comprised between I: and 4:1.

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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)
• Nitrogen Condensed Heterocyclic Rings (AREA)

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Citations (6)

• 0
  • BE BE790629D patent/BE790629A/nl unknown
• 1971
  • 1971-11-10 GB GB5228871A patent/GB1409657A/en not_active Expired
• 1972
  • 1972-11-03 US US00303406A patent/US3841877A/en not_active Expired - Lifetime
  • 1972-11-10 DE DE2255032A patent/DE2255032A1/de active Pending

Patent Citations (6)

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