Classifications

• • 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, 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
• • 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
  • C09B55/00—Azomethine dyes
  • C09B55/002—Monoazomethine dyes
  • C09B55/003—Monoazomethine dyes with the -C=N- group attached to an heteroring
• • 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
  • G03C1/36—Desensitisers
• • 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
  • Y10S430/167—X-ray

Definitions

• R represents an alkyl group, an unsaturated aliphatic group, or an aryl group
• Z represents a heterocyclic nucleus of the thiazole series, benzothiazole series, naphthothiazole series, thiadiazole series, oxazole series, benzoxazole series, naphthoxazole series, selenazole series, benzoselenazole series, naphthoselenazole series, 2-quinoline series, pyrimidine series, quinoxaline series, quinazoline series, l-phthalazine series, thionaphtheno [7,6-d]thiazole series, 2-pyridine series, and benzimidazole series,
• L represents a methine radical
• Ar represents a bivalent aromatic radical
• n 1 or 2
• X represents an anion, but isnot present when R, itself contains an anionic group
• each of R, and R represents alkyl, aryl, or R, and R together represent the atoms necessary to close a heterocyclic nucleus is described.
• This invention relates to photographic elements for use in the recording of high-energy short wavelength electromagnetic radiation.
• This object has been accomplished by providing a photographic material containing a silver halide emulsion layer for recording information in the form of very short wavelength invisible electromagnetic radiation known as X-ray, wherein the sensitivity of said layer for ultraviolet light and visible light is strongly reduced without substantially affecting the X-ray sensitivity of said material by incorporating therein an appropriate amount of a selective densitizing compound according to the following general formula:
• R represents a substituent known in cyanine chemistry on the quaternated nitrogen atom of a heterocyclic nucleus, e. g. an alkyl radical including substituted alkyl of the type generally known in cyanine'dye chemistry, such as C -C alkyl including alkyl in substituted form, e.g.
• A represents a methylene radical, an ethylene radical, a propylene radical or a butylene radical
• B represents an alkyl group, an amino group, a substituted amino group and also a hydrogen atom in the case V is a single bond
• W and V each represents a -CO-- radical, a -SO radical or a single bond, but at least one of them is a SO radical as described in the U.K. Pat. Specification No. 904,332 filed July 5, 1957 by Gevaert Photo-Producten N.V., an unsaturated aliphatic radical, e.g.
• aralkyl including substituted aralkyl e.g. benzyl and carboxybenzyl, aryl including substituted aryl, e.g. phenyl and carboxyphenyl, a cycloalkyl radical such as cyclohexyl and cyclopentyl;
• Z represents the necessary atoms to complete a heterocyclic nucleus of the type used in the production of cyanine dyes, e.g. a nucleus of the thiazole series (e.g. thiazole, 4- methylthiazole, 4-methyl-5-carbethoxythiazole, 4-phenylthiazole, S-methylthiazole, S-phenylthiazole, 4-(mtolyl)-thiazle, 4-(p-bromophenyl)-thiazole, 4,5- dimethylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)- thiazole, 4(m-nitrophenyl)-thiazole, a nucleus of the benzoithiazole series (e.g.
• benzothiazole 4- chlorobenzothiazole, S-chlorobenzothiazole, 6- chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, -methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 6- bromobenzothiazole, 6-sulphobenzothiazole, 4- phenybenzothiazole, S-phenylbenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole, 6-methoxybenzothiazole, S-iodobenzothiazole, 6- iodobenzothiazole, 4-ethoxybenzothiazole, S-ethoxybenzothiazole, 4,5,6,7-tetrahydrobenzothiazole, 5,6- dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, S-hydroxybenzothiazole, 6-hydroxybenzo
• naphtho [2,ld] thiazole naphtho [l,2-dl-thiazole, S-methoxynaphtho 1 ,2-d]-thiazole, 5-ethoxynaphtho[ l ,2-d]- thiazole, 8-methoxynaphtho[2,l-d]thiazole, 7-methoxynaphtho[2,l-d]-thiazole), a nucleus of the thionaphtheno[7,6-d]thiazole series (e.g. 7-methoxythionaphtheno[7,6-d]thiazole), a nucleus of the thiadiazole series (e.g.
• 4-phenylthiadiazole nucleus of the oxazole series (e.g. 4-methyloxazole, 5-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole, 4,5dimethyloxazole, 5-phenyloxazole), a nucleus of the benzoxazole series (e.g.
• benzoxazole 5- chlorobenzoxazole, S-methylbenzoxazole, 5-phenylbenzoxazole, G-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, S-methoxybenzoxazole, 6-methoxybenzoxazole, S-hydroxybenzoxazole, 6- hydroxybenzoxazole), a nucleus of the naphthoxazole series (e.g. naphtho[2,l-d]oxazole, naphtho[l,2-d]oxazole), nucleus of the selenazole series (e.g.
• naphtho[ 1,2-dselenazole), those of the 2quinoline series e.g. quinoline, 3-methyl-quinoline, S-methyl-quinoline, 7-methyl-quinoline, S-methyl-quinoline, fi-chloro-quinoline, 8-chloro-quinoline, -methoxy-quinoline, 6-ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.
• a nucleus of the pyrimidine series a nucleus of the quinoxaline series, a nucleus of the quinazoline series, a nucleus of the l-phthalazine series, a nucleus of the 2- pyridine series (e.g. pyridine, S-methylpyridine, 3- nitropyridine), a nucleus of the benzimidazole series (e.g.
• benzimidazole 5,6-dichlorobenzimidazole, 5- chlorobenzimidazole, 5 ,-dibromobenzimidazole, 5- chloro-6-aminobenzimidazole, 5-chloro-6- bromobenzimidazole, S-phenylbenzimidazole, 5- fluorobenzimidazole, 5,o-difiuorobenazimidazole, 5- cyanobenzimidazole, 5 ,tS-dicyanobenzimidazole, 5-
• chloro--cyanobenzimidazole 5-fluoro-6- cyanobenzimidazole, 5-acetylbenzimidazole, 5-chloro-6- fluorobenzimidazole, S-carboxybenzimidazole, 7-carboxybenzimidazole, 5-carbethoxybenzimidazole, 7-carbethoxybenzimidazole, 5-sulphamylbenzimidazole, or 5- N-ethylsulphamybenzimidazole;
• L represents methine including substituted methine, e.g. a
• Ar represents a bivalent aromatic radical, e.g. a phenylene radical, n represents a positive integer l or 2, x represents an 4 k)? 3 BIL 3,00 3 Q and but X" is not present when R, itself contains an anionic group, and
• H can I Ca s s CH: 0,N on,
• the quantity of desensitizing azomethine dye relative to silver halide for use according to the present invention has to be adapted depending upon the particular silver halide emulsion and the particular desensitizing compound used, the ratio of gelatin or other colloid binder to silver halide, the ingredients used e.g. stabilizers and the thermal treatment of the emulsion before coating.
• azomethine dye per mole of silver halide are useful for obtaining the desired difference in sensitivity between visible light and X-rays.
• a preferred range of dye concentration lies between 1 and 100 mg. per mole of silver halide since thereby for a relatively strong reduction in visible light sensitivity the X-ray sensitivity of the emulsion is not substantially lowered.
• the azomethine desensitizing dyes used according to the present invention substantially lower the fog level of the developed material which is to be considered as a very interesting advantage.
• silver halide e.g. silver chloride, silver bromide, silver chlorobromide, silver chloroiodide and silver bromoiodide
• iodide containing bromide emulsions preferably containing at most 2.5 mole percent iodide are especially useful for X-ray recording.
• an adequate amount of ultraviolet absorbing substance and dye e.g. a yellow dye may be used.
• the filter dye may be incorporated in the emulsion layer, topcoat or protective layer and/or in the base or a backing layer.
• the desensitizing dyes used according to the present invention can be added to the light sensitive silver halide emulsion during different preparation steps of the light sensitive material. For example they can be incorporated therein by a separate addition, e.g. from a solution or dispersion, or they can be added as a mixture with one or more ingredients used in the formation of the silver halide grains, during the physical or chemical ripening or during another step preceding the coating of the emulsion.
• the desensitizing dyes can also be incorporated in a water-permeable layer adjacent to the silver halide emulsion layer, but have then to come by diffusion in working contact with the light sensitive silver halide.
• the said desensitizing compounds are preferably used in combination with water-soluble alkylene oxide trialkylsulphonium products or polymers, e.g. as
• the selective desensitizing compounds can further be combined with chemical sensitizers known in the art e.g. sulfurcontaining compounds such as allyl isothiocyanate, allyl thiourea, or sodium thiosulfate, reducing compounds such as the tin compounds described in the Belgian Pat. Specification Nos. 493,464 filed Jan. 24, 1950 and 568,687 filed June 18, 1958 both by Gevaert Photo-Producten N.V., the iminoaminomethane sulfinic acid compounds described in the British Pat. Specification No. 798,823 filed Dec. 11, 1956 by Mullard Ltd., or noble metal compounds such as gold, platinum, palladium, iridium, ruthenium and rhodium compounds.
• chemical sensitizers known in the art e.g. sulfurcontaining compounds such as allyl isothiocyanate, allyl thiourea, or sodium thiosulfate
• reducing compounds such as the tin compounds described
• the desensitizing compounds used according to the present invention can also be used in combination with known stabilizing agents for silver halide emulsions, e.g. mercury compounds, sulfur compounds such as I-phenyI-Z-tetramline-S- thion, the compounds described in the Belgian Pat. Specification No. 571,916 and 571,917 both filed Oct. 10, 1958 by Gevaert Photo-Producten N.V., either or not in combination with chemically sensitizing and stabilizing cadmium salts in the light sensitive material as well as in the developer.
• known stabilizing agents for silver halide emulsions e.g. mercury compounds, sulfur compounds such as I-phenyI-Z-tetramline-S- thion, the compounds described in the Belgian Pat. Specification No. 571,916 and 571,917 both filed Oct. 10, 1958 by Gevaert Photo-Producten N.V., either or not in combination with chemically sensitizing and stabilizing cadmi
• derivatives of tetra-azaindenes e.g. having the following general formula can be used as fog-inhibiting compounds in the light sensitive material:
• each of R, and R represents a hydrogen atom, an alkyl, an
• R represents a hydrogen atom, an alkyl, a carboxy, or an alkoxy-carbonyl group.
• the selective desensitized silver halide emulsions can be applied by usual coating techniques to any type of support known in silver halide photography e.g. paper, cellulose triacetate or polyester resin support.
• Example 1 An ordinary coarse-grained silver bromoiodide (2 mole percent iodide) emulsion of the type normally used in radiography, which had been chemically sensitized to its optimum speed was divided into two portions. One portion was then treated with a desensitizing compound of the structural formula 1 above, the other portion of the emulsion remained untreated and served as a control. Each of the portions of the emulsions was then coated on an ordinary cellulose triacetate film base, and the coatings dried.
• the films obtained were then divided in two identical strips one of which was exposed to kilovolt X-rays through an aluminum step wedge and the other strip was exposed through a grey-wedge to an incandescent bulb emitting in the visible region of the spectrum, and provided with a filter to correct its emission spectrum towards the normal spectrum of daylight. Each strip was then developed for 4 minutes in the following developer at 20 C.
• Example 1 is repeated but with a silver bromoiodide emulsion containing 2.5 mole percent iodide and with a dye of structural formula VIII.
• the sensitometric results are listed in table 2.
• Example 3 The foregoing examples were repeated with a silver bromoiodide emulsion containing 0.35 mole percent iodide and with dyes as indicated in the following table 3 wherein the results obtained are listed.
• a photographic material comprising an X-ray sensitive silver halide emulsion layer, containing a desensitizing compound, which decreases the sensitivity to ultra violet radiation and visible light of the emulsion layer to a greater extent than its sensitivity to X'rays wherein said compound is used in said emulsion layer in an amount of from about 1 to 100 mg. per mole of silver halide such as not to decrease the X-ray sensitivity of the emulsion layer below about 70 percent of its inherent value and retaining the desensitization of the emulsion to ultraviolet and visible light and wherein said compound corresponds with the general formula:
• X represents an anion, but is not present when R, itself contains an anionic group
• each of R and R represents alkyl aryl, or R, and R together represent the atoms necessary to close a heterocyclic nucleus.
• R represents C ,-C alkyl
• Z represents the necessary atoms to complete a nucleus of the 2-quinoline series or a nucleus of the benzothiazole series
• L represents a methine radical
• Ar represents a p-phenylene radical
• X' represents an anion, but is not present when R, itself contains an anionic group.
• each of R, and R represents alkyl.

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• 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)

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Cited By (16)

Citations (3)

• 1966
  • 1966-07-01 GB GB29579/66A patent/GB1183317A/en not_active Expired
• 1967
  • 1967-05-31 US US642355A patent/US3630744A/en not_active Expired - Lifetime
  • 1967-06-21 NL NL6708637A patent/NL6708637A/xx unknown
  • 1967-06-30 BE BE700717D patent/BE700717A/xx unknown
  • 1967-06-30 DE DE19671597462 patent/DE1597462A1/de active Pending

Patent Citations (3)

Non-Patent Citations (1)

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