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
  • C09B23/14—Styryl dyes
  • C09B23/145—Styryl dyes the ethylene chain carrying an heterocyclic residue, e.g. heterocycle-CH=CH-C6H5
• • 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
  • C09B23/02—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups
  • C09B23/04—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups one >CH- group, e.g. cyanines, isocyanines, pseudocyanines
• • 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
• • 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
  • C09B23/08—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines
  • C09B23/083—Methine or polymethine dyes, e.g. cyanine dyes the polymethine chain containing an odd number of >CH- or >C[alkyl]- groups more than three >CH- groups, e.g. polycarbocyanines five >CH- groups
• • 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
  • C09B23/10—The polymethine chain containing an even number of >CH- groups
• • 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
  • C09B23/10—The polymethine chain containing an even number of >CH- groups
  • C09B23/105—The polymethine chain containing an even number of >CH- groups two >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
  • 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

Definitions

• the present invention relates to a photographic silver halide emulsion and more particularly to a fine grain silver halide photographic emulsion which has been sensitized over the region from the specific absorption wave length region of the silver halide in the silver halide emulsion to a spectrally sensitized wave length region.
• the first technique for light-sensitization is further divided generally into either chemical sensitization or spectral sensitiztaion (cf., E. K. Mees and T. H. James, The Theory of the Photographic Process, 3rd ed., par. 12, Mac- Millan Co. (1966).
• Chemical sensitization includes such sensitizing methods as reduction sensitization, sulfur sensitization, noble metal sensitization (for example, salts of gold, platinum, palladium, iridinum or rhodium with thiocyanates), and combinations thereof. But, the application of any of these chemical sensitizations increases only the sensitivity of a specific absorption wave length region of the silver halide. On the other hand, spectral sensitization extends the photosensitive wave length region from the specific wave length region of absorption of silver halide toward the absorption of longer wave lengths.
• the photographic silver halide emulsion used is not chemically ripened or is a silver iodobromide emulsion having internal sensitivity
• the silver halide emulsion is, on the contrary, sensitized by a socalled desensitizing dye.
• This phenomenon is well known as the Capri-blue etfect [see, for example, Tamura & Hada, On the Desensitization of Silver Halide Emulsion by Dyes, Journal of Photographic Science, II (2), 87 (1967 )1.
• the sensitivity of a photographic silver halide emulsion can be markedly increased over the whole visible wave length regions by the addition of the dye to the silver halide emulsion.
• an object of the present invention is to provide a photographic silver halide emulsion having fine silver halide grains and at the same time having a high sensitivity over a region from the specific absorption region of silver halide emulsion in which at least of silver SUMMARY OF THE INVENTION
• the above-mentioned object of the present invention can be achieved by incorporating a dye having an oxidation potential value of less than 0.9 volt in a photographic silver halide emulsion in which at least 95% of silver halide grains contained in the silver halide emulsion have grain sizes less than 0.20 micron or in which the mean grain size of silver halide grains is less than 0.18 micron.
• the dye having the above-mentioned properties is particularly preferable in the present invention to incorporate the dye having the above-mentioned properties into a photographic silver halide emulsion which has been subjected to chemical ripening procedure.
• oxidation potential used in the present specification means the potential at which the dye is oxidized by the anode (cf., P. Delahay, New Instrumental Methods in Electrochemistry, Interscience Publishers (1954), and L. Meites, Polarographic Techniques, 2nd ed., Interscience Publishers (1965).
• the oxidation potential described in the present specification is the half-way potential of a voltage-current curve obtained by using a rotary platinum electrode and a saturated calomel electrode as the electrodes and also using sodium perchlorate as the supporting electrolyte.
• the dye is used as an acetonitrile solution having a concentration of from 1X mole to 1X10 mole [cf., A. Stanienda, Naturmaschineen, 47, 353 and 512 (1960)].
• a series of observed oxidation potentials of dyes may have a deviation of about 100 millivolts by the influence of the contact potential difference between liquids, the temperature of measuring the electric resistance of the solution of dye, and the anions of the dyes.
• the reproducibility of the measurement of the oxidation potential can be secured.
• suitable emulsions are a silver iodobromide emulsion, a silver bromide emulsion, a silver chlorobromide emulsion, and a silver iodobromo-chloride emulsion. More particularly, a silver iodobromide emulsion and a silver bromide emulsion are preferred.
• the use of a silver chloride emulsion is, however, unprofitable in the present invention.
• the particular sensitization elfect of the present invention in the specific absorption wave length region of a silver halide emulsion depends on the grain size of silver halide particles in the emulsion, even when the halogen atom composition of the photographic emulsion is the same.
• the sensitization of the photographic silver halide emulsion of the present invention can be applied to a sensitizing method such as a sulfur sensitization, a reduction sensitization and/or a noble metal sensitization.
• the sensitization in the present invention can be applied to a sensitizing method in a developing process.
• the particular sensitization eifect of the present invention in the specific absorption region of silver halide is more marked as the size of the silver halide grains in the silver halide emulsion to which the dye is added is reduced below 0.20 micron.
• the larger the silver halide grains the more the sensitization effect by the present invention is reduced.
• the sensitizing effect by the addition of the dye is lost or is converted into a desensitization function usually observed in the case of using a conventional sensitizing dye.
• a silver iodobromide emulsion sufiiciently subjected to chemical ripening was mixed with 1X10 mole/liter of a methanol solution of a thiacarbocyanine in an amount of 8 ml. per 100 g. of the silver halide emulsion and the resultant silver halide emulsion was applied to a support to provide a light-sensitive element, which was subjected to sensitometry using blue light.
• the sensitivity obtained is compared with that Mean grain size (in microns) 0. 30 sensitizing percent From the results it will be understood that the size of silver halide grains used in the emulsion is a very important factor for the specific effect of the present invention.
• the sensitization effect of the present invention in the specific absorption wave length region is fundamentally different from the above-described Capri-blue effect.
• the specific absorption wave length region of silver halide is sensitized, while the phenosafranine shows only a desensitization effeet to the fine grain silver iodobromide emulsion employed in the present invention.
• the dyes used in the present invention include merocyanine dyes, cyanine dyes, hemicyanine dyes, rhodacyanine dyes, trinuclear cyanine dyes, and styryl dyes. Suitable dyes for use have an oxidation potential lower than 0.90 volt.
• the dyes used in the present invention can be prepared by known methods, that is, can be generally prepared as follows:
• the trimethine dye, Dye I can be prepared by condensing a quaternary ammonium salt represented by the general Formula I and an ortho-formic acid ester in pyridine in the presence of a base such as triethylamine.
• the pentamethine dye, Dye H can be prepared by using in the above described condensation reaction 1,3,3-triethoxypropene and the like instead of the orthoformic acid ester.
• the monomethine dye, Dye V, or Comparative Dye C can be prepared by condensing a quaternary ammonium salt intermediate product represented by the general Formula II shown below.
• the benzimidazolocarbocyanine dye, Dye II or IV can be prepared by condensing a quaternary ammonium salt intermediate product represented by the following general Formula III and an ortho-formic acid ester in nitrobenzene in the presence of a base such as triethylamine or condensing the said quaternary ammonium salt intermediate product and a chloral in an alcohol in the presence of an alcoholate.
• the styryl base dye, Dye XIV or XV can be prepared by condensing a compound represented by the following general Formula IV -N (IV) and a p-dialkylaminobenzaldehyde in the presence of zinc chloride.
• merocyanine dyes can be prepared by condensing a ketomethylene compound represented by the following general Formula V and an intermediate product represented by the following general Formula VI or VII R X" (VII) 10 in an alcohol (e.g. methanol or ethanol) or pyridine in the presence of a base such as triethylamine.
• Z and Z each represents an atomic group necessary to complete a nitrogencontaining heterocyclic ring, such as a benzothiazole, a naphthothiazole, a benzoselenazole, a naphthoselenazole, a benzoxazole, a naphthoxazole, a quinoline, a benzimidazole, a thiazole, an oxazole, or a terazole ring;
• Z" represents an atomic group necessary to complete a benzimidazole ring;
• R, R, and R" each represents an alkyl group such as a methyl group, an ethyl group, or a n-propyl group; a substituted alkyl group such as a fi-hydroxyethyl group, a fi-carboethoxyethyl group, a carboxymethyl group, a fl-carboxyethyl group, a
• the above-mentioned dyes in the present invention can be used together with other additives such as stabilizers, antifoggants, sensitizing dyes, hardening agents, wetting agents, water-soluble high molecular weight compounds, e.g., gelatin or gelatin derivatives, film-denaturing agents, and couplers if desired. Also, it is especially suitable that the dye in the present invention be used as a dye having the above-mentioned specific sensitizing effect and a spectral sensitization function.
• the photographic silver halide emulsion of the present invention can be applied to any suitable support such as a glass plate, a triacetyl cellulose film, a polyethylene terephthalate film, other plastic films, a plastic sheet, a baryta-coated paper, a resin-laminated paper, and the like.
• EXAMPLE 1 A silver iodobromide emulsion was prepared in a conventional manner and was subjected to physical ripening or chemical ripening in the conventional manner.
• the silver halide emulsion contained 1 mole percent of iodide ion and the mean size of the silver halide grains in the emulsion was 0.06 micron.
• Fifty grams (50 g.) of the silver halide emulsion was placed in a beaker and melted by heating the beaker in a bath at 40 C.
• a specific amount of a solution of the dye of the present invention having a concentration of 1X10" mole/liter was added to the molten emulsion with stirring and 7 ml. of the resultant emulsion was applied to a glass plate of cabinet size and dried.
• the light-sensitive plate was exposed by optical wedge to a tungsten light of a color temperature of 2854 K. by means of a S-type sensitometer made by Fuji Photo Film Co., through a blue filter No. K-31 or a yellow filter No. K-12. Subsequently, the photographic plate was developed for 10 minutes at 20 C. in a developer having the following composition, and then fixed.
• the optical density of the photographic plate thus treated was measured by using a S-type sensitometer made 1 1 by Fuji Photo Film Co. and the results of the relative blue filter sensitivity, Sb, and the relative yellow filter sensitivity, Sy, at the point where the optical density was fog+0.2 are shown in the following table.
• a photographic negative silver halide emulsion containing a silver halide, excluding silver chloride, and a sensitizing dye
• the improvement which comprises at least 95% of the silver halide having a grain size less than 0.2 micron, said dye having an oxidation potential of less than 0.90 volt and being a member selected from the group consisting of a merocyanine dye, a cyanine dye, a hemicyanine dye, a rhodacyanine dye, a trinuclear cyanine dye, and styryl dye.
• a photographic negative silver halide emulsion containing a silver halide, excluding silver chloride, and a sensitizing dye
• the improvement which comprises the silver halide having a mean grain size less than 0.18 micron, said dye having an oxidation potential of less than 0.90 volt, and being a member selected from the group consisting of a merocyanine dye, a cyanine dye, a hemicyanine dye, a rhodacyanine dye, a trinuclear cyanine dye and a styryl dye.
• a photographic negative light-sensitive element comprising a support and one or' more photographic silver halide emulsion layers coated thereon, the improvement which comprises at least one of the layers containing a photographic silver halide emulsion as claimed in claim 1.
• a photographic light-sensitive element comprising a support and oneprzmore photographic @silver halide emulsion layers; coated thereon, the improvement which comprises at least one of the layers'ac'ontaining a photographic silver halide emulsion as claimed in claim 5.
• a photographic negative light-sensitive element comprising a support and one or more photographic silver halide emulsion layers coated thereon, ,-.the improvement which comprises at least one of the layers containing a photographic silver halide emulsion as claimed in claim 2.
• a photographic light-sensitive element comprising a support and one or more photographic silver halide emulsion layers coated thereon, the improvement which comprises at least one of the layers containing a photographic silver halide emulsion as claimedin claim 9.

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

Applications Claiming Priority (1)

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Country Status (6)

Cited By (13)

• 1969
  • 1969-03-07 JP JP1726169A patent/JPS565981B1/ja active Pending
  • 1969-12-29 BE BE743790D patent/BE743790A/xx unknown
• 1970
  • 1970-01-01 GB GB1297901D patent/GB1297901A/en not_active Expired
  • 1970-01-08 CA CA071,669A patent/CA960900A/en not_active Expired
  • 1970-02-24 US US13774A patent/US3706566A/en not_active Expired - Lifetime
  • 1970-03-06 DE DE19702010762 patent/DE2010762A1/de active Pending

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