US3769025A - Spectrally sensitized silver halide photographic emulsion - Google Patents

Spectrally sensitized silver halide photographic emulsion Download PDF

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Publication number
US3769025A
US3769025A US00150606A US3769025DA US3769025A US 3769025 A US3769025 A US 3769025A US 00150606 A US00150606 A US 00150606A US 3769025D A US3769025D A US 3769025DA US 3769025 A US3769025 A US 3769025A
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United States
Prior art keywords
silver halide
emulsion
halide photographic
silver
group
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Expired - Lifetime
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US00150606A
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English (en)
Inventor
K Ohkubo
K Shiba
A Sato
A Ogawa
J Noguchi
K Ohmura
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • 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
    • G03C1/28—Sensitivity-increasing substances together with supersensitising substances
    • G03C1/29—Sensitivity-increasing substances together with supersensitising substances the supersensitising mixture being solely composed of dyes ; Combination of dyes, even if the supersensitising effect is not explicitly disclosed

Definitions

  • the emulsion is spectrally sensitized over a wide green light wavelength range of from 500 580 nm and has high sensitivity to green light in flash exposure. Photographic materials produced by using this emulsion are especially useful for information transmitting systems such as a press facsimile.
  • a press facsimile system for transmitting a newspaper manu: script rapidly to a remote locality a high speed photo typesetting system for rapidly setting up a form
  • a cathode ray tube display system which, immediately transforms the information produced by an electronic computer into letters or figures. Exposure for a time as short as less than I 100,000th of a second, especially about 1/l,000,000th of a second, is frequently used in the equipment for these rapid information transmitting systems. In recent years, there has been a very brisk demand for photographic materials for use in such systems.
  • l-ligh illuminance light sources such as a xenon arc lamp or a high pressure mercury lamp in combination with a high speed shutter, or a xenon flash lamp or cathode ray tube are used as light sources in such equipment.
  • cathode ray tube those generally known to be used for flying spot which have a fluorescent substance with a short afterglow time are used.
  • fluorescent substances which are called P-ll, P45, P-l6, and P-24 are used. It is known that in an emission spectroscopic energy distribution, a peak exists at 460 nm for P-l 1, and at 385 nm for P-l 6.
  • the xenon lamp emits light over a relatively wide range of wavelengths. Radiation which has left the light source converges through a condenser lens, a negamatrix, a main lens, a prism, a reflector, or a special lens or prism for letter deformation or other purposes, and forms an image on the light-sensitive surface of a photographic material. Because of the optical system used in the path of these systems, light radiation of shorter wavelengths is absorbed to a greater extent, and the light which reaches the light-sensitive surface contains a reduced proportion of radiation in the range from ultraviolet to blue, and a larger proportion of green light or radiation of longer wavelengths. For this reason, it becomes essential to subject the photographic material to green color sensitization so that its overall sensitivity will be increased.
  • the afterglow time of the luminescence of a cathode ray tube is asshort as 2 l/10,000,000th of a second to 1/100,000th of a second.
  • the xenon flash lamp used in the above-described information transmitting systems also has an afterglow time much the same as this.
  • flash exposure as used in the present specification, generically refers to such a short time exposure to these light sources.
  • the strong sensitizing ability of the longer wavelength region of a sensitizing dye having a spectral sensitivity maximum in the longer wavelength region is influenced markedly by the other sensitizing dye. having a spectral sensitivity in a shorter wavelength region. This frequently results in a reduced sensitizing ability in the longer wavelength region.
  • spectral sensitization techniques is considered to be the discovery of sensitizing dyes which, when used in combination, do not adversely affect each other,and which preferably have an increased spectral sensitivity.
  • strict selectiv-. ity is required between two groups of dyes which, when used in combination, increase in sensitizing ability.
  • An apparently slight difference in the chemical structural formula often exerts a marked influence on the strength of the spectral sensitizing action. it is generally thought therefore that the photographic effect of sensitizing dyes is difficult to predict from their chemical structural formulas alone.
  • the present invention concerns the spectral sensitization by flash exposure.
  • Known methods of increasing spectral sensitivity are generally. based on the results obtained from experiments on the exposure time longer than l/l ,000th of a second.
  • the spectral sensitizing action by flash exposure differs unexpectedly from that of exposure for the previously known duration. This difference is outstanding especially with sensitizing dyes intended for a region of relatively short wavelengths and used for sensitizing the green light region at 500 to 580 nm. This'is considered to be due to the diversity of the oxidizability-reducibility of the absorbed dye itself. Furthermore, the difference is much more marked in the case of strong spectral sensitizing action in a green region.
  • An object of the present invention is to provide a photographic material which is spectrally sensitized over a wide green light wavelength region at 500 to 580 nm and which has a high sensitivity to green light in flash exposure so-that it can be used commonly for information transrnitting' systems using various light sources.
  • R R R and R is an alkyl group such as a methyl, an ethyl, an n-propyl, or an n-butyl group, or a substituted alkyl group such as a B-hydroxyethyl, a B-acetoxyethyl, a B-cyanoethyl, a y-methoxypropyl, a -y-carboxypropyl, a 'y-sulfopropyl, a vinyl methyl, or a benzyl group, with the proviso that at least one of R R R and R 'is a carboxyalkyl group such as a carboxymethyl, a B-carboxyethyl, a y-carboxyprop
  • each of R R and R is an alkyl group such as a methyl, an ethyl, or an n-propyl group, or a substituted alkyl group such as a B-hydroxyethyl, a fi-acetoxyethyl, a B-cyanoethyl, a -y-methoxypropyl, a y-car- .boxypropyl, a 'y-sulfopropyl, a vinyl methyl or a benzyl group, with the proviso that at least one of R R and R, is a carboxyalkyl group such as a carboxymethyl, a B-carboxyethyl, a 'y-carboxypropyl, a S-carboxybutyl, or an w-carboxypentyl group, Y is a halogen atom such as a fluorine, a chlorine, or a bro
  • Thespectral sensitization curve obtained when a dye of the formula (I) is added to a silver halide photographic emulsion is shown in FIG. with respect to a dye of the formula lA given later in the specification. It is seen from this curve that a spectral sensitization maximum exists at 565-580 nm,'and the spectral sensitization characteristics to light having a wavelength of less than 555 nm are poor.
  • the spectral sensitization curve obtained when a dye of the formula (11) is added to a silver halide photographic emulsion is shown in FIG. 3 with respect to a dye of the formula A given later'in the specification.
  • FIG. 3 shows that a spectral sensitization maximum exists at 540-560 nm, and the dye hardly is sensitive to light having a wavelength of greater than 565 nm.
  • the spectral sensitization curve obtainedwhen both of the dyes of the formulas (I) and (II) are added in this order to a silver halide photographic emulsion is shown in FIG. '4 with respect to dyes of the formulas IA and A, which indicates that the emulsion is spectrally sensitized over the range of 500 to 580 nm.
  • sensitizing dyes often cannot be added to photographic emulsions in sufficient concentrations because of their low solubility organic solvents such as ethanol or methanol.
  • the sensitizing dyes used in the present invention have good solubility in organic solvents, and therefore are easily purified on synthesis, and form into solutions. Thus, it becomes easy to add the dye solution to a photographic emulsion.
  • the sensitizing dyes used in the invention are especially useful with a gelatin-silver halide emulsion such as a silver chloride, silver bromide, silver chlorobromide, silver iodobromide, or silver chloroiodobromide emulsion, but are also capable of fully sensitizing photographic emulsions containing water-permeable col-' loids, water-soluble cellulose derivatives, polyvinyl alcohol, or other hydrophilic synthetic or natural resins or polymers instead of gelatin.
  • a gelatin-silver halide emulsion such as a silver chloride, silver bromide, silver chlorobromide, silver iodobromide, or silver chloroiodobromide emulsion
  • the photographic emulsion of the present invention may be prepared by adding the two kinds of dyes to a photographic emulsion in a conventional manner. It is the general practice to add the dyes as a solution in a suitable solvent. The concentrations of the dyes in the emulsion can be varied over a wide range of l to 200 mg per kilogram of the emulsion according to the desired effect.
  • Additives usually employed in the production of photographic emulsions such as stabilizers, toning agents, hardening agents, wetting agents, antifoggants, plasticiz'ers, development accelerators, fluorescent bleaching agents, and developing agents for activator development, may also be added to the emulsion using customary techniques.
  • the emulsion so prepared may be coated conventionally on a suitable support, such as a film of a cellulose derivative, a film of a synthetic resin, glass, or baryta paper.
  • a suitable support such as a film of a cellulose derivative, a film of a synthetic resin, glass, or baryta paper.
  • a photographic material which has a high sensitivity in the orthochromatic spectral region and a sufficiently low sensitivity to red light, and in which the sensitizing dyes are readily bleached by processing including development, fixation, and rinsing or a processing including activator development and stabilization and remain colorless after the processing.
  • Such photographic materials are especially suitable for use in the rapid information processing described above.
  • sensitizing dyes expressed by the formulas (I) and (11) used in the invention can be synthesized easily by those skilled in the art by known methods. Typical examples of the synthesis of the sensitizing dyes used in the invention will be given briefly below.
  • the precipitate was washed with water, and crystallized with ethanol.
  • the crystals obtained were recrystallized from ethanol to yield a dye having a melting point of 262C in an amount of 1.1 g.
  • the dye had a spectral absorption maximum at 513.5 nm (in methanol).
  • EXAMPLE Four photographic emulsions were prepared each weighing 100 g and containing a silver halide composed of 29 mole percent silver chloride, 70 mole percent silver bromide and 1 mole percent silver iodide (each emulsion containing 45 milligram equivalents of silver and 12 g of gelatin). Four samples were prepared by adding the dyes of the formulas (IA) and (HA) in the amounts indicated below:
  • the photographic materials so obtained were each exposed for l/ 100th of a second and l/ 1,000,000 of a second respectively through a V--Y 50 color glass fil ter (Tokyo Shibaura Electric Co., Ltd.) and an optical wedge using a Mark'VlI sensitometer (EG & G Company, U.S.A.).
  • the above-described color glass filter absorbs light corresponding to the sensitivity region inherent to silver halide, and allows transmission of light corresponding to a spectral sensitization region of about 500 nm or more.
  • Each of the exposed samples was developed for 2 minutes at C in a developing solution of the following formulation.
  • Relative Sensitivity Relative Sensitivity to green to green light in exposure for light in exposure for Samples lIlQOth of a second i] l,000,000th a second I Not Sensitive Not Sensitive 2 210
  • the sensitivity values were measured as follows: The reflection density of the resulting image was measured, and the reciprocal of the ratio of the amount of light which gave a density of 0.5 was employed as the sensitivity value. Since the absolute amount-of light through a filter was not measured, the sensitivity values are relative ones. But in the above table, the sensitivities for a given exposure time could be compared The results shown above demonstrate that the Dyes IA and HA in combination have sufficient sensitivity even in flash exposure 8 What is claimed is: I.
  • each of R R and R is selected from the group consisting of an alkyl group and a substituted alkyl group, said substituents being selected from the group consisting of a hydroxy group, an acetoxy group, a cyano group, a carboxy group, a sulfo group, a vinyl group, and an aryl group, at least one of R R and R being a carboxyalkyl group, Y is a halogen atom, n" is l or 2, X is an anion, and I is 1 or 2.
  • sensitizing dye of formula (I) is a compound represented by the following formula:
  • sensitizing dye of the formula (II) is wherein X is Cl, Br, or I. selected from the group consisting of v

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Organic Chemistry (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)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US00150606A 1970-06-05 1971-06-07 Spectrally sensitized silver halide photographic emulsion Expired - Lifetime US3769025A (en)

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JP45048546A JPS4912656B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1970-06-05 1970-06-05

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JP (1) JPS4912656B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
BE (1) BE768187A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CA (1) CA962881A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2128296C3 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR2096029A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1300880A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947275A (en) * 1970-05-01 1976-03-30 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
US4544628A (en) * 1983-02-02 1985-10-01 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US4555481A (en) * 1983-01-25 1985-11-26 Fuji Photo Film Co., Ltd. Silver halide photographic emulsions containing benzimidazolocarbocyanine dye having fluoroalkyl group at the nitrogen atom of benzimidazole
US5135845A (en) * 1990-04-10 1992-08-04 Eastman Kodak Company Sensitizing dye for photographic materials
US5866315A (en) * 1996-05-24 1999-02-02 Konica Corporation Silver halide photographic light sensitive material
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59188641A (ja) * 1983-04-11 1984-10-26 Fuji Photo Film Co Ltd ハロゲン化銀写真乳剤

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2973264A (en) * 1957-03-06 1961-02-28 Gevaert Photo Prod Nv Sensitized photographic emulsions
US3173791A (en) * 1962-09-27 1965-03-16 Eastman Kodak Co Supersensitized photographic silver halide emulsions
US3364031A (en) * 1963-06-24 1968-01-16 Eastman Kodak Co Supersensitized photographic silver halide emulsions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2973264A (en) * 1957-03-06 1961-02-28 Gevaert Photo Prod Nv Sensitized photographic emulsions
US3173791A (en) * 1962-09-27 1965-03-16 Eastman Kodak Co Supersensitized photographic silver halide emulsions
US3364031A (en) * 1963-06-24 1968-01-16 Eastman Kodak Co Supersensitized photographic silver halide emulsions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Defensive Publication, T875,028, 875O.G.714 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3947275A (en) * 1970-05-01 1976-03-30 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
US4555481A (en) * 1983-01-25 1985-11-26 Fuji Photo Film Co., Ltd. Silver halide photographic emulsions containing benzimidazolocarbocyanine dye having fluoroalkyl group at the nitrogen atom of benzimidazole
US4544628A (en) * 1983-02-02 1985-10-01 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
US5135845A (en) * 1990-04-10 1992-08-04 Eastman Kodak Company Sensitizing dye for photographic materials
US5866315A (en) * 1996-05-24 1999-02-02 Konica Corporation Silver halide photographic light sensitive material
EP1750173A1 (en) 2005-08-04 2007-02-07 Fuji Photo Film Co., Ltd. Silver halide photosensitive material and packaged body containing the same

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Publication number Publication date
BE768187A (fr) 1971-11-03
DE2128296C3 (de) 1975-06-19
DE2128296A1 (de) 1971-12-09
JPS4912656B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1974-03-26
GB1300880A (en) 1972-12-20
CA962881A (en) 1975-02-18
FR2096029A5 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1972-02-11
DE2128296B2 (de) 1974-10-31

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