US3545975A - Optically sensitized light-sensitive material - Google Patents

Optically sensitized light-sensitive material Download PDF

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Publication number
US3545975A
US3545975A US709194A US3545975DA US3545975A US 3545975 A US3545975 A US 3545975A US 709194 A US709194 A US 709194A US 3545975D A US3545975D A US 3545975DA US 3545975 A US3545975 A US 3545975A
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US
United States
Prior art keywords
sensitizing
dyes
emulsion
silver
dye
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US709194A
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English (en)
Inventor
Helmut Kampfer
Marie Hase
Harald Von Rintelen
Oskar Riester
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Agfa Gevaert AG
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Agfa Gevaert AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Publication date
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Publication of US3545975A publication Critical patent/US3545975A/en
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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
    • 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
    • G03C1/22—Methine and polymethine dyes with 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
    • C09B23/102—The polymethine chain containing an even number of >CH- groups two heterocyclic rings linked carbon-to-carbon

Definitions

  • the adsorption of the sensitizers on the silver halide should be so strong that the sensitizing effect will be impaired as little as possible by the other necessary additives such as wetting agents and emulsifiers, stabilizers, color couplers, dyes that can be bleached out, white toners, etc. 'It must also be possible to carry out sensitization under extreme conditions such as elevated temperature and high moisture-content. Furthermore, the sensitizing dyes must not increase the fog as is the case with the known basic cyanine dyes. For these reasons, there is considerable interest in finding new sensitizing dyes.
  • sensitizing dyes for spectrally sensitizing light-sensitive layers especially silver halide emulsion layers, that do not suffer the above-mentioned disadvantages.
  • the object of the present invention is to provide sensitizing dyestuffs for sensitizing of light-sensitive layers, more especially silver halide emulsion layers, which have a particularly high sensitization intensity in the blue spectral region with a steepest possible decrease towards long wavelengths.
  • X represents a sulfur or selenium atom
  • R' represents a sulfo-substituted or carboxyl-substituted
  • R"' represents (1) hydrogen, (2) a saturated or unsaturated aliphatic group, advantageously with up to 5 carbon atoms, which may be substituted, for example with sulfo, carboxyl, halogen such as chlorine, hydroxyl, alkoxy or the like, (3) aryl, advantageously phenyl, (4) cycloalkyl, advantageously cyclohexyl, or (5) heterocyclic ring, advantageously a saturated N- containing ring, such as morpholino, or piperidino, and the aryl, cycloalkyl or heterocyclic ring can be substituted, for example with sulfo or carboxyl groups.
  • the sensitizing dyes used according to the invention are advantageous in many respects, due to the fact that the radical R itself can be increased as desired.
  • the sensitizing dyes of the present invention have a maximum of high intensity in the shortwave range of the visible spectrum, between approximately 450 and 480 me. With most of these dyes, the maximum is between 460 and 470 In,u..
  • the dyes are characterized by a steep flank on the long-wave side of the maximum. Consequently, photographic material sensitized with the dyes show 'an excellent safety in the dark-room.
  • the aforementioned dyes can be prepared by known methods.
  • the preparation of dye No. 2 is described in detail hereafter.
  • the other sensitizing dyes are prepared in analogous manner.
  • the other sensitizing dyes have melting points as follows:
  • the preparation of photographic silver halide emulsions substantially comprises three steps:
  • the sensitizing dyes according to the present invention can be used in any silver halide emulsions.
  • Suitable silver halides are silver chloride, silver bromide or mixtures thereof, if desired containing a small amount of silver iodide up to 10 mole percent.
  • the silver halides may be dispersed in the usual hydrophilic compounds, for example, carboxymethylcellulose, polyvinyl alcohol, polyvinyl pyrrolidone, alginic acid and its salts, esters, or amides or preferably gelatin.
  • the sensitizing dyes to be used according to the present invention are advantageously added to the photographic emulsion before the chemical ripening or before casting.
  • the methods employed for this are generally known to persons skilled in this art.
  • the sensitizing dyes are generally incorporated in the emulsion in the form of solutions, e.g., in alcohol or mixtures of alcohol and Water.
  • the solvents must, of course, be compatible with gelatin and must not have any adverse effects on the photographic properties of the emulsion. Water, methanol or mixtures thereof are generally used as solvents.
  • the quantity of sensitizing dye added may vary within wide limits, e.g., between 2 and 200 mg. preferably between 10 and mg. per kg. of the silver halide emulsion.
  • the concentration of dye may be adapted to the particular requirements, depending on the type of emulsion, the desired sensitizing effect, etc. The most suitable concentration for any given emulsion can easily be determined by the usual tests employed in the art of emulsion making
  • the emulsions may also contain chemical sensitizers, e.g., reducing agents such as stannous salts, polyamines such as diethylentriamine, or sulfur compounds as described in US. Pat. No. 1,574,944. Furthermore, salts of noble metals, such as ruthenium, rhodium, palladium, iridium, platinum or gold may be contained in the emulsions for chemcial sensitization, as described in the article by R. Koslowsky, Z. Wiss. Phot. 46, -72 (1951).
  • the emulsions may also contain, as chemical sensitizers, polyalkylene oxides, especially polyethylene oxide and derivatives thereof.
  • the emulsions according to the present invention may contain the usual stabilizers such as homopolar or salttype compounds of mercury with aromatic or heterocyclic rings, such as mercaptotriazoles, simple mercury salts, sulfonium mercury double salts and other mercury compounds.
  • suitable stabilizers are azaindenes, especially tetraor pentaazaindenes, in particular those that are substituted with hydroxyl or amino groups. Compounds of this type are described in the article by Birr, Z. Wiss. Phot. 47, 2-58 (1952).
  • Other suitable stabilizers include heterocyclic mercapto compounds, e.g., phenylmercaptotetrazole, quaternary benzothiazole derivatives and benzotriazole.
  • the emulsions may be hardened in the usual manner, for example, with formaldehyde or by use of halogen-substituted aldehydes which contain a carboxyl group, e.g., mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
  • formaldehyde or by use of halogen-substituted aldehydes which contain a carboxyl group, e.g., mucobromic acid, diketones, methanesulfonic acid esters and dialdehydes.
  • the emulsions according to the invention may be used for all sorts of different photographic processes, for example, for copying materials, for reproduction photography, for X-ray films, for materials which are suitable for use in the silver salt diffusion process, for color photographic materials for the silver dye bleaching process, etc.
  • the sensitizers used according to the invention are in addition suitable for the spectral sensitization of electrophotographic layers, advantageously those layers which contain photoconductive zinc oxide distributed in an insulating binder.
  • EXAMPLE 30 mg. of the sensitizing dye No. 2 are added to a conventional photographic gelatino-silver chlorobromide emulsion, which is chemically sensitized with gold-III- chloride and is stabilized by addition of 7 ml. of a 1% methanolic solution of phenylmercaptotetrazole.
  • the emulsion is applied in the usual manner onto a baryta-coated paper support and dried.
  • the light-sensitive layer is exposed behind a stepped wedge; development takes place for 1 /2 minutes in a developer having the following composition:
  • the sensitizing action is not impaired if color couplers, e.g. yellow couplers, are added to the above emulsion.
  • the sensitization intensity and the stability under tropical conditions are excellent. Equally good results are also obtained by using other emulsions, such as silver bromide emulsions with a particularly steep gradation.
  • composition of claim 1 in which the light-sensitive material is a silver halide emulsion.
  • composition of claim 2 wherein the emulsion is a silver chloride or silver chlorobromide emulsion.
  • composition of claim 2, wherein the sensitizing compound has the formula:

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  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Organic Chemistry (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US709194A 1967-03-11 1968-02-29 Optically sensitized light-sensitive material Expired - Lifetime US3545975A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEA0055135 1967-03-11

Publications (1)

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US3545975A true US3545975A (en) 1970-12-08

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Country Status (7)

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US (1) US3545975A (en。)
BE (1) BE711378A (en。)
CH (1) CH497716A (en。)
DE (1) DE1522432C3 (en。)
FR (1) FR1559295A (en。)
GB (1) GB1221875A (en。)
NL (1) NL6802465A (en。)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS576092B2 (en。) * 1971-12-28 1982-02-03

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385707A (en) * 1963-05-18 1968-05-28 Agfa Ag Optically sensitized photographic materials containing neutrocyanine dyes

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3385707A (en) * 1963-05-18 1968-05-28 Agfa Ag Optically sensitized photographic materials containing neutrocyanine dyes

Also Published As

Publication number Publication date
DE1522432A1 (de) 1969-07-24
BE711378A (en。) 1968-08-28
CH497716A (de) 1970-10-15
FR1559295A (en。) 1969-03-07
NL6802465A (en。) 1968-08-26
DE1522432C3 (de) 1975-01-30
GB1221875A (en) 1971-02-10
DE1522432B2 (de) 1974-06-12

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