US3671260A - Organic thioether or selenoether silver complexes as emulsion sensitizers - Google Patents

Organic thioether or selenoether silver complexes as emulsion sensitizers Download PDF

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US3671260A
US3671260A US106531A US3671260DA US3671260A US 3671260 A US3671260 A US 3671260A US 106531 A US106531 A US 106531A US 3671260D A US3671260D A US 3671260DA US 3671260 A US3671260 A US 3671260A
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silver
photographic
emulsion
complex
dye
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Edwin N Oftedahl
Thomas J Huttemann Jr
Charles A Goffe
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Eastman Kodak Co
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    • 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
    • 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
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • 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
    • G03C1/346—Organic derivatives of bivalent sulfur, selenium or tellurium

Definitions

  • Photographic silver bromoiodide emulsions are spectrally sensitized by adding thereto a mixture comprising a photographic spectral sensitizing dye and a complex of silver with an organic thioether or an organic selenoether.
  • Addition of the silver complex reduces the blue desensitization caused by the sensitizing dye and thus increases spectral sensitization efficiency. Incubation stability of the emulsion is also enhanced.
  • This invention relates to photographic materials, and more particularly to a method for spectrally sensitizing photographic silver halide emulsions.
  • the poly(thiaalkylene diols) probably formed a complex with silver present in the silver halide crystals, and the silverpoly(thiaall ylene diol) complex possibly functioned to decrease the blue desensitization normally caused by photographic spectral sensitizing dyes. It would be desirable to provide still further decreases in the amount of gesensitization caused by photographic spectral sensitizing yes.
  • One object of this invention is to reduce the blue de- (siensitization caused by photographic spectral sensitizing yes.
  • Another object of this invention is to increase the efficiency of photographic spectral sensitization.
  • Still another object of this invention is to enhance the incubation stability of spectrally sensitized photographic silver halide emulsions.
  • a photographic silver bromoiodide emulsion is spectrally sensitized by adding thereto a mixture comprising a photographic spectral sensitizing dye and a complex of silver with an organic thioether or an organic selenoether.
  • Photographic emulsions spectrally sensitized in accordance with this invention exhibit reduced bluedesensitization caused by the dye.
  • the process of the invention increases the efficiency of spectral sensitization, both for molecular and l-band absorption.
  • the invention also enhances the incubation stability of photographic emulsions, particularly those Patented June 20, 1972 emulsions sensitized with red and infrared photographic spectral sensitizing dyes.
  • the mixture of photographic spectral sensitizing dye and the silver complex are heated prior to incorporation in the silver bromoiodide emulsion.
  • the heating step results in decreased dye desensitization, increased spectrally sensitized speeds and reduced fog.
  • photographic silver bromoiodide emulsions treated with a mixture comprising a photographic spectral sensitizing dye and a complex of silver with an organic thioether or selenoether are hypersensitized.
  • Any of the conventional prior art hypersensitizing treatments can be utilized, including those mentioned by Mees and James, The Theory of the Photographic Process, 3rd Edition, published by the Macmillan Co., 1966, page 252, and including bathing the finished coating in Water, an amine such as diethylamine, an ammoniacal solution or a solution of a silver salt, such as an aqueous solution of silver nitrite.
  • Coated emulsions are advantageously hypersensitized, e.g., by bathing in a dilute ammoniacal solution, such as 2 parts of 28% ammonia diluted with parts water for 2 to 3 minutes at about 5 C.
  • a dilute ammoniacal solution such as 2 parts of 28% ammonia diluted with parts water for 2 to 3 minutes at about 5 C.
  • Other suitable means for hypersensitizing photographic emulsions appear in an article by Miller et al., Journal of the Photographic Society of America, vol. 12, pages 5866l0, No. 10, November 1946.
  • photographic spectral sensitizing dye is used herein and in the appended claims as a word of art which denotes dyes employed as spectral sensitizers in negative, developing-out silver halide emulsions. Such dyes generally have a polarographic cathodic halfwave potential more positive than about l.05 volts.
  • cathodic measurements are made with a l 1O molar solution of the dye in a solvent, for example, methanol which is 0.05 molar in lithium chloride using a dropping mercury electrode with the polarographic halfwave potential for the most positive cathodic wave being designated E
  • Anodic measurements are made with 1X 10* molar aqueous solvent solution, for example, methanolic solutions of the dye which are 0.05 molar in sodium acetate and 0.05 molar in acetic acid using a carbon paste of pyrolytic graphite electrode, with the voltametric half peak potential for the most negative anodic response being designated E
  • the reference electrode is an aqueous silver-silver chloride (saturated potassium chloride) electrode at 20 C.
  • Electrochemical measurements of this type are known in the art and are described in New Instrumental Methods in Electrochemistry, by Delahay, Interscience Publishers, New York, N.Y., 1954; Polarography, by Kolthoff and Lingane, 2nd Edition, Interscience Publishers, New York, N.Y., 1952; Analytical Chemistry, 36, 2426 (1964) by Elving; and Analytical Chemistry, 30, 1576 (1958) by Adams.
  • the less negative (more positive) the cathodic (reduction) potential the greater is the electron affinity of a dye and conversely the less positive (more negative) the anodic (oxidation) potential of a dye, the greater is its electron-donating ability.
  • the useful photographic spectral sensitizing dyes include the methine dyes, such as the cyanine, merocyanine, hemicyanine, oxonol and styryl dyes.
  • Typical useful methine dyes are described in Brooker U.S. Pats. 1,846,- 301, issued Feb. 23, 1932; 1,846,302, issued Feb. 23,
  • L represents a methine group, such as those mentioned above;
  • Z is selected from a value given for Z and Z above;
  • R is an alkyl or aryl group, such as those referred to above; 1' and k each represents a positive integer of from 1 to 2;
  • Q represents the non-metallic atoms necessary to complete a heterocyclic ketomethylene nucleus of the type used in merocyanine dyes typically containing hetero atoms selected from nitrogen, sulfur, selenium and oxygen, such as a 1,3-dioxane-4,6-dione nucleus, e.g., 2,2-dialkyl-1,3-dioxane-4,6-dione, etc.; a 2-pyrazolin-5-one nucleus; e.g., 3-methyl-1-phenyl-2- pyrazolin-S-one
  • thiazolidinedione nucleus i.e., the 2-thio-2,5-(3H,4H)- thiazoledione series), e.g., 3-ethyl-2-thio-2,5-thiazolidinedione, etc.; a 2,4-thiazolidinedione nucleus, e.g., 2,4- thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl- 2,4 thiazolidinedione, 3-a-naphthyl-2,4-thiazolidinedione, etc.; a thiazolidinone nucleus, e.g., 4-thiazolidinone, 3-ethyl-4-thiazolidinone, 3-phenyl-4-thiazolidinone, 3-0:- naphthyl-4-thiazolidinone, etc.; a 2-thiazolin-4-one nucleus, e.g., 2-
  • Q and Q each represents the atoms to complete a ring containing from 3 to 4 carbon atoms, one nitrogen atom and one atom selected from the group consisting of nitrogen, oxygen, sulfur and selenium.
  • Typical useful merocyanine dyes are described, for example, in Brooker et al. Pats. 2,493,747 and 2,493,748, both issued Jan. 10, l 0.
  • Any silver complex with an organic thioether compound or an organic selenoether compound can be utilized in the practice of this invention.
  • a preferred class of complexes are those of silver with an alkane or cycloalkane containing from 5 to 30 carbon atoms in which from 2 to 6 -'CH groups, but not more than one half of the total number of CH groups, are replaced with a divalent selenium or, preferably, a divalent sulfur atom.
  • Dithia-tetraoxacyclooctadecanes are especially useful silver complexing agents.
  • the complexing agent is mixed with a suitable source, such as silver nitrate in a common solvent.
  • a suitable source such as silver nitrate
  • the mixture of sensitizing dye and silver complexing agent can be formulated in any convenient manner.
  • a silver source such as silver nitrate
  • the solvent is not critical; any solvent is useful which dissolves the dye, silver source, complexing agent and the silver complex formed.
  • Methanol is a solvent for many photographic sensitizing dyes and provides good results.
  • Other typical useful solvents include ethanol, isopropanol, pyridine, etc.
  • the mixture of dye and silver-organic thioether or selenoether complex is heated just prior to incorporation in the emulsion.
  • Heating a solution of dye and silver-organic complex to temperatures of about 30 to C., and preferably about 40 to 60 C., and maintaining the solution at that temperature from about 2 minutes to one hour, and preferably about 5 to 10 minutes, provides excellent increases in the spectrally sensitized speed of emulsions sensitized.
  • the photographic spectral sensitizing dye is incorporated in the emulsions in concentrations suflicient to spectrally sensitize the emulsion.
  • Typical dyes function as efficient spectral sensitizers in concentrations of from about .001 to about .300 gram per mole of silver in the emulsion.
  • the silver-organic complex is incorporated in the emulsions in concentrations sufficient to decrease the blue desensitization caused by the photographic sensitizing dye, and to increase the eflic'iency of spectral sensitization by the dye. Amounts of about 0.25 to about 0.75 gram of silver complex per mole of silver halide in the emulsions provide satisfactory results.
  • the process of the invention is useful in spectrally sensitizing photographic silver bromoiodide emulsions.
  • the halide of such emulsions preferably contains .at least 60%, and preferably at least 80 to bromide.
  • Other photographic silver halides, such as silver chlorobromide, are ripened (i.e., the grains grow larger) by the complexing agents employed herein.
  • Emulsions sensitized as described herein can be coated on any suitable photographic support, such as glass, film base such as cellulose acetate, cellulose acetate butyrate, polyesters such as poly(ethylene terephthalate), paper, baryta coated paper, polyolefin coated paper, e.g., polyethylene or polypropylene coated paper, which may be electron bombarded to promote emulsion adhesion, to produce the novel photographic elements of the invention.
  • film base such as cellulose acetate, cellulose acetate butyrate
  • polyesters such as poly(ethylene terephthalate), paper, baryta coated paper, polyolefin coated paper, e.g., polyethylene or polypropylene coated paper, which may be electron bombarded to promote emulsion adhesion, to produce the novel photographic elements of the invention.
  • Emulsions sensitized in accordance with this invention can contain addenda such as chemical sensitizers, e.g., sulfur sensitizers (e.g., allyl thiocarbamate, thiourea, allylisothiocyanate, cystine, etc.) various gold compounds (e.g., potassium chloroaurate, auric trichloride, etc. (see Baldsiefen US. Pat. 2,540,085, issued Feb. 6, 1951; Damschroder US Pat. 2,597,856, issued May 27, 1952 and Yutzy et al. US. Pat. 2,597,915, issued May 27, 1952), various palladium compounds such as palladium chloride (Baldsiefen US.
  • chemical sensitizers e.g., sulfur sensitizers (e.g., allyl thiocarbamate, thiourea, allylisothiocyanate, cystine, etc.)
  • gold compounds e.g., potassium chloroau
  • the silver halide emulsions of the invention can be hardened with any suitable hardener, including aldehyde hardeners such as formaldehyde, and mucochloric acid, aziridine hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides such as oxy starch or oxy plant gums, and the like.
  • aldehyde hardeners such as formaldehyde, and mucochloric acid
  • aziridine hardeners hardeners which are derivatives of dioxane, oxypolysaccharides such as oxy starch or oxy plant gums, and the like.
  • the emulsion layers can also contain additional additives, particularly those known to be beneficial in photographic emulsions, including, for example, lubricating materials, stabilizers, speed-increasing materials, absorbing dyes, plasticizers, and the like. These photographic emulsions can also contain additional spectral sensitizing dyes. Furthermore, these emulsions can contain color-forming couplers or can be developed in solutions containing couplers or other colorgenerating materials. Among the useful color formers are the monomeric and polymeric color formers, e.g., pyrazolone color formers, as well as phenolic, heterocyclic and open-chain couplers having a reactive methylene group.
  • the color-forming couplers can be incorporated into the photographic silver halide emulsion using any suitable technique, e.g., techniques of the type shown in Jelley et al. US. Pat. 2,322,027, issued June 15, 1943, Fierke et al. US. Pat. 2,801,171, issued July 30, 1957, Fisher U.S. Pats. 1,055,155 and 1,102,028, issued Mar. 4, 1913 and June 30, 1914, respectively, and Wilmanns US. Pat. 2,186,849, issued Jan. 9, 1949. They can also be developed using incorporated developers such as polyhydroxybenzenes, aminophenols, 3-pyrazolidones, and the like.
  • EXAMPLE 1 A sulfur and gold sensitized, large grain, liquid gelatin silver bromoiodide (about 6 mole percent of the halide being iodide) emulsion is stirred thoroughly, combined with a suitable surfactant (e.g., saponin) and hardener (e.g., formaldehyde) and coated on a cellulose acetate support at a coverage of 350 mg. silver and 810 mg. gelatin per square foot.
  • a suitable surfactant e.g., saponin
  • hardener e.g., formaldehyde
  • One set of coatings is exposed to tungsten light on an Eastman 1B sensitometer and processed for minutes at 20 C. in Kodak D-SO developer.
  • the relative speed values obtained are given in Table I.
  • the relative blue speed is obtained by exposing the element through a combination of filters: Wratten 35 plus 38A plus a blue filter that absorbs green and red light and transmits blue light.
  • Example 2 The procedure of Example 1 is followed except that infrared sensitizing dyes I and II (identified at the end of Table I) are added to the emulsion along with the silver complexing agent 1,10-dithio 4,7,13,16 tetraoxacyclooctadecane (which forms a silver complex with silver ion in the emulsion).
  • the infrared speed is determined by exposure on the sensitometer through a Wratten 89B filter. The results appear in Table I.
  • EXAMPLES 6-8 The procedure of Examples 3-5 is repeated except that the methanolic solution of sensitizing dyes, silver complexing agent and silver nitrate is heated to 50 C., held at that temperature for 6 minutes, and then added to the emulsion. The results are shown in Table I.
  • Table I shows that the ex situ preparation of the silver complex-dye mixture is more efiicient than the in situ formation of the silver complex of the organic ligand, D (Example 2 versus Examples 3-8).
  • Examples 3-5 and 6-8 indicate that the amount of silver nitrate available to form the silver complex has a marked influence on the efiiciency of the supersensitization.
  • a heat treatment during the pre-mixing step causes a further gain in spectrally sensitized speed.
  • EXAMPLE 9 A non-spectrally sensitized control coating is prepared and coated as in Example 1. The dried element is exposed and processed as in Examples 1-8, except that a Wratten 29 filter (red) is substituted for the Wratten 89B filter. An additional set of coatings is hypersensitized by bathing for 2 to 3 minutes in a 5 C. solution consisting of 2 parts 28% aqueous ammoniacal solution and 100 parts water, rinsed in methanol, dried, immediately exposed and processed as the control coating. The unhypered coating is assigned a blue speed of 100 and has a minimum density of 0.04. The ammonia hypered coating has a relative blue speed of 138 and a minimum density of 0.06.
  • Example 9 The procedure set out in Example 9 is followed with the exception that the emulsion is spectrally sensitized with a pre-mixed, pre-heated solution consisting of a spectral sensitizing dye (at various levels), and 0.6 gram of silver complex per silver mole of emulsion.
  • the silver complexing agent (D) is identical to the one used in Examples 2-8.
  • the sensitometric data obtained from these unhypered and hypered coatings are listed in Table II. The following individual sensitizing dyes are incorporated in the coatings:
  • the method of spectrally sensitizing a photographic show equal or nearly equal red speeds in comparison with 25 silver bromoiodide emulsion which comprises adding to the hypered coat ngs containmg an equal amount of sensaid emulsion a mixture comprising a photographic specsitizing dye anclno silver complex. For instance, compare tral sensitizing dye and a complex of silver with an or- Example 13 (unhypered) with Example 11 (hypered), ganic thioether or an organic selenoether. Example 17 (unhypered) with Example 15 (hypered), 2.
  • the method of spectrally sensitizing a photographic Example 21 (unhypered) with Example 19 (hypered) and silver bromoiodide emulsion which comprises adding to Example 23 (u yp Wlth f p 22 yp fimsaid emulsionamixture comprising: in most cases the yp cotmgs l
  • a photographic spectral sensitizing dye having one some examples the hypered coatings contammg a silver f h following formulas; complexing agent have more speed than hypered coatings containing a. sensitizing dye and no complexing agent.
  • a photographic spectral sensitizing dye having one some examples the hypered coatings contammg a silver f h following formulas; complexing agent have more speed than hypered coatings containing a. sensitizing dye and no complexing agent.
  • F 9 represents alkyl g p an alkylene group use of a silver complexing agent with a spectral sensitizing Joined to a methme llnkfige. an Y p; Q dye duplicates the sensitometric advanges of low pAg represents the Rolf-Install atoms l'equlred to coatings with the dye alone, without an increase in fog- Plate a hetefocycllc ketofnethylene 1111016138 9 ging propensity upon incubation.
  • the emulsion, coating mg from 5 to 6 atoms 1n the heterocyclic rmg; m format, exposure and processing procedures are the same represents an nteger of from 1 to 5 d, n and 1' each as in Examples 9-23.
  • the final pAg of the final emulsion represents an integer of from 1 to 2; k represents an composition is adjusted with a solution of silver nitrate. integer of from 1 to 3; and X represents an acid Table III contains the sensitometric data obtained from anion; and these examples.
  • the complexing agent is 1,10-dithia-4,7, (b) a complex of silver w1th an alkane or cycloalkane 13,16-tetraoxacyclooctadecane (D).
  • Oomplexing Agent D 1,10-dithia4,7,13,1otetraoxacyclooctadecane. Exposure: 1/5 second 500W 5,400 K. Processing: 5 minutes Kodak D-50 developer.
  • the metod of spectrally sensitizing a photographic silver bromoiodide emulsion which comprises adding to 11 said emulsion a methanolic solution comprising the photographic spectral sensitizing dyes 3,3'-diethylselenodicarbocyanine salt and anhydro-1-ethyl-3-(3-sulfobutyl)thia- 2'-cyanine salt, and a complex of silver with 1,10-dithia- 4,7,13,16-tetraoxacyclooctadecane.
  • the method of spectrally sensitizing a photographic silver bromoiodide emulsion which comprises heating a solution of a silver salt, an organic thioether or an organic selenoether, and a photographic spectral sensitizing dye; and, adding said heated solution to said silver bromoiodide emulsion.
  • Z, Z and Z each represents the non-metallic atoms required to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring
  • each L represents a methine linkage
  • R R and R each represents an alkyl group, an alkylene group joined to a methine linkage, or an aryl group
  • Q represents the non-metallic atoms required to complete a heterocyclic ketomethylene nucleus containing from 5 to 6 atoms in the heterocyclic ring
  • m represents an integer of from 1 to 5
  • d n and j each represents an integer of from 1 to 2
  • k represents an integer of from 1 to 3
  • X represents an acid anion
  • the method of spectrally sensitizing a photographic silver bromoiodide emulsion which comprises heating for 5 to 10 minutes, at 40 to 60 C. a methanolic solution containing the sensitizing dyes 3,3'-diethylselenodicarbocyanine salt and anhydro-1-ethyl-3-(3-sulfobutyl)thia-2'- cyanine salt and, a complex of silver with 1,10-dithia-4,7, 13,16-tetraoxacyclooctadecane; and, adding said heated solution to said emulsion.
  • Z, Z and Z each represents the non-metallic atoms required to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring; each L represents a methine linkage; R R and R each represents an alkyl group, an alkylene group joined to a methine linkage, or an aryl group; Q represents the non-metallic atoms required to complete a heterocyclic ketomethylene nucleus containing from 5 to 6 atoms in the heterocyclic ring; In represents an integer of from 1 to 5; d, n and j each represents an integer of from 1 to 2; k represents an integer of from 1 to 3; and, X represents an acid anion; and v p (b) a complex of silver with an alkane or cycloalkane containing from 5 to 20 carbon atoms in which from 2 to 6 -CH groups, but not more than one half the total number of -CH-,-- groups, are replaced with a divalent sulfur or se
  • the method of spectrally sensitizing a photographic silver bromoiodide emulsion which comprises heating for 5 to 10 minutes, at 40 to 60 C. a methanolic solution containing the sensitizing dyes 3,3'-diethylselenodicarbocyanine salt; anhydro 1 ethyl-3-(3-sulfobutyl)thia-2'- cyanine salt and, a complex of silver with 1,10-dithia-4,7, 13,16-tetraoxacyclooctadecane; coating said emulsion on a support; and, bathing said emulsion for 2 to 3 minutes in anamrnoniacal bath consisting essentially of 2 parts of 28% aqueous ammoniacal solution and parts water, said bath being maintained at about 5 C. during hypersensitization.
  • anamrnoniacal bath consisting essentially of 2 parts of 28% aqueous ammoniacal solution and parts water

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Abstract

PHOTOGRAPHIC SILVER BROMOIODIDE EMULSIONS ARE SPECTRALLY SENSITIZED BY ADDING THERETO A MIXTURE COMPRISING A PHOTOGRAPHIC SPECTRAL SENSITIZING DYE AND A COMPLEX OF SILVER WITH AN ORGANIC THIOETHER OR AN ORGANIC SELENOETHER. ADDITION OF THE SILVER COMPLEX REDUCES THE BLUE DESENSITIZATION CAUSED BY THE SENSITIZING DYE AND THUS INCREASES SPECTRAL SENSITIZATION EFFICIENCY, INCUBATION STABILITY OF THE EMULSION IS ALSO ENHANCED.

Description

United States Patent 3,671,260 ORGANIC THIOETHER 0R SELENOETHER SILVER COMPLEXES AS EMULSION SENSITIZERS Edwin N. Oftedahl, Rochester, Thomas J. Huttemann,
Jr., Henrietta, and Charles A. Gotle, Brockport, N.Y.,
assignors to Eastman Kodak Company, Rochester, NY. No Drawing. Filed Jan. 14, 1971, Ser. No. 106,531
Int. Cl. G03c N28 US. Cl. 96-122 11 Claims ABSTRACT OF THE DISCLOSURE Photographic silver bromoiodide emulsions are spectrally sensitized by adding thereto a mixture comprising a photographic spectral sensitizing dye and a complex of silver with an organic thioether or an organic selenoether.
Addition of the silver complex reduces the blue desensitization caused by the sensitizing dye and thus increases spectral sensitization efficiency. Incubation stability of the emulsion is also enhanced.
This invention relates to photographic materials, and more particularly to a method for spectrally sensitizing photographic silver halide emulsions.
Williams and Cossar in US. Pat. 3,021,215, issued Feb. 13, 1962, in column 14, lines 27-33 describe the addition of poly(thiaalkylene diols) to spectrally sensitized gelatin silver bromoiodide emulsions. Such compounds increase the speed of photographic silver halide emulsions. Applicants investigation of the use of various complexes in spectrally sensitizing silver halide emulsions indicates that an unrecognized phenomenon probably occurred when Williams and Cossar added poly(thiaalkylene diols) to spectrally sensitized silver bromoiodide emulsions. The poly(thiaalkylene diols) probably formed a complex with silver present in the silver halide crystals, and the silverpoly(thiaall ylene diol) complex possibly functioned to decrease the blue desensitization normally caused by photographic spectral sensitizing dyes. It would be desirable to provide still further decreases in the amount of gesensitization caused by photographic spectral sensitizing yes.
One object of this invention is to reduce the blue de- (siensitization caused by photographic spectral sensitizing yes.
Another object of this invention is to increase the efficiency of photographic spectral sensitization.
Still another object of this invention is to enhance the incubation stability of spectrally sensitized photographic silver halide emulsions.
Other objects of this invention will be apparent from this disclosure and the appended claims.
In accordance with this invention, a photographic silver bromoiodide emulsion is spectrally sensitized by adding thereto a mixture comprising a photographic spectral sensitizing dye and a complex of silver with an organic thioether or an organic selenoether. Photographic emulsions spectrally sensitized in accordance with this invention exhibit reduced bluedesensitization caused by the dye. The process of the invention increases the efficiency of spectral sensitization, both for molecular and l-band absorption. The invention also enhances the incubation stability of photographic emulsions, particularly those Patented June 20, 1972 emulsions sensitized with red and infrared photographic spectral sensitizing dyes.
In accordance with a preferred embodiment of this invention, the mixture of photographic spectral sensitizing dye and the silver complex are heated prior to incorporation in the silver bromoiodide emulsion. The heating step results in decreased dye desensitization, increased spectrally sensitized speeds and reduced fog.
In still another embodiment of this invention, photographic silver bromoiodide emulsions treated with a mixture comprising a photographic spectral sensitizing dye and a complex of silver with an organic thioether or selenoether are hypersensitized. Any of the conventional prior art hypersensitizing treatments can be utilized, including those mentioned by Mees and James, The Theory of the Photographic Process, 3rd Edition, published by the Macmillan Co., 1966, page 252, and including bathing the finished coating in Water, an amine such as diethylamine, an ammoniacal solution or a solution of a silver salt, such as an aqueous solution of silver nitrite.
Coated emulsions are advantageously hypersensitized, e.g., by bathing in a dilute ammoniacal solution, such as 2 parts of 28% ammonia diluted with parts water for 2 to 3 minutes at about 5 C. Other suitable means for hypersensitizing photographic emulsions appear in an article by Miller et al., Journal of the Photographic Society of America, vol. 12, pages 5866l0, No. 10, November 1946.
The term photographic spectral sensitizing dye is used herein and in the appended claims as a word of art which denotes dyes employed as spectral sensitizers in negative, developing-out silver halide emulsions. Such dyes generally have a polarographic cathodic halfwave potential more positive than about l.05 volts. In accordance with the present invention, cathodic measurements are made with a l 1O molar solution of the dye in a solvent, for example, methanol which is 0.05 molar in lithium chloride using a dropping mercury electrode with the polarographic halfwave potential for the most positive cathodic wave being designated E Anodic measurements are made with 1X 10* molar aqueous solvent solution, for example, methanolic solutions of the dye which are 0.05 molar in sodium acetate and 0.05 molar in acetic acid using a carbon paste of pyrolytic graphite electrode, with the voltametric half peak potential for the most negative anodic response being designated E In each measurement, the reference electrode is an aqueous silver-silver chloride (saturated potassium chloride) electrode at 20 C. Electrochemical measurements of this type are known in the art and are described in New Instrumental Methods in Electrochemistry, by Delahay, Interscience Publishers, New York, N.Y., 1954; Polarography, by Kolthoff and Lingane, 2nd Edition, Interscience Publishers, New York, N.Y., 1952; Analytical Chemistry, 36, 2426 (1964) by Elving; and Analytical Chemistry, 30, 1576 (1958) by Adams. The less negative (more positive) the cathodic (reduction) potential, the greater is the electron affinity of a dye and conversely the less positive (more negative) the anodic (oxidation) potential of a dye, the greater is its electron-donating ability.
The useful photographic spectral sensitizing dyes include the methine dyes, such as the cyanine, merocyanine, hemicyanine, oxonol and styryl dyes. Typical useful methine dyes are described in Brooker U.S. Pats. 1,846,- 301, issued Feb. 23, 1932; 1,846,302, issued Feb. 23,
1932; and 1,942,854, issued Jan. 9, 1934; White US. Pat. 11,990,507, issued Feb. 12, 1935; Brooker and White U .8. Patents 2,112,140, issued Mar. 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued Jan. 10, 1950, and 2,739,964, issued Mar. 27, 1956; Brooker and Keyes US. Pat. 2,493,748, issued J an. 10, 1950; Sprague U.S. Pats. 2,503,776, issued Apr. 11, 1950, and 2,519,001, issued Aug. 15, 1950; 'Heseltine and Brooker U.S. Pat. 2,666,761, issued Jan. 19, 1954; Heseltine US. Pat. 2,734,900, issued Feb. 14, 1956; Van Lare US. Pat. 2,739,149, issued Mar. 20, 1956; and Kodak Limited British 'Pat. 450,958, accepted July 15, 1936.
:Preferred cyanine dyes which can be employed in accordance with this invention have the following genwherein d and it each represents a positive integer of from 1 to 2, m represents a positive integer of from 1 to 5, each L represents a methine group (e.g., CH=, -C(CH etc.), and Z and Z each represents the non-metallic atoms necessary to complete a heterocyclic nucleus containing from to 6 atoms in the heterocyclic ring, e.g., thiazole, 4-phenylthiazole, 4,5-diphenylthiazole, 4-(2-thienyl)thiazole, 4-methylthiazole, 'benzothiazole, 4- chlorobenzothiazole, 4-methylbenzothiazole, 4-methoxybenzothiazole, 4-ethoxybenzothiazole, 4-phenylbenzothiazole, S-chlorobenzothiazole, 5-bromobenzothiazole, 5- methylbenzothiazole, S-methoxybenzothiazole, 5-ethoxybenzothiazole, S-phenylbenzothiazole, 6-chlorobenzothiazole, 6-bromobenzothiazole, 6-methylbenzothiazole, 6- methoxybenzothiazole, 'fi-ethoxybenzothiazole, 4-phenyloxazole, benzoxazole, 5 chlorobenzoxazole, S-methylbenzoxazole, 5 bromobenzoxazole, 5 methoxybenzoxazole, 5-ethoxybenzoxazole, S-phenylbenzoxazole, 1,3-dialkyl, 1,3-diaryl or 1-al'kyl-3-ary1, imidazoles and benzimidazoles, such as 5-chloro-l,3-dial'kyl benzimidazoles, 5-chlor0-1,3-diaryl benzimidazoles, 5,6-dichloro -1,3 dialkyl benzimidazoles, 5,6-dichloro 1,3 diaryl benzimidazoles, 5-methoxy-1,3-dialkyl benzimidazoles, S-methoxy- 1,3-diaryl benzimidazoles, 5-cyano-1,3-dialkyl benzimidazoles, 5-cyano 1,3 diaryl benzimidazoles, 1,3-dia1kylnaphth[1,2-d]imidazole, 1,3 diarylnaphth[2,1-d]imidazole, 4-methylselenazole, 4-phenylselenazole, selenazole, benzoselenazole, 5-chlorobenzoselenazole, a-naphthothiazole, fl-naphthothiazole, quinoline, G-methylquinoline, 6- methoxyquinoline, 6-ethoxyquinoline, 6-chloroquinoline, 4 methoxyquinoline, 4 ethoxyquinoline, 4-methylquinoline, 8-methoxyquinoline, fi-methylquinoline, 4-chloroquinoline, 3,3-dimethylindolenine, etc.; X represents an acid anion, such as chloride, bromide, p-toluene sulfonate, methane sulfonate, methylsulfate, ethylsulfate, perchlorate, etc.; R and R each represents an alkyl group (including substituted alkyl) having from 1 to 118, and preferably 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, hexyl, dodecyl, octadecyl, benzyl, p-phenylethyl sulfoalkyl such as S-sulfoethyl, 'ysulfopropyl, -sulfobutyl, a-sulfobutyl, etc.; carboxyalkyl such as B-carboxyethyl, 'y-carboxypropyl, 6-carboxybutyl, etc.; sulfatoalkyl such as 'y-sulfatopropyl and fi-sulfatobutyl, etc., or an alkylene chain which joins with a methine linkage, such as a butylene or neopentylene linkage, or an aryl group such as phenyl, naphthyl, tolyl, pchlorophenyl, etc. It will be noted that in some instances, the acid anion, represented by X in the above formula, is included in the substituent represented by R such as dyes containing the betaine type structure. Some specific useful cyanine dyes are listed below:
'1',3-diethylthia-2'-cyanine chloride 1,l'-diethyl-2,'2'-cyanine chloride 3,3'-diethy1oxacarbocyanine iodide 5,5-dichloro-3,3'-diethylthiacarbocyanine iodide l,1'-diethyl-2,2'-carbocyanine iodide 3,3'-diethylthiazolocarbocyanine iodide 3,3'-diethyl-4,4'-dephenylthiazolocarbocyanine iodide 3,3'-diethyl-9-methylthiacarbocyanine iodide 1,3,3 -triethylbenzimidazole-oxacarbocyanine iodide 5-chloro-l,3,3-triethylbenzimidaZolo-oxacarbocyanine iodide 5,6-dichloro-1,3,3'-triethylbenzimidazolothiacarbocyanine iodide l,1'-3-triethylbenzimidaZol0-2-carbocyanine iodide 1,1',3-triethylbenzimidazolo-4'-carbocyanine iodide 1,1'-diethyl-2,4-carbocyanine iodide 1,3-diethyl-4-methylthiazo1o-2-carbocyanine iodide 3,3-diethylthiadicarbocyanine iodide 1, 1 '-diethyl-2,2-dicarbocyanine iodide 1',3-diethylthia-2'-dicarbocyanine iodide Anhydro-5,5'-6,6-te-trachloro-1,1,3-triethy1-3'-(4-su1fobutyl)benzimidazolocarbocyanine hydroxide Anhydro-5,6-dichloro-1-ethy1-3-(3-sulfobutyl)-3'-(3- sulfopropyl)-4',5'-benzobenzimidazolothiacarboy cyanine hydroxide 1,1',3,3 -tetraethyl-naphth[1,2-d]imidazolocarbocyanine iodide Anhydro-5,'6-dichloro-1,3-diethyl-(3-sulfobutyl)-benzimidazoloselenacarbocyanine hydroxide 1,2-diethylthia-4-carbocyanine iodide Anhydro-5,5',6,6'-tetrachloro-1,1'-diethy1-3,3'-di(4- sulfobutyl)-benzimidazolocarbocyanine hydroxide Merocyanine dyes especially useful in this invention have the following formula:
,-Q-, R,-I 'I -0H=0H)i-lo= LL)k-1=o-o=o wherein L represents a methine group, such as those mentioned above; Z is selected from a value given for Z and Z above; R is an alkyl or aryl group, such as those referred to above; 1' and k each represents a positive integer of from 1 to 2; and Q represents the non-metallic atoms necessary to complete a heterocyclic ketomethylene nucleus of the type used in merocyanine dyes typically containing hetero atoms selected from nitrogen, sulfur, selenium and oxygen, such as a 1,3-dioxane-4,6-dione nucleus, e.g., 2,2-dialkyl-1,3-dioxane-4,6-dione, etc.; a 2-pyrazolin-5-one nucleus; e.g., 3-methyl-1-phenyl-2- pyrazolin-S-one, 1-phenyl-2-pyrazolin-5-one, 1-(2-benzothiazolyl)-3-methyl-2-pyrazolin-5-one, etc.; an isoxazolone nucleus, e.g., 3-phenyl 5 (4H)-isoxazolone, 3-methyl- 5(4H)-isoxazolone, etc.; an oxindole nucleus, e.g., l-alkyl- 2-oxindoles, etc.; a 2,4,6-triketohexahydropyrimidine nucleus, e.g., barbituric acid or 2-thiobarbituric acid as well as their l-alkyl (e.g., l-methyl, l-ethyl, l-propyl, l-heptyl, etc.) or 1,3-dialkyl (e.g., 1,3-dimethyl, 1,3-diethyl, 1,3- dipropyl, 1,3 diisopropyl, 1,3 dicyclohexyl, 1,3 di(flmethoxyethyl), etc.; or 1,3-diaryl (e.g., 1,3-diphenyl, 1,3- di(p chlorophenyl), 1,3 di(p ethoxycarbonylphenyl), etc.); or l-aryl (e.g., l-phenyl, l-p-chlorophenyl, l-pethoxycarbonylphenyl), etc.) or 1-alkyl-3-aryl (e.g., 1-ethy1-3-phenyl, 1-n-heptyl-3-phenyl, etc.) derivatives, 21 rhodanine nucleus (i.e., 2 thio 2,4 thiazolidinedione series), such as rhodanine, 3-alkylrhodanines, e.g., 3-ethylrhodanine, 3-ally1rhodanine, etc., S-carboxyalkylrhodanines, e.g., 3-(2-carboxyethyl)rhodanine, 3-(4-carboxybutyl)rhodanine, etc., 3-sulfoa1kylrhodanines, e.g., 3-(2- sulfoethyl)rhodanine, 3-(3-sulfopropyl)rhodanine, 3-(4- sulfobutyl)rhodanine, etc., or 3-arylrhodanines, e.g., 3-phenylrhodanine, etc., a 2-(3H)-imidazo[1,2-a]pyridone nucleus; a 5,7-dioxo-6,7-dihydro-5-thiazolo[3,2-a]pyrimidine nucleus, e.g., 5,7-dioxo-3-phenyl-6,7-dihydro-5-thiazolo[3,2-a]pyrimidine, etc.; a 2-thio-2,4-oxazolidinedione nucleus (i.e., those of the 2-thio-2,4(3H,5H)-oxazoledione series) e.g., 3-ethyl-2-thio-2,4-oxazolidinedione, 3-(2-su1foethyl)-2-thio 2,4 oxazolidinedione, 3-(4-sulfobutyl)-2-thio-2,4-oxazolidinedione, 3 (3carboxypropyl)- 2-thio-2,4-oxazolidinedione, etc.; a thianaphthenone nucleus, e.g., 3-(2H)-thianaphthenone, etc.; a 2-thio-2,5-
thiazolidinedione nucleus (i.e., the 2-thio-2,5-(3H,4H)- thiazoledione series), e.g., 3-ethyl-2-thio-2,5-thiazolidinedione, etc.; a 2,4-thiazolidinedione nucleus, e.g., 2,4- thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl- 2,4 thiazolidinedione, 3-a-naphthyl-2,4-thiazolidinedione, etc.; a thiazolidinone nucleus, e.g., 4-thiazolidinone, 3-ethyl-4-thiazolidinone, 3-phenyl-4-thiazolidinone, 3-0:- naphthyl-4-thiazolidinone, etc.; a 2-thiazolin-4-one nucleus, e.g., 2-ethylmercapto-2-thiazolin-4-one, 2-alky1- phenylamino-Z-thiazolin 4 one, 2-diphenylamino-2-thiazolin-4-one, etc.; a 2-imino-4-oxazolidinone (i.e., pseudohydantoin) nucleus; 21 2,4-imidazolidinedione (hydantoin) nucleus, e.g., 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, 3-phenyl-2,4-imidazolidinedione, 3-u-naphthyl- 2,4-imidazolidinedione, l,3-diethyl-2,4-imidazolidinedione, l-ethyl 3 phenyl 2,4 imidazolidinedione, l-ethyl-3-anaphthyl-2,4-imidazolidinedione, 1,3-diphenyl 2,4 imidazolidinedione, etc.; a 2-thio-2,4-imidazolidinedione (i.e., 2-thiohydantoin) nucleus, e.g., 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione, 3-(4-sulfobutyl)-2-thio-2,4-imidazolidinedione, 3-(2-carboxyethyl)- 2-thio-2,4-imidazolidinedione, 3-phenyl 2 thio-2,4-imidazolidinedione, 3 a naphthyl 2 thio-2,4-imidazolidine dione, 1,3-diethyl-2-thio-2,4-imidazolidinedione, l-ethyl- 3-phenyl-2-thio2,4-imidazolidinedione, 1 ethyl-3-a-naphthyl-2-thio 2,4 imidazolidinedione, 1,3-diphenyl-2-thio- 2,4-imidazolidinedione, etc.; a Z-imidazolin-S-one nucleus, e.g., 2-propylmercapto-Z-imidazolin-S-one, etc. Preferably, Q and Q each represents the atoms to complete a ring containing from 3 to 4 carbon atoms, one nitrogen atom and one atom selected from the group consisting of nitrogen, oxygen, sulfur and selenium. Typical useful merocyanine dyes are described, for example, in Brooker et al. Pats. 2,493,747 and 2,493,748, both issued Jan. 10, l 0.
Particularly good results are obtained with the following cyanine and merocyanine dyes:
3,3'-diethyl-9, l 1,15,17-dineopentylenethiapentacarbocyanine iodide 3,3'-diethylselenadicarbocyanine iodide 1,3-diethyl-5- [4-( 3-ethyl-2-benzothiazolinylidene -2- butenylidene]-2-thiobarbituric acid 3,3'-diethylthiacarbocyanine chloride 3,3'-diethylcyanine chloride 3,3-diethylcarbocyanine iodide 5,5',6,6'-tetrachloro-1,1',3,3-tetraethylbenzimidazolocarbocyanine chloride Anhydro-5,5,6,6'-tetrachloro-1,1-diethyl-3,3'-di(3-sulfobutyl)benzimidazolocarbocyanine hydroxide Anhydro-S,5,6,6'-tetrachloro-1,l,3-triethyl3-(3- sulfobutyl)benzimidazolocarbocyanine hydroxide 5,5'-dichloro-3,3-diethyl-9-phenylselenacarbocyanine iodide 3,3,9-triethyl-5,6,5',6'-dibenzothiacarbocyanine p-toluenesulfonate If desired, combinations of photographic spectral sensitizing dyes can be employed in the practice of the invention.
Any silver complex with an organic thioether compound or an organic selenoether compound can be utilized in the practice of this invention. A preferred class of complexes are those of silver with an alkane or cycloalkane containing from 5 to 30 carbon atoms in which from 2 to 6 -'CH groups, but not more than one half of the total number of CH groups, are replaced with a divalent selenium or, preferably, a divalent sulfur atom. Dithia-tetraoxacyclooctadecanes are especially useful silver complexing agents. Some organic thioether and selenoether compounds which form particularly useful silver complexes are set out below:
l,4-bis( 5-hydroxy-3-thiapentyl) piperazine 3,4-diaza-1,16-dithia-9,12,l5-trioxa-2,4 cycloheptadecadiene-2,5-sulfide.
Poly [2,2-thiodiethylsuccinate] l,l0-dithia-4,7,13,16-tetraoxacyclooctadecane 4,7,13,16-tetraoxa-l,lO-diselenocyclooctadecane Poly[thiodiethylene glutarate] 1,3-bis(4-phenyl-1,2,4-triazol-3-ylthio) propane 1,8-dihydroxy-3,6-d-ithiaoctane Bis(3-oxapentamethylene carbamyloxyethyldisulfide) The complex of silver with the organic thioether or selenoether can be prepared in any convenient manner prior to incorporation in the emulsion. Advantageously, the complexing agent is mixed with a suitable source, such as silver nitrate in a common solvent. The mixture of sensitizing dye and silver complexing agent can be formulated in any convenient manner. For example, a silver source, such as silver nitrate, can be added to a solution containing the organic thioether or selenoether complexing agent and dye. The solvent is not critical; any solvent is useful which dissolves the dye, silver source, complexing agent and the silver complex formed. Methanol is a solvent for many photographic sensitizing dyes and provides good results. Other typical useful solvents include ethanol, isopropanol, pyridine, etc.
Preferably the mixture of dye and silver-organic thioether or selenoether complex is heated just prior to incorporation in the emulsion. Heating a solution of dye and silver-organic complex to temperatures of about 30 to C., and preferably about 40 to 60 C., and maintaining the solution at that temperature from about 2 minutes to one hour, and preferably about 5 to 10 minutes, provides excellent increases in the spectrally sensitized speed of emulsions sensitized.
The photographic spectral sensitizing dye is incorporated in the emulsions in concentrations suflicient to spectrally sensitize the emulsion. Typical dyes function as efficient spectral sensitizers in concentrations of from about .001 to about .300 gram per mole of silver in the emulsion.
The silver-organic complex is incorporated in the emulsions in concentrations sufficient to decrease the blue desensitization caused by the photographic sensitizing dye, and to increase the eflic'iency of spectral sensitization by the dye. Amounts of about 0.25 to about 0.75 gram of silver complex per mole of silver halide in the emulsions provide satisfactory results.
The process of the invention is useful in spectrally sensitizing photographic silver bromoiodide emulsions. The halide of such emulsions preferably contains .at least 60%, and preferably at least 80 to bromide. Other photographic silver halides, such as silver chlorobromide, are ripened (i.e., the grains grow larger) by the complexing agents employed herein.
Emulsions sensitized as described herein can be coated on any suitable photographic support, such as glass, film base such as cellulose acetate, cellulose acetate butyrate, polyesters such as poly(ethylene terephthalate), paper, baryta coated paper, polyolefin coated paper, e.g., polyethylene or polypropylene coated paper, which may be electron bombarded to promote emulsion adhesion, to produce the novel photographic elements of the invention.
Emulsions sensitized in accordance with this invention can contain addenda such as chemical sensitizers, e.g., sulfur sensitizers (e.g., allyl thiocarbamate, thiourea, allylisothiocyanate, cystine, etc.) various gold compounds (e.g., potassium chloroaurate, auric trichloride, etc. (see Baldsiefen US. Pat. 2,540,085, issued Feb. 6, 1951; Damschroder US Pat. 2,597,856, issued May 27, 1952 and Yutzy et al. US. Pat. 2,597,915, issued May 27, 1952), various palladium compounds such as palladium chloride (Baldsiefen US. Patent 2,540,086, issued Feb. 6, 1951), potassium chloropalladate (Stauffer et al. U.S. Patent 2,598,079, issued May 27, 1952), etc., or mixtures of such sensitizers; antifoggants such as ammonium chloroplatinate (Trivelli et al. US. Patent 2,- 566,245, issued Aug. 28, 1951), ammonium chloroplatinate (Trivelli et al. US. Patent 2,566,263, issued Aug.
28, 1951), benzotriazole, nitrobenzimidazole, S-nitroimidazole, benzidine, mercaptans, etc. (see Mees and James, The Theory of the Photographic Process, Macmillan Publishers, 1942, page 460), or mixtures thereof. The silver halide emulsions of the invention can be hardened with any suitable hardener, including aldehyde hardeners such as formaldehyde, and mucochloric acid, aziridine hardeners, hardeners which are derivatives of dioxane, oxypolysaccharides such as oxy starch or oxy plant gums, and the like. The emulsion layers can also contain additional additives, particularly those known to be beneficial in photographic emulsions, including, for example, lubricating materials, stabilizers, speed-increasing materials, absorbing dyes, plasticizers, and the like. These photographic emulsions can also contain additional spectral sensitizing dyes. Furthermore, these emulsions can contain color-forming couplers or can be developed in solutions containing couplers or other colorgenerating materials. Among the useful color formers are the monomeric and polymeric color formers, e.g., pyrazolone color formers, as well as phenolic, heterocyclic and open-chain couplers having a reactive methylene group. The color-forming couplers can be incorporated into the photographic silver halide emulsion using any suitable technique, e.g., techniques of the type shown in Jelley et al. US. Pat. 2,322,027, issued June 15, 1943, Fierke et al. US. Pat. 2,801,171, issued July 30, 1957, Fisher U.S. Pats. 1,055,155 and 1,102,028, issued Mar. 4, 1913 and June 30, 1914, respectively, and Wilmanns US. Pat. 2,186,849, issued Jan. 9, 1949. They can also be developed using incorporated developers such as polyhydroxybenzenes, aminophenols, 3-pyrazolidones, and the like.
The following examples are included for a further understanding of this invention.
EXAMPLE 1 A sulfur and gold sensitized, large grain, liquid gelatin silver bromoiodide (about 6 mole percent of the halide being iodide) emulsion is stirred thoroughly, combined with a suitable surfactant (e.g., saponin) and hardener (e.g., formaldehyde) and coated on a cellulose acetate support at a coverage of 350 mg. silver and 810 mg. gelatin per square foot. One set of coatings is exposed to tungsten light on an Eastman 1B sensitometer and processed for minutes at 20 C. in Kodak D-SO developer. The relative speed values obtained are given in Table I. The relative blue speed is obtained by exposing the element through a combination of filters: Wratten 35 plus 38A plus a blue filter that absorbs green and red light and transmits blue light.
EXAMPLE 2 The procedure of Example 1 is followed except that infrared sensitizing dyes I and II (identified at the end of Table I) are added to the emulsion along with the silver complexing agent 1,10-dithio 4,7,13,16 tetraoxacyclooctadecane (which forms a silver complex with silver ion in the emulsion). The infrared speed is determined by exposure on the sensitometer through a Wratten 89B filter. The results appear in Table I.
EXAMPLES 3-5 The procedure of Example 2 is repeated except that the complexing agent and sensitizing dyes I and II are dissolved in methanol with varying amounts of silver nitrate and the mixture obtained is added to the emulsion. The results appear in Table I.
EXAMPLES 6-8 The procedure of Examples 3-5 is repeated except that the methanolic solution of sensitizing dyes, silver complexing agent and silver nitrate is heated to 50 C., held at that temperature for 6 minutes, and then added to the emulsion. The results are shown in Table I.
TABLE I Com- Mg. Relative Relative plexing AgNO; blue infrared agent mole Ag speed speed min.
1 331 06 D 100 06 D 1 120 115 06 D 1 240 138 145 06 D 1 480 151 182 10 D 2 120 04 D 2 240 115 138 06 D 2 480 159 209 06 1 chemicals pre-mixed in methyl alcohol, then added to the em 1011.
2 All chemicals pre-mixed in methyl alcohol, heated to 50 0., held 6 min., and then added to the emulsion.
Dye II: D: 1,10
The data in Table I shows that the ex situ preparation of the silver complex-dye mixture is more efiicient than the in situ formation of the silver complex of the organic ligand, D (Example 2 versus Examples 3-8). Examples 3-5 and 6-8 indicate that the amount of silver nitrate available to form the silver complex has a marked influence on the efiiciency of the supersensitization. In addition, a heat treatment during the pre-mixing step causes a further gain in spectrally sensitized speed. It is believed that the ex situ mixing of silver nitrate, organic ligand and sensitizing dye alone or with a heat treatment, facilitates the formation of the silver complex which in turn acts as a more efficient supersensitizer for the sensitizing dye combination (Dye I and Dye II). Note that the heat treatment step prevents the undue formation of fog (Example 5 versus 8). The ex situ preparation of the silver-organic complex, and the pre-mixing of the sensitizing dye and the silver-organic complex, produces increased blue (intrinsic) sensitivity, higher spectral sensitivity and reduced minimum densities. Results generally similar to those in Table I are obtained when other spectral sensitizing dyes, such as those mentioned above, and when other organic thioether or selenoether complexing agents, are used in place of Dyes I and II and Complexing Agent D. Dyes which spectrally sensitize to shorter wavelengths than infrared are useful in the invention, and are supersensitized in the general region in which they spectrally sensitize.
EXAMPLE 9 A non-spectrally sensitized control coating is prepared and coated as in Example 1. The dried element is exposed and processed as in Examples 1-8, except that a Wratten 29 filter (red) is substituted for the Wratten 89B filter. An additional set of coatings is hypersensitized by bathing for 2 to 3 minutes in a 5 C. solution consisting of 2 parts 28% aqueous ammoniacal solution and 100 parts water, rinsed in methanol, dried, immediately exposed and processed as the control coating. The unhypered coating is assigned a blue speed of 100 and has a minimum density of 0.04. The ammonia hypered coating has a relative blue speed of 138 and a minimum density of 0.06.
EXAMPLES 10-23 The procedure set out in Example 9 is followed with the exception that the emulsion is spectrally sensitized with a pre-mixed, pre-heated solution consisting of a spectral sensitizing dye (at various levels), and 0.6 gram of silver complex per silver mole of emulsion. The silver complexing agent (D) is identical to the one used in Examples 2-8. The sensitometric data obtained from these unhypered and hypered coatings are listed in Table II. The following individual sensitizing dyes are incorporated in the coatings:
(HI) 5,5'-dichloro-3,3'-diethyl-9-phenylselenacarbocyanine iodide 9 (IV) 3,3'-9 triethyl-5,6,5',6'-dibenzothiacarbocyanine p-toluenesulfonate (V) 5,5-dichloro-3,3,9-triethylthiacarbocyanine bromide (VI) 3,3'-dimethyl-9-phenylthiacarbocyanine iodide 10 The invention has been described in detail with particular reference to preferred embodiments thereof, but it will be understood that variations and modifications can be effected within the spirit and scope of the invention described hereinabove and in the appended claims.
TABLE II F: Unhypered Ammonia hypered Format Relative Relative Relative Relative Dye at mgJmole silver :1: blue red blue red Example complex at 0.6 g./mole silver speed speed Dmin speed speed Dmin 9 None- 100 .04 138 .06 10.... 83 105 .00 120 417 .08 11 53 110 .08 91 525 .10 12--- 120 39s .06 120 692 .08 13... 110 525 .08 115 795 .10 14. 95 159 .00 105 302 1s 87 219 10 91 380 14 16. 105 219 0s 95 251 10 11- 110 380 .12 83 363 .14 18. 100 219 .06 105 417 .08 19..- g y 80 251 .10 73 39s .12 150 mg. dye V plus complex 115 316 06 95 363 08 21 300 mg. dye V Iplus complex"..- 100 380 14 80 417 14 22 250 mg;dyeV 42 21 .10 4e 83 .10 23 250 mg. dye VI plus complex.... 76 55 10 73 132 12 A study of the data in Table II reveals that unhypered We claim: coatings, containing both the dye and the silver complex, 1. The method of spectrally sensitizing a photographic show equal or nearly equal red speeds in comparison with 25 silver bromoiodide emulsion which comprises adding to the hypered coat ngs containmg an equal amount of sensaid emulsion a mixture comprising a photographic specsitizing dye anclno silver complex. For instance, compare tral sensitizing dye and a complex of silver with an or- Example 13 (unhypered) with Example 11 (hypered), ganic thioether or an organic selenoether. Example 17 (unhypered) with Example 15 (hypered), 2. The method of spectrally sensitizing a photographic Example 21 (unhypered) with Example 19 (hypered) and silver bromoiodide emulsion which comprises adding to Example 23 (u yp Wlth f p 22 yp fimsaid emulsionamixture comprising: in most cases the yp cotmgs l In (a) a photographic spectral sensitizing dye having one some examples the hypered coatings contammg a silver f h following formulas; complexing agent have more speed than hypered coatings containing a. sensitizing dye and no complexing agent. For we 9 example, compare the hypered coatings of Examples 10 x and 11 (no complex) with Examples 12 and 13 (comand plex). Z Q
2 2 a 2 r a EXAMPLES 4-3 40 R3N(-CH=CH) 1o=(L-L)k 1=o o=o Mees and James in The Theory of the Photographic Process 3rd Edition published by the Macmillan C0 wherein Z, Z and Z each represents the non-metallic New York, 1966, state at page 258, that dye desensitizaatoms: Peqmred to Complete heterocychc l l tion increases with increasing pAg. However, lowering the contammg from 5 to 6 the h'eterocychc nng; pAg of a coating causes a loss in storage stability and each L represents a methme lmkage, R2 and R3 an increase in fog. These examples demonstrate that the F 9 represents alkyl g p an alkylene group use of a silver complexing agent with a spectral sensitizing Joined to a methme llnkfige. an Y p; Q dye duplicates the sensitometric advanges of low pAg represents the Rolf-Install atoms l'equlred to coatings with the dye alone, without an increase in fog- Plate a hetefocycllc ketofnethylene 1111016138 9 ging propensity upon incubation. The emulsion, coating mg from 5 to 6 atoms 1n the heterocyclic rmg; m format, exposure and processing procedures are the same represents an nteger of from 1 to 5 d, n and 1' each as in Examples 9-23. The final pAg of the final emulsion represents an integer of from 1 to 2; k represents an composition is adjusted with a solution of silver nitrate. integer of from 1 to 3; and X represents an acid Table III contains the sensitometric data obtained from anion; and these examples. The complexing agent is 1,10-dithia-4,7, (b) a complex of silver w1th an alkane or cycloalkane 13,16-tetraoxacyclooctadecane (D).
containing from 5 to 20 carbon atoms in which from TABLE III 160 m d e mole 1 wk. 120 F.
Ag dz con i piex at Relative Relative 50% RH. Example 0.6 g./mole Ag pAg blue speed red speed Fog incubation fog 24 None control 8. 2 100 06 04 25-.- Dye 8. 2 40 87 06 06 26--. Dye III plus complex 8. 2 67 263 .06 06 27- None (control) 7. 8 110 04 05 28. Dye III 7. 8 58 132 08 06 29. Dye III plus complex. 7. 8 73 302 07 07 30. None (control) 7.4 63 .36 .52 31. Dye III 7.4 95 276 .16 .15 32 Dye III plus complex- 7. 4 69 316 14 20 Norm-Dye III:
55-d1ehlore-3,3-diethyl-Q-phenylselenaearbocyanine iodide. Oomplexing Agent D: 1,10-dithia4,7,13,1otetraoxacyclooctadecane. Exposure: 1/5 second 500W 5,400 K. Processing: 5 minutes Kodak D-50 developer.
2 to 6 CH groups, but not more than one half the total number of CH: groups, are replaced with a divalent sulfur or selenium atom. 3. The process of claim 2 wherein said complex of silver is a silver-dithia-tetraoxacyclooctadecane complex.
4. The metod of spectrally sensitizing a photographic silver bromoiodide emulsion which comprises adding to 11 said emulsion a methanolic solution comprising the photographic spectral sensitizing dyes 3,3'-diethylselenodicarbocyanine salt and anhydro-1-ethyl-3-(3-sulfobutyl)thia- 2'-cyanine salt, and a complex of silver with 1,10-dithia- 4,7,13,16-tetraoxacyclooctadecane.
5. The method of spectrally sensitizing a photographic silver bromoiodide emulsion which comprises heating a solution of a silver salt, an organic thioether or an organic selenoether, and a photographic spectral sensitizing dye; and, adding said heated solution to said silver bromoiodide emulsion.
6. The method of spectrally sensitizing a photographic silver bromoiodide emulsion which comprises heating for about 2 minutes to one hour, at about 30 to 80 C., a solution comprising:
(a) a photographic spectral sensitizing dye having one of the following formulas:
R l I(L=L)d1b=L(L=L)m-1dLL=)n =1 R x and I "Z2 I R I I(GH==CH)i-1b=(LL)k-i==0 wherein Z, Z and Z each represents the non-metallic atoms required to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring; each L represents a methine linkage; R R and R each represents an alkyl group, an alkylene group joined to a methine linkage, or an aryl group; Q represents the non-metallic atoms required to complete a heterocyclic ketomethylene nucleus containing from 5 to 6 atoms in the heterocyclic ring; m represents an integer of from 1 to 5; d n and j each represents an integer of from 1 to 2; k represents an integer of from 1 to 3; and, X represents an acid anion;
(b) a complex of silver with an alkane or cycloalkane containing from 5 to 20 carbon atoms in which from 2 to 6 -CH groups, but not more than one half the total number of CH- groups, are replaced with a divalent sulfur or selenium atom; and adding said heated solution to said emulsion.
7. The method of claim 6 wherein said heat treatment is conducted for about 5 to 10 minutes at a temperature of between 40 and 60 C.
8. The method of spectrally sensitizing a photographic silver bromoiodide emulsion which comprises heating for 5 to 10 minutes, at 40 to 60 C. a methanolic solution containing the sensitizing dyes 3,3'-diethylselenodicarbocyanine salt and anhydro-1-ethyl-3-(3-sulfobutyl)thia-2'- cyanine salt and, a complex of silver with 1,10-dithia-4,7, 13,16-tetraoxacyclooctadecane; and, adding said heated solution to said emulsion.
9. The process of sensitizing a photographic silver bromoiodide emulsion which comprises adding to said emulsion a mixture comprising a photographic spectral sensitizing dye and a complex of silver with an organic thioether or selenoether; coating said emulsion on a support; and, bathing said coated emulsion in a hypersensitizing bath.
10. The process of sensitizing a photographic silver bromoiodide emulsion which comprises adding to said emulsion a mixture comprising:
(a) a photographic spectral sensitizing dye having one of the following formulas;
wherein Z, Z and Z each represents the non-metallic atoms required to complete a heterocyclic nucleus containing from 5 to 6 atoms in the heterocyclic ring; each L represents a methine linkage; R R and R each represents an alkyl group, an alkylene group joined to a methine linkage, or an aryl group; Q represents the non-metallic atoms required to complete a heterocyclic ketomethylene nucleus containing from 5 to 6 atoms in the heterocyclic ring; In represents an integer of from 1 to 5; d, n and j each represents an integer of from 1 to 2; k represents an integer of from 1 to 3; and, X represents an acid anion; and v p (b) a complex of silver with an alkane or cycloalkane containing from 5 to 20 carbon atoms in which from 2 to 6 -CH groups, but not more than one half the total number of -CH-,-- groups, are replaced with a divalent sulfur or selenium atom; coating said emulsion on a support; and, bathing said emulsion in an aqueous ammoniacal hypersensitizing bath. 11. The method of spectrally sensitizing a photographic silver bromoiodide emulsion which comprises heating for 5 to 10 minutes, at 40 to 60 C. a methanolic solution containing the sensitizing dyes 3,3'-diethylselenodicarbocyanine salt; anhydro 1 ethyl-3-(3-sulfobutyl)thia-2'- cyanine salt and, a complex of silver with 1,10-dithia-4,7, 13,16-tetraoxacyclooctadecane; coating said emulsion on a support; and, bathing said emulsion for 2 to 3 minutes in anamrnoniacal bath consisting essentially of 2 parts of 28% aqueous ammoniacal solution and parts water, said bath being maintained at about 5 C. during hypersensitization.
References Cited UNITED STATES PATENTS 3,598,590 8/1971 Hiickstadt et a1. -2 96-107 3,536,492 10/1970 Luchs 96-110 3,057,724 10/1962 Lovett et a1 96-107 3,046,135 7/1962 Beavers 96-107 3,046,134 7/1962 Dann et al. 96-107 3,046,133 7/1962 Minsk 96-107 3,046,129 7/1962 Graham et al. 96-107 FOREIGN PATENTS 1,209,813 10/ 1970 Great Britain 96-109 OTHER REFERENCES Beavers, Def. Pub. of Ser. No. 825,420, filed May 16, 1969, published 866 O6 703, Sept. 16, 1969.
NORMAN G. TORCHIN, Primary Examiner J. WINKELMAN, Assistant Examiner U.S. c1. X.R.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3837862A (en) * 1971-09-02 1974-09-24 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US3881933A (en) * 1971-05-18 1975-05-06 Fuji Photo Film Co Ltd Light-sensitive material undergoing little change of latent image formed therein
US3951666A (en) * 1973-08-06 1976-04-20 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
US3953216A (en) * 1973-08-16 1976-04-27 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
GB2243923A (en) * 1990-01-15 1991-11-13 Forte Fotokemiai Ipar Silver halide photographic emulsions

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3881933A (en) * 1971-05-18 1975-05-06 Fuji Photo Film Co Ltd Light-sensitive material undergoing little change of latent image formed therein
US3837862A (en) * 1971-09-02 1974-09-24 Fuji Photo Film Co Ltd Spectrally sensitized silver halide photographic emulsion
US3951666A (en) * 1973-08-06 1976-04-20 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
US3953216A (en) * 1973-08-16 1976-04-27 Fuji Photo Film Co., Ltd. Spectrally sensitized silver halide photographic emulsion
EP0124795A2 (en) 1983-04-11 1984-11-14 Fuji Photo Film Co., Ltd. Silver halide photographic emulsion
GB2243923A (en) * 1990-01-15 1991-11-13 Forte Fotokemiai Ipar Silver halide photographic emulsions
GB2243923B (en) * 1990-01-15 1993-10-06 Forte Fotokemiai Ipar Silver halide photographic emulsions

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