US3676147A - Method of spectrally sensitizing photographic silver halide emulsions - Google Patents

Method of spectrally sensitizing photographic silver halide emulsions Download PDF

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US3676147A
US3676147A US880944A US3676147DA US3676147A US 3676147 A US3676147 A US 3676147A US 880944 A US880944 A US 880944A US 3676147D A US3676147D A US 3676147DA US 3676147 A US3676147 A US 3676147A
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dye
silver halide
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Simone J Boyer
Roger Caridi
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Eastman Kodak Co
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    • GPHYSICS
    • G03PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03CPHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00Photosensitive materials
    • G03C1/005Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08Sensitivity-increasing substances
    • G03C1/10Organic substances
    • G03C1/102Organic substances dyes other than methine dyes

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  • This invention relates to novel photographic processes and more particularly to novel processes for spectrally sensitizing photographic silver halide emulsions. It also relates to novel photographic materials and processes.
  • the conventional method of sensitizing light sensitive silver halide consists of dissolving the sensitizing dye in an appropriate organic solvent, such as methyl alcohol, ethyl alcohol, acetone, etc., and adding the resulting solution to a liquid photographic silver halide emulsion. While this general method has provided a commercially feasible means for incorporating sensitizing dyes into silver halide emulsions, it still requires considerable care and extra manipulative steps in adjusting the volume of solvent to quantities that are compatible with the particular emulsion and still produce the desired results. Also, it is well known that excessive solvent engenders disadvantageous diffusion or wandering of the sensitizing dyes in the emulsions.
  • an object of this invention to provide a new method for spectrally sensitizing light sensitive silver halide.
  • Another object of this invention is to provide novel dispersions of spectral sensitizing dye.
  • a process for spectrally sensitizing photographic silver halide which comprises: dispersing a substantially water-insoluble photographic spectral sensitizing dye into a water-soluble organic liquid without dissolving the dye; and, incorporating the dispersion into a liquid photographic silver halide emulsion.
  • novel dye dispersions comprise undissolved particles of a photographic spectral sensitizing dye in a water-soluble organic liquid.
  • compositions which comprise a hydrophilic colloid containing undissolved particles of photographic spectral sensitizing dye in a water-soluble organic liquid in which said dye is substantially insoluble.
  • Such composition can be either liquid or solid; either form is useful for spectrally sensitizing liquid photographic silver halide emulsions.
  • the dye dispersions of the invention are especially useful in coating processes which require low amounts of organic solvent.
  • the dye dispersions are stable and can be conveniently stored or transported.
  • compositions of dye in organic liquid can be prepared in any convenient manner. Ball milling the dye and organic liquid gives highly satisfactory results. Ad-
  • the liquid contains dye particles which have an average diameter of up to about 1.0 micron.
  • Organic liquids which can be used in the practice of this invention are water-soluble materials, and are liquids below about 30 C.
  • Organic liquids can be used which are not solvents for the photographic sensitizing dye that is being used.
  • Such organic liquids are oily materials. They should not have any adverse effects on the photographic emulsion in which they are incorporated.
  • organic liquids which are solvents for the dye.
  • Such organic liquids e.g., methanol, ethanol or isopropanol are used at sufficiently low levels, compared to the quantity of dye, that only very small amounts of dye are dissolved. Both types of liquids function to separate, or prevent agglomeration of the dye particles. Such separation is essential to eflective spectral sensitization.
  • Typical organic liquids that are not dye solvents which can be used in the invention are represented by the following formula:
  • R represents a hydrogen atom or a lower alkyl group containing 1 to 4 carbon atoms, e.g., methyl, ethyl, butyl, etc.; R represents a hydrogen atom or a methyl group; R represents a hydrogen atom, an alkyl group containing from 1 to 3 carbon atoms, e.g., methyl, ethyl, propyl or isopropyl, a hydroxymethyl group or an acetoxymethyl group; and R represents a divalent alkylene group containing from 1 to 4 carbon atoms, e.g., -CH a)s 2)2, 2)3 0T and wherein the sum of the carbon atoms in said R R and R is a positive integer of from 1 to 4.
  • Typical useful liquids embraced by Formula I above include glycerol, monoacetin, ethylene glycol, methylglycol, (monomethyl ether of ethylene glycol), ethyl glycol ether, propyl glycol ether, butyl glycol ether, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, isobutylene glycol (Z-methyl-1,2-propanediol), 2-methyl-2, 3-butanediol, 3-methyl-l,3-butanediol, 1,2-pentanediol, l, 4-pentanediol, 2,3-pentanediol, 1,5-pentanediol, etc.
  • Glycerol and methylglycol are the preferred solvents herein.
  • organic liquids which are solvents for spectral sensitizing dyes. Such liquids are used in sufiiciently small amounts, relative to the quantity of spectral sensitizing dye, that no substantial amounts of dye are dissolved. Preferably, such liquids have a dissolving power for the dyes of less than 10 grams of dye per liter of solvent at 20 C.
  • Useful organic liquids of this class include alcohols having from 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol or tert butanol; acetone; and, dimethylformamide. Such solvents provide less tacky dye dispersions than similar dispersions made with relatively high boiling organic liquids.
  • a typical useful solvent mixture of this type is a mixture of methanol (which is a solvent for most sensitizing dyes) together with glycerol (which is a non-solvent for most sensitizing dyes).
  • a typical useful solvent mixture of this type is a mixture of methanol (which is a solvent for most sensitizing dyes) together with glycerol (which is a non-solvent for most sensitizing dyes).
  • an organic liquid mixture comprising about to 95 parts by weight solvent (e.g., methanol) and 20 to 5 parts by weight of a non-solvent liquid (e.g., glycerol) and preferably about parts by Weight solvent and 10 parts by weight non-solvent.
  • the spectral sensitizing dye is dispersed in the organic liquid without dissolving the dye.
  • the term without dissolving the dye means that no substantial amount of dye is dissolved. Preferably, less than about by weight of the total dye mixed with the liquid is dissolved. Essentially no dye is dissolved when the dye is insoluble in the organic liquid.
  • the solvent is used in such small concentrations relative to the total amount of dye that no substantial amount of dye is dissolved.
  • Typical solutions of sensitizing dye in organic solvent e.g., methanol, contain about 1 to 3 grams dye per liter of solvent. In accordance with this invention, preferably about 5 to 20 cc. of solvent are used per gram of dye.
  • This invention can be practiced with any of the photographic spectral sensitizing dyes.
  • the invention is especially useful with the dyes that are substantially insoluble in aqueous solutions, e.g., dyes which have a solubility in water (at 20 C.) of less than about 1%.
  • Typical dyes which can be used in the practice of this invention are described in the following patents, the disclosure of which are incorporated herein by reference.
  • I, II, III and V include not only the specified iodide and bromide salts, but also the chloride, sulfamate, thiocyanate, perchlorate, ptoluenesulfonate, methyl sulfate, etc. salts. Also, Dye N0. XI includes any of the alkali metal salts such as lithium, potassium, etc.
  • the weight proportions of the water-soluble liquid (which is a non-solvent for the dyes) to dye can vary over a wide range, such as from about :5 to 100 150, but preferably from about 100:10 to 100240, respectively.
  • Liquids which are dye solvents are advantageously used in weight proportions of about 5 to 20 parts solvent per each part by weight of dye.
  • dispersions of the invention containing a binder such as gelatin can vary widely in the proportions of dye to gelatin, but the best results for sensitizing purposes are obtained with compositions wherein the dye varies from 20 to 40%, based on the total weight of dye plus binder.
  • the dispersions of the dyes can also contain two or more dyes in each dispersion or dispersions containing a single dye can also be used in combinations of two or more such dispersions.
  • the concentration of dye incorporated into the emulsions by the method of the invention for optimum sensitivity varies depending on the dye and emulsion about from 0.20 to 4.0 grams of dye per mole of silver halide in the emulsion.
  • the dye dispersions of the invention can be readily incorporated into the emulsions by any suitable method such as mixing, mechanical blending, etc.
  • compositions of the invention consisting essentially of organic liquid and dye can be added directly to liquid photographic silver halide emulsions to obtain good spectral sensitization.
  • the composition of the invention can be dispersed in a hydrophilic colloid.
  • the dispersion of dye-organic liquid in hydrophilic colloid can be used in liquid or solid form to sensitize liquid silver halide emulsions.
  • the hydrophilic colloid used with the dye-organic liquid can be any colloid which is compatible with the photographic emulsions, such as any of the hydrophilic colloids referred to below. Gelatin is especially useful.
  • the colloid is preferably free from silver halide, or, the mixture comprises a substantial amount of dye which is unadsorbed on any silver halide present in the colloid.
  • the light sensitive silver halide can be dispersed in any hydrophilic colloid (binder) that is satisfactory for dispersing silver halides, for example, gelatin, albumin, agar-agar, gum arabic, alginic acid, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose ethers, partially hydrolyzed cellulose acetate, and the like.
  • the hydrophilic colloid can also contain dispersed polymerized vinyl compounds, such as those disclosed in U.S. Pats.
  • 3,142,568; 3,193,386; 3,062,674 and 3,220,844 and include the water insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates and the like.
  • silver bromoiodide emulsions While the examples herein are illustrated with silver bromoiodide emulsions, it will be apparent that other silver halide emulsions such as silver chloride, silver bromide, silver chlorobromide, silver chlorobromoiodide, etc. can also be efliciently sensitized in like manner with the novel dye dispersions of the invention.
  • the emulsions prepared in accordance with the invention may be coated on any suitable photographic support such as cellulose acetate, cellulose acetate butyrate, polyesters such as poly(ethylene terephthalate), polyethylene,
  • the photographic emulsions prepared in accordance with the novel method of this invention may contain such addenda 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, U.S. Pat. No. 2,540,085, issued Feb. 6, 1951; Damschroder, U.S. Pat. No. 2,597,856, issued May 27, 1952 and Yutzy et a1.
  • chemical sensitizers e.g., sulfur sensitizers (e.g., allyl thiocarbamate, thiourea, allylisothiocyanate, cystine, etc.)
  • gold compounds e.g., potassium chloroaurate, auric trichloride, etc.
  • 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 in some cases additional spectral sensitizing dyes. Furthermore, these emulsions can contain color forming couplers or can be developed in solutions containing couplers or other color generating materials.
  • 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. U.S. Pat. 2,322,027, issued June 15, 1943, Fierke et al. U.S. 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 U.S. Pat. 2,186,849, issued Jan. 9, 1940. They can also be developed using incorporated developers such as polyhydroxybenzenes, aminophenols, 3 pyrazolidones, and the like.
  • EXAMPLE 1 1.350 g. of Dye No. I are milled for 6 hours in a ballmill with 6 cc. of methylglycol to give a dye dispersion wherein the dye particles have an average diameter less than about 1 micron. To this dispersion 18 g. of a gelatin solution are then added. The mixture is homogenized in a ball-mill for 15 minutes. The mixture is then air dried, formed into flakes so as to be readily bottled and stored at room temperature in a brown glass bottle. A suitable sample of the mixture is used to determine the dye content of the mixture. In the present example, the dye concentration is 31.5% by weight.
  • Each of these two emulsions is kept at 40 C. for 20 minutes and then each is coated onto a separate cellulose acetate film support.
  • the coated samples are sensitometrically tested by successive exposures of each sample to white light and through Wratten Filters No. 25 which transmits light at wavelengths longer than about 590 nm., No. 47 which transmits light in the region of about from 350 to 530 nm., and No. 58 which transmits light in the region of about from 470 to 615 nm., followed by development for about 6 minutes at room temperature in Kodak D-19 developer which has the following composition:
  • EXAMPLE 13 The photographic tests carried out in this example are similar to those described in above Example 12, except that the preparation of the milled dyes dispersed in gelatin were made 3 months before.
  • EXAMPLE 14 A negative silver halide emulsion similar to that described in above Example 12 is optically sensitized with the dye mixture:
  • EXAMPLE 15 A mixture of Dye Nos. I, II an III, in the proportions given in above Example 12, is milled with 10 cc. of methyl glycol until the dye particles have an average diameter less than about 1 micron. The resulting dye paste is dispersed in 12 g. of a 15% aqueous gelatin solution, dried and then used to sensitize a photographic silver halide emulsion, as described in Example 12. The sensitivity of this emulsion is substantially the same as that of the emulsion prepared in Example 12 by method (a), except that the speed loss in white light as compared to the control is 0.08 log E.
  • EXAMPLE 16 This example is identical with that of Example 15, except that the mixture of dyes is milled with 12 cc. of glycerol and taken up with 20 g. of a 10% aqueous gelatin solution.
  • the sensitometric results of this example are identical with those of above Example 15.
  • EXAMPLE 17 The mixture of dyes described in Example 14 is milled with 10 cc. of methylglycol, taken up with 30 g. of 10% gelatin solution and dried. The dry mixture is used for optically sensitizing a photographic emulsion by the method described in Example 12.
  • the emulsion sensitized with the solid mixture shows a speed loss of 0.10 log E as compared to the control (method a), in white light.
  • EXAMPLE 18 This example and results thereof are identical with those of Example 17, except that the dye mixture is milled with 15 cc. of glycerin.
  • EXAMPLE 19 500 mg. of Dye II are milled for 24 hours in a ballmill in the presence of cc. of methanol. Less than 5% by Weight of the total amount of dye is dissolved in methanol. 50 cc. of a aqueous gelatin solution are then added and the mixture is effected in the same ballmill at 40 C. for 2 hours.
  • This mixture is coated on unsubbed poly(ethylene terephthalate) support, in the form of a film having a thickness of 30,11. to 40 After drying, the film which adheres to the support due to the effect of electrostatic charges is readily stripped from the base. It is broken into flakes by being passed through a grate under the action of compressed air. It is then readily weighed, titrated and stored.
  • the mixture which contains about 8% by weight of dye, is used to spectrally sensitize an emulsion as described in Example 12.
  • the spectral sensitometric results obtained, as in Example 12, are identical with those obtained by conventional spectral sensitization methods (i.e., when the dye is dissolved in an aqueous solution of methanol and added to the emulsion).
  • EXAMPLE 20 The procedure of Example 19 is repeated except that the 5 cc. of methanol are replaced with 5 cc. of a 90:10 methanol-glycerin mixture. Identical sensitometric results are obtained.
  • any other of the dyes mentioned in Table 1 above, as well as still other known cyanine sensitizing dyes that are Waterinsoluble, can be substituted in the procedures of the above examples to give generally similar useful results.
  • any other of the mentioned water-soluble dihydroxyalkanes or lower monoalkyl ether derivatives thereof which are non-solvents for the sensitizing dyes glycerol, monoacetin, ethylene glycol, methylglycol, ethyl glycol ether, propyl glycol ether, butyl glycol ether, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, isobutylene glycol, 2-methyl-2,3-butanediol, 3- methyl-1,3-butanediol, 1,2-pentanediol, 1,4-pentanediol, 2,3-pentaned
  • a process for spectrally sensitizing photographic silver halide which comprises: dispersing a substantially water-insoluble photographic spectral sensitizing dye in a water-soluble organic liquid which is a non-solvent for said dye; and, incorporating said dispersion into a liquid photographic silver halide emulsion, said organic liquid having the following formula:
  • R represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 4 carbon atoms
  • R represents a member selected from the group consisting of a hydrogen atom and a methyl group
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 3 carbon atoms, a hydroxy-alkyl group of from 1 to 3 carbon atoms and an acetoxymethyl group
  • R represents a divalent alkylene group containing from '1 to 4 carbon atoms, the sum of the carbon atoms in said R R and R being from 1 to 4.
  • the process for spectrally sensitizing silver halide which comprises: dispersing a substantially water-insoluble photographic spectral sensitizing dye in an organic liquid selected from the group consisting of glycerol, monoacetin, ethylene glycol, methylglycol, ethyl glycol ether, propyl glycol ether, butyl glycol ether, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3- butylene glycol, isobutylene glycol, 2-methyl-2,3-butanediol, 3-methyl-1,3butanediol, 1,2-pentanediol, 1,4-pentanediol, 2,3-pentanediol, and 1,5-pentanediol; and, incorporating said dispersion into a liquid photographic silver halide emulsion to spectrally sensitize the silver halide.
  • an organic liquid selected from
  • the dispersion of dye in organic liquid is mixed with an aqueous solution of a hydrophilic colloid to form a homogenous mixture and said mixture is incorporated into the light-sensitive silver halide emulsion.
  • a process for spectrally sensitizing photographic silver halide which comprises: dispersing in methylglycol a photographic spectral sensitizing dye selected from the group consisting of 1'ethyl-2-methylthia-4'-cyanine salt;
  • a process for spectrally sensitizing photographic silver halide which comprises: dispersing in glycerol a photographic spectral sensitizing dye selected from the group consisting of 1'-ethyl-2-methylthia-4'-cyanine salt;
  • a process for spectrally sensitizing photographic silver halide which comprises: dispersing a substantially water-insoluble photographic spectral sensitizing dye in a water-soluble organic liquid mixture without dissolving the dye, said organic liquid mixture comprising about to parts by weight of an organic liquid selected from the group consisting of an alcohol having from 1 to 4 carbon atoms, acetone and dimethylformamide, and, about 20 to 5 parts by weight of an organic liquid having the following formula:
  • R represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 4 carbon atoms
  • R represents a member selected from the group consisting of a hydrogen atom and a methyl group
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 3 carbon atoms, a hydroxyalkyl group of from 1 to 3 carbon atoms and an acetoxymethyl group
  • R represents a divalent alkylene group containing from 1 to 4 carbon atoms, the sum of the carbon atoms in said R R and R being from 1 to 4; and, incorporating said dispersion into a liquid photographic silver halide emulsion to spectrally sensitize the silver halide.
  • a process as defined in claim 9 wherein said organic liquid mixture comprises about 80 to 95 parts by weight methanol and about 20 to 5 parts by weight glycerol.
  • a process for spectrally sensitizing silver halide which comprises: dispersing, in about 5 cc. of an organic liquid mixture comprising 9 parts by weight methanol and 1 part by weight glycerol, about .5 gram of 3-ethyl-5-[(3- ethyl 2(3H) benzothiazolylidene)isopropylidene] 2- thio-2,4-oxazolidinedione.
  • a mixture comprising a hydrophilic colloid and a dispersion of a photographic spectral sensitizing dye in a water-soluble organic liquid in which the dye is insoluble, said organic liquid having the following formula:
  • R represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 4 carbon atoms
  • R represents a member selected from the group consisting of a hydrogen atom and a methyl group
  • R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 3 carbon atoms, a hydroxyalkyl group of from 1 to 3 carbon atoms and an acetoxymethyl group
  • R represents a divalent alkylene group containing from 1 to 4 carbon atoms, the sum of the carbon atoms in said R R and R being from 1 to 4.
  • a mixture comprising a hydrophilic colloid and a dispersion as defined in claim 12 wherein said organic liquid is selected from the group consisting of glycerol, monoacetin, ethylene glycol, methylglycol, ethyl glycol ether propyl glycol ether, butyl glycol ether, 1,3-propylene glycol, 1,3-butylene glycol, 1,4 butylene glycol, 2,3-butylene glycol, isobutylene glycol, 2-methyl-2,3-butanediol, 3- methyl 1,3-butanediol, 1,2-pentanediol, 1,4-pentanediol, 2,3-pentanediol and 1,5-pentanediol.
  • said organic liquid is selected from the group consisting of glycerol, monoacetin, ethylene glycol, methylglycol, ethyl glycol ether propyl glycol ether, butyl

Abstract

LIGHT SENSITIVE SILIVER HALIDE IS SPECTRALLY SENSITIZED BY DISPERSING A SUBSTANTIALLY WATER-INSOLUBLE PHOTOGRAPHIC SPECTRAL SENSITIZING DYE INTO A WATER-SOLUBLE ORGAINC LIQUID WITHOUT DISSOLVING THE DYE, AND INCORPORATING THE DISPERSION INOT A LIQUID PHOTOGRAPHIC SILVER HALIDE EMULSION. NOVEL DISPERSIONS OF DYES ARE ALSO PROVIDED.

Description

United States Patent "ice 180,194 Int. Cl. G03c 1/16', 1/18, 1/20 US. Cl. 96-130 13 Claims ABSTRACT OF THE DISCLOSURE Light sensitive silver halide is spectrally sensitized by dispersing a substantially water-insoluble photograph c spectral sensitizing dye into a water-soluble organic hquid without dissolving the dye, and incorporating the dispersion into a liquid photographic silver halide emulsion. Novel dispersions of dyes are also provided.
This invention relates to novel photographic processes and more particularly to novel processes for spectrally sensitizing photographic silver halide emulsions. It also relates to novel photographic materials and processes.
The conventional method of sensitizing light sensitive silver halide consists of dissolving the sensitizing dye in an appropriate organic solvent, such as methyl alcohol, ethyl alcohol, acetone, etc., and adding the resulting solution to a liquid photographic silver halide emulsion. While this general method has provided a commercially feasible means for incorporating sensitizing dyes into silver halide emulsions, it still requires considerable care and extra manipulative steps in adjusting the volume of solvent to quantities that are compatible with the particular emulsion and still produce the desired results. Also, it is well known that excessive solvent engenders disadvantageous diffusion or wandering of the sensitizing dyes in the emulsions.
It is, accordingly, an object of this invention to provide a new method for spectrally sensitizing light sensitive silver halide.
Another object of this invention is to provide novel dispersions of spectral sensitizing dye.
Other objects of this invention will be apparent from this disclosure and the appended claims.
'In accordance with one embodiment of this invention, a process is provided for spectrally sensitizing photographic silver halide which comprises: dispersing a substantially water-insoluble photographic spectral sensitizing dye into a water-soluble organic liquid without dissolving the dye; and, incorporating the dispersion into a liquid photographic silver halide emulsion.
In accordance with another embodiment of this invention, novel dye dispersions are provided which comprise undissolved particles of a photographic spectral sensitizing dye in a water-soluble organic liquid.
In still another embodiment of this invention, novel compositions are provided which comprise a hydrophilic colloid containing undissolved particles of photographic spectral sensitizing dye in a water-soluble organic liquid in which said dye is substantially insoluble. Such composition can be either liquid or solid; either form is useful for spectrally sensitizing liquid photographic silver halide emulsions.
The dye dispersions of the invention are especially useful in coating processes which require low amounts of organic solvent. The dye dispersions are stable and can be conveniently stored or transported.
The compositions of dye in organic liquid can be prepared in any convenient manner. Ball milling the dye and organic liquid gives highly satisfactory results. Ad-
3,676,147 Patented July 11, 1972 vantageously, the liquid contains dye particles which have an average diameter of up to about 1.0 micron.
Organic liquids which can be used in the practice of this invention are water-soluble materials, and are liquids below about 30 C. Organic liquids can be used which are not solvents for the photographic sensitizing dye that is being used. Such organic liquids are oily materials. They should not have any adverse effects on the photographic emulsion in which they are incorporated. Also useful are organic liquids which are solvents for the dye. Such organic liquids, e.g., methanol, ethanol or isopropanol are used at sufficiently low levels, compared to the quantity of dye, that only very small amounts of dye are dissolved. Both types of liquids function to separate, or prevent agglomeration of the dye particles. Such separation is essential to eflective spectral sensitization.
Typical organic liquids that are not dye solvents which can be used in the invention are represented by the following formula:
wherein R represents a hydrogen atom or a lower alkyl group containing 1 to 4 carbon atoms, e.g., methyl, ethyl, butyl, etc.; R represents a hydrogen atom or a methyl group; R represents a hydrogen atom, an alkyl group containing from 1 to 3 carbon atoms, e.g., methyl, ethyl, propyl or isopropyl, a hydroxymethyl group or an acetoxymethyl group; and R represents a divalent alkylene group containing from 1 to 4 carbon atoms, e.g., -CH a)s 2)2, 2)3 0T and wherein the sum of the carbon atoms in said R R and R is a positive integer of from 1 to 4. Typical useful liquids embraced by Formula I above include glycerol, monoacetin, ethylene glycol, methylglycol, (monomethyl ether of ethylene glycol), ethyl glycol ether, propyl glycol ether, butyl glycol ether, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, isobutylene glycol (Z-methyl-1,2-propanediol), 2-methyl-2, 3-butanediol, 3-methyl-l,3-butanediol, 1,2-pentanediol, l, 4-pentanediol, 2,3-pentanediol, 1,5-pentanediol, etc. Glycerol and methylglycol are the preferred solvents herein.
Also useful in the practice of this invention are organic liquids which are solvents for spectral sensitizing dyes. Such liquids are used in sufiiciently small amounts, relative to the quantity of spectral sensitizing dye, that no substantial amounts of dye are dissolved. Preferably, such liquids have a dissolving power for the dyes of less than 10 grams of dye per liter of solvent at 20 C. Useful organic liquids of this class include alcohols having from 1 to 4 carbon atoms, such as methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol or tert butanol; acetone; and, dimethylformamide. Such solvents provide less tacky dye dispersions than similar dispersions made with relatively high boiling organic liquids.
Especially good results are obtained with a mixture of one or more organic liquids which are non-solvents for the dye, together with one or more organic liquids which are solvents for the dye. A typical useful solvent mixture of this type is a mixture of methanol (which is a solvent for most sensitizing dyes) together with glycerol (which is a non-solvent for most sensitizing dyes). Particularly good results are obtained with an organic liquid mixture comprising about to 95 parts by weight solvent (e.g., methanol) and 20 to 5 parts by weight of a non-solvent liquid (e.g., glycerol) and preferably about parts by Weight solvent and 10 parts by weight non-solvent.
The spectral sensitizing dye is dispersed in the organic liquid without dissolving the dye. As used herein, the term without dissolving the dye means that no substantial amount of dye is dissolved. Preferably, less than about by weight of the total dye mixed with the liquid is dissolved. Essentially no dye is dissolved when the dye is insoluble in the organic liquid. When the organic liquid is one which will dissolve the dye, the solvent is used in such small concentrations relative to the total amount of dye that no substantial amount of dye is dissolved. Typical solutions of sensitizing dye in organic solvent, e.g., methanol, contain about 1 to 3 grams dye per liter of solvent. In accordance with this invention, preferably about 5 to 20 cc. of solvent are used per gram of dye.
This invention can be practiced with any of the photographic spectral sensitizing dyes. The invention is especially useful with the dyes that are substantially insoluble in aqueous solutions, e.g., dyes which have a solubility in water (at 20 C.) of less than about 1%. Typical dyes which can be used in the practice of this invention are described in the following patents, the disclosure of which are incorporated herein by reference.
Zeh et al. U.S. Pat. No. 2,068,047, issued 1/19/37 Brooker U.S. Pat. No. 2,078,233, issued 4/27/37 Koslowsky U.S. Pat. No. 2,107,379, issued 2/ 8/ 38 Mees U.S. Pat. No. 2,158,883, issued 5/16/39 Brooker et al. U.S. Pat. No. 2,161,331, issued 6 /6/39 Brooker U.S. Pat. No. 2,170,807, issued 8/29/39 Brooker U.S. Pat. No. 2,177,402, issued 24/ 39 Brooker U.S. Pat. No. 2,177,403, issued 10/24/39 Carroll et a1. U.S. Pat. No. 2,177,635, issued 10/31/39 Carroll U.S. Pat. No. 2,206,076, issued 7/2/40 Brooker U.S. Pat. No. 2,211,762, issued 8/20/40 Brooker et al. U.S. Pat. No. 2,213,238, issued 9/3/40 Brooker U.S. Pat. No. 2,307,916, issued 1/ 12/43 Brooker et al. US. Pat. No. 2,313,922, issued 3/16/43 Schneider U.S. Pat. No. 2,374,505, issued 4/24/43 Falleson et al. U.S. Pat. No. 2,378,917, issued 6/26/45 Brooker U.S. Pat. No. 2,454,629, issued 11/23/48 Thompson U.S. Pat. No. 2,535,993, issued 12/26/50 Carroll et al. U.S. Pat. No. 2,950,196, issued 8/23/60 Brooker et al. U.S. Pat. No. 2,955,939, issued 10/11/60 Jones U.S. Pat. No. 2,961,318, issued 11/22/60 Brooker et al. U.S. Pat. No. 2,194,805, issued 7/13/65 Tabor et al. U.S. Pat. No. 3,335,010, issued 8/8/67 Brooker et al. U.S. Reissue No. 24,292, reissued 3/ 19/57 1.6., British Pat. No. 434,235, accepted 8/28/ 35 The following table lists a number of cyanine dyes that are used in the examples hereinafter to illustrate the invention.
TABLE 1 Dye No.: Compound I 1'-ethyl-2-methylthia-4'-cyanine iodide II 3,3'-diethyl-9-methylselenacarbocyanine bromide III 1,1'-diethyl-2,2'-cyanine iodide IV 3-ethyl-5-[ 3-ethyl-2(3H) -benzothiazolylidene isopropylidene] -2-thjo-2,4-oxazolidinedione V 9-ethyl-3,3'-di(B-methoxyethyl)-5,5-
diphenyloxacarbocyanine iodide VI Anhydro-5,5,6,6-tetrachloro-1,1-diethyl- 3,3'-di(3-sulfobutyl)benzimidazolocarbocyanine hydroxide VII 5 (3-ethyl-2(3H) -naphtho[2,1]oxazolylidene )ethylene] -3-n-heptyl-1-phenyl-2- thiohydantoin VIII 5-(3-ethy1-2(3H)-benzoxazolylidene)-3- phenylrhodanine 1X Anhydro-5,5'-dichloro-3,9-diethyl-3-(3- sulfobutyl)thiacarbocyanine hydroxide lylidene) isopropylene] -1,3-di-(flmethoxyethyl)barbituric acid TABLE IContinuecl Dye No.: Compound XI 3-ethyl-5-[1-(4-sulfobutyl)-4( 1H) -pyridylidene]rhodanine, sodium salt XII Anhydro-3-ethyl-9-methyl-3-(3-sulfobutyl)thiacarbocyanine hydroxide It will be understood that cyanine dye salts such as above Dye Nos. I, II, III and V include not only the specified iodide and bromide salts, but also the chloride, sulfamate, thiocyanate, perchlorate, ptoluenesulfonate, methyl sulfate, etc. salts. Also, Dye N0. XI includes any of the alkali metal salts such as lithium, potassium, etc.
In preparing the novel dispersions of the invention, the weight proportions of the water-soluble liquid (which is a non-solvent for the dyes) to dye can vary over a wide range, such as from about :5 to 100 150, but preferably from about 100:10 to 100240, respectively. Liquids which are dye solvents are advantageously used in weight proportions of about 5 to 20 parts solvent per each part by weight of dye.
Those dispersions of the invention containing a binder such as gelatin can vary widely in the proportions of dye to gelatin, but the best results for sensitizing purposes are obtained with compositions wherein the dye varies from 20 to 40%, based on the total weight of dye plus binder. For spectrally sensitizing photographic silver halide emulsions, the dispersions of the dyes can also contain two or more dyes in each dispersion or dispersions containing a single dye can also be used in combinations of two or more such dispersions. Generally, the concentration of dye incorporated into the emulsions by the method of the invention for optimum sensitivity varies depending on the dye and emulsion about from 0.20 to 4.0 grams of dye per mole of silver halide in the emulsion. The dye dispersions of the invention can be readily incorporated into the emulsions by any suitable method such as mixing, mechanical blending, etc.
Compositions of the invention consisting essentially of organic liquid and dye can be added directly to liquid photographic silver halide emulsions to obtain good spectral sensitization. If desired, the composition of the invention can be dispersed in a hydrophilic colloid. The dispersion of dye-organic liquid in hydrophilic colloid can be used in liquid or solid form to sensitize liquid silver halide emulsions. The hydrophilic colloid used with the dye-organic liquid can be any colloid which is compatible with the photographic emulsions, such as any of the hydrophilic colloids referred to below. Gelatin is especially useful. The colloid is preferably free from silver halide, or, the mixture comprises a substantial amount of dye which is unadsorbed on any silver halide present in the colloid.
This invention is useful in spectrally sensitizing any liquid photographic silver halide emulsion. The light sensitive silver halide can be dispersed in any hydrophilic colloid (binder) that is satisfactory for dispersing silver halides, for example, gelatin, albumin, agar-agar, gum arabic, alginic acid, polyvinyl alcohol, polyvinyl pyrrolidone, cellulose ethers, partially hydrolyzed cellulose acetate, and the like. The hydrophilic colloid can also contain dispersed polymerized vinyl compounds, such as those disclosed in U.S. Pats. 3,142,568; 3,193,386; 3,062,674 and 3,220,844 and include the water insoluble polymers of alkyl acrylates and methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates and the like.
While the examples herein are illustrated with silver bromoiodide emulsions, it will be apparent that other silver halide emulsions such as silver chloride, silver bromide, silver chlorobromide, silver chlorobromoiodide, etc. can also be efliciently sensitized in like manner with the novel dye dispersions of the invention.
The emulsions prepared in accordance with the invention may be coated on any suitable photographic support such as cellulose acetate, cellulose acetate butyrate, polyesters such as poly(ethylene terephthalate), polyethylene,
polypropylene, paper, glass, and the like, to produce spectrally sensitized photographic elements.
The photographic emulsions prepared in accordance with the novel method of this invention may contain such addenda 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, U.S. Pat. No. 2,540,085, issued Feb. 6, 1951; Damschroder, U.S. Pat. No. 2,597,856, issued May 27, 1952 and Yutzy et a1. U.S. Pat. No. 2,597,915, issued May 27, 1952), various palladium compounds such as palladium chloride (Baldsiefen, U.S. Pat. No. 2,540,086, issued Feb. 6, 1951), potassium chloropalladate (Stauifer et al., U.S. Pat. No. 2,598,079, issued May 27, 1952), etc., or mixtures of such sensitizers, antifoggants such as ammonium chloroplatinate (Trivelli et al., U.S. Pat. No. 2,566,245, issued Aug. 28, 1951), ammonium chloroplatinite (Trivelli et al., U.S. Pat. No. 2,566,263, issued Aug. 28, 1951), benzotriazole, nitrobenzirnidazole, S-nitroimidazole, benzidine, mercaptans, etc. (see Mees-The Theory of the Photographic Process, MacMillan Pub., 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 in some cases additional spectral sensitizing dyes. Furthermore, these emulsions can contain color forming couplers or can be developed in solutions containing couplers or other color generating 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. U.S. Pat. 2,322,027, issued June 15, 1943, Fierke et al. U.S. 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 U.S. Pat. 2,186,849, issued Jan. 9, 1940. 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 1.350 g. of Dye No. I are milled for 6 hours in a ballmill with 6 cc. of methylglycol to give a dye dispersion wherein the dye particles have an average diameter less than about 1 micron. To this dispersion 18 g. of a gelatin solution are then added. The mixture is homogenized in a ball-mill for 15 minutes. The mixture is then air dried, formed into flakes so as to be readily bottled and stored at room temperature in a brown glass bottle. A suitable sample of the mixture is used to determine the dye content of the mixture. In the present example, the dye concentration is 31.5% by weight.
EXAMPLES 2-11 The procedure described in above Example 1 is repeated with each of the other dyes listed in Table 1 above, namely, Dye Nos. II to XI to give the corresponding dye dispersions in the concentrations listed in the following table.
TAB LE 2 Gone. 01-- Gelatin solution Dye cone. Methyl- Total Gone. in final Dye glycol soln. gelatin mix (wt. (grams) (co (grams) (grams) percent) EXAMPLE 12 A negative gelatino silver bromoiodide emulsion is digested to optimum sensitivity with a labile sulfur compound and a soluble gold salt. It is then divided into two portions (a) and (b) and each portion is optically sensiper 10 moles of silver halide in the emulsion. In portion (a), the dye mixture is added in solution in conventional solvents such as methanol. In portion (b), the dye mixture is milled with methyl glycol and dispersed in gelatin as described in above Example 1 and the resulting dispersion is then added to the emulsion.
Each of these two emulsions is kept at 40 C. for 20 minutes and then each is coated onto a separate cellulose acetate film support. The coated samples are sensitometrically tested by successive exposures of each sample to white light and through Wratten Filters No. 25 which transmits light at wavelengths longer than about 590 nm., No. 47 which transmits light in the region of about from 350 to 530 nm., and No. 58 which transmits light in the region of about from 470 to 615 nm., followed by development for about 6 minutes at room temperature in Kodak D-19 developer which has the following composition:
G. N-methyl-p-aminophenol sulfate 2.0 Sodium sulfite (anhydrous) 90.0 Hydroquinone 8.0 Sodium carbonate (monohydrate) 52.5 Potassium bromide 5.0
Water to make 1.0 liter.
then fixed, washed and dried. The resulting speed values for the emulsions sensitized by processes (a) and (b) are shown to be identical by the test procedure of this example. Similar good results of sensitization are likewise obtained when the dispersion of the dyes in methylglycol is used directly, without binder or drying, in the silver halide emulsion.
EXAMPLE 13 The photographic tests carried out in this example are similar to those described in above Example 12, except that the preparation of the milled dyes dispersed in gelatin were made 3 months before. The sensitometric results, which are identical with those described in the preceding example, show the good keeping properties of the dye dispersions of the invention.
EXAMPLE 14 A negative silver halide emulsion similar to that described in above Example 12 is optically sensitized with the dye mixture:
G. Dye No. IV 1.00 Dye No. V 1.13
Dye N0. VI 1.13
per 10 moles of silver halide in the emulsion, in accordance with methods (a) and (b) described in Example 12. The tests show that the speeds of the emulsions optically sensitized by methods (a) and (b) in this example are identical to white light, to light transmitted through Wratten Filter No. 47 and to light transmitted through Wratten Filter No. 58.
EXAMPLE 15 A mixture of Dye Nos. I, II an III, in the proportions given in above Example 12, is milled with 10 cc. of methyl glycol until the dye particles have an average diameter less than about 1 micron. The resulting dye paste is dispersed in 12 g. of a 15% aqueous gelatin solution, dried and then used to sensitize a photographic silver halide emulsion, as described in Example 12. The sensitivity of this emulsion is substantially the same as that of the emulsion prepared in Example 12 by method (a), except that the speed loss in white light as compared to the control is 0.08 log E.
EXAMPLE 16 This example is identical with that of Example 15, except that the mixture of dyes is milled with 12 cc. of glycerol and taken up with 20 g. of a 10% aqueous gelatin solution. The sensitometric results of this example are identical with those of above Example 15.
EXAMPLE 17 The mixture of dyes described in Example 14 is milled with 10 cc. of methylglycol, taken up with 30 g. of 10% gelatin solution and dried. The dry mixture is used for optically sensitizing a photographic emulsion by the method described in Example 12.
The emulsion sensitized with the solid mixture (method b) shows a speed loss of 0.10 log E as compared to the control (method a), in white light.
EXAMPLE 18 This example and results thereof are identical with those of Example 17, except that the dye mixture is milled with 15 cc. of glycerin.
In Examples 15, 16, 17 and 18, the small loss in sensitivity appears to result from loss of dyes when the mixtures are recovered from the ball-mills.
EXAMPLE 19 500 mg. of Dye II are milled for 24 hours in a ballmill in the presence of cc. of methanol. Less than 5% by Weight of the total amount of dye is dissolved in methanol. 50 cc. of a aqueous gelatin solution are then added and the mixture is effected in the same ballmill at 40 C. for 2 hours. This mixture is coated on unsubbed poly(ethylene terephthalate) support, in the form of a film having a thickness of 30,11. to 40 After drying, the film which adheres to the support due to the effect of electrostatic charges is readily stripped from the base. It is broken into flakes by being passed through a grate under the action of compressed air. It is then readily weighed, titrated and stored. The mixture, which contains about 8% by weight of dye, is used to spectrally sensitize an emulsion as described in Example 12. The spectral sensitometric results obtained, as in Example 12, are identical with those obtained by conventional spectral sensitization methods (i.e., when the dye is dissolved in an aqueous solution of methanol and added to the emulsion).
EXAMPLE 20 The procedure of Example 19 is repeated except that the 5 cc. of methanol are replaced with 5 cc. of a 90:10 methanol-glycerin mixture. Identical sensitometric results are obtained.
EXAMPLES 2 l-26 The procedures of Examples 19 and 20 are repeated, except that in each Example Dye II is replaced with 500 mg. of Dyes I, III and XII. The sensitometric results, obtained as in Example 12, are identical to those ob tained when the dyes are added to the same emulsion from methanol solutions.
It is well known in the photographic art that effective spectral sensitization of light sensitive silver halide depends on the dyes being adsorbed to the silver halide grains. See Mees and James, The Theory of the Photographic Process, 3d. edition, published by the MacMillan Company, 1966, page 236, column 2. One skilled in the photographic art would not expect particles of spectral sensitizing dyes, which are insoluble in aqueous systems, to migrate through a hydrophilic colloid and become efiiciently adsorbed to the silver halide.
It will be apparent from all the foregoing that any other of the dyes mentioned in Table 1 above, as well as still other known cyanine sensitizing dyes that are Waterinsoluble, can be substituted in the procedures of the above examples to give generally similar useful results. Also, any other of the mentioned water-soluble dihydroxyalkanes or lower monoalkyl ether derivatives thereof which are non-solvents for the sensitizing dyes, glycerol, monoacetin, ethylene glycol, methylglycol, ethyl glycol ether, propyl glycol ether, butyl glycol ether, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, isobutylene glycol, 2-methyl-2,3-butanediol, 3- methyl-1,3-butanediol, 1,2-pentanediol, 1,4-pentanediol, 2,3-pentanediol, 1,5-pentanediol, etc. can be substituted for the methylglycol and glycerol components in the procedures of the above examples with similar resulting ad- Vantage.
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.
We claimzi II. A process for spectrally sensitizing photographic silver halide which comprises: dispersing a substantially water-insoluble photographic spectral sensitizing dye in a water-soluble organic liquid which is a non-solvent for said dye; and, incorporating said dispersion into a liquid photographic silver halide emulsion, said organic liquid having the following formula:
wherein R represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 4 carbon atoms; R represents a member selected from the group consisting of a hydrogen atom and a methyl group; R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 3 carbon atoms, a hydroxy-alkyl group of from 1 to 3 carbon atoms and an acetoxymethyl group; and, R represents a divalent alkylene group containing from '1 to 4 carbon atoms, the sum of the carbon atoms in said R R and R being from 1 to 4.
2. The process for spectrally sensitizing silver halide which comprises: dispersing a substantially water-insoluble photographic spectral sensitizing dye in an organic liquid selected from the group consisting of glycerol, monoacetin, ethylene glycol, methylglycol, ethyl glycol ether, propyl glycol ether, butyl glycol ether, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 2,3- butylene glycol, isobutylene glycol, 2-methyl-2,3-butanediol, 3-methyl-1,3butanediol, 1,2-pentanediol, 1,4-pentanediol, 2,3-pentanediol, and 1,5-pentanediol; and, incorporating said dispersion into a liquid photographic silver halide emulsion to spectrally sensitize the silver halide.
in accordance with claim 1 wherein the dispersion of dye in organic liquid is mixed with an aqueous solution of a hydrophilic colloid to form a homogenous mixture and said mixture is incorporated into the light-sensitive silver halide emulsion.
4. The process for spectrally sensitizing silver halide in accordance wtih claim 3 wherein said aqueous mixture of dye, organic liquid and hydrophilic colloid is dried prior to incorporation into said light-sensitive silver halide emulsion.
5. A process for spectrally sensitizing photographic silver halide which comprises: dispersing in methylglycol a photographic spectral sensitizing dye selected from the group consisting of 1'ethyl-2-methylthia-4'-cyanine salt;
3,3-diethyl-9-methylselenacarbocyanine salt;
3-ethyl-5-[ (3-ethyl-2 3H) -benzothiazlylidene) isopropylidene]-2-thio-2,4-oxazolidinedione;
9-ethyl-3,3-di( fi-methoxyethyD-S ,5 -diphenyloxacarbocyanine salt;
anhydro-S,5,6, 6-tetrachloro-1,l'-diethyl-3,3'-di(3-sulfo= =butyl)-benzimidazolocarbocyanine hydroxide;
-[ (3-ethyl-2 3H) -n'aphtho [2,t1 oxazolylidene) ethylene] 3-n-heptyl-1-phenyl-2-thiohydantoin;
5- 3-ethyl-2 3H -benzoxazolylidene) -3-phenylrhodanine;
anhydro-S,5-dichloro-3,9-diethyl-3-(3-sulfobutyl)thiacarbocyanine hydroxide;
5- [di 3-ethyl-2( 1H)-naphtho[1,2]thiazolylidene)isopropylene]-1,3-di(,B-methoxyethyl) barbituric acid; and
3-ethyl-5- l- (4-sulfobutyl) -4( 1H) -pyridylidene] rhodanine, sodium salt;
and incorporating said dispersion into an aqueous gelatin photographic silver halide emulsion to epectcally sensitize the silver halideJ 6. The process in accordance with claim 5 wherein the dispersion of dye in methylglycol is mixed with an aqueous solution of gelatin to form a homogeneous mixture, and said mixture is incorporated into said photographic silver halide emulsion.
7. The process for spectrally sensitizing silver halide in accordance with claim 5 wherein said mixture is dried prior to incorporation into the photographic silver halide emulsion.
8. A process for spectrally sensitizing photographic silver halide which comprises: dispersing in glycerol a photographic spectral sensitizing dye selected from the group consisting of 1'-ethyl-2-methylthia-4'-cyanine salt;
3,3'-diethyl-9-methylselenacarbocyanine salt;
1,1'-diethyl-2,2'-cyanine salt;
3-ethyl-5- 3-ethyl-2 3H) -'benzothiazolylidene) -isopropylidene] -2-thio-2,4-oxazolidinedione;
9-ethyl-3,3 '-di( B-methoxyethyl) -5 ,5 '-diphenyloxacarbocyanine salt;
anhydro-5,5','6, 6'-tetrachloro-l,1'-diethyl-3,3'-di(3-sulfobutyl)benzimidazolocarbocyanine hydroxide;
5- [3-ethyl-2 3H)naphtho [2, l oxazolylidene) ethylene] -3- n-heptyl-il-phenyl-2-thiohydantoin;
5- 3-ethyl-2( 3 H) -b enzoxazolylidene) -3-phenylrhodanine;
anhydro-S ,5 '-dichloro-3,9-diethyl-3-(3-sulfobutyl)thiacarbocyanine hydroxide;
5- [di 3-ethyl-2( 1H )-naphtho[ 1,2] thiazolylidene) isopropylene]-1,3-di(fl-methoxyethyl)barbituric acid; and
3-ethyl-5- [.l- (4-sulfobutyl -4( 1H) -pyridylidene] rhodanine, sodium salt;
and, incorporating said dispersion into an aqueous gelatin photographic silver halide emulsion.
9. A process for spectrally sensitizing photographic silver halide which comprises: dispersing a substantially water-insoluble photographic spectral sensitizing dye in a water-soluble organic liquid mixture without dissolving the dye, said organic liquid mixture comprising about to parts by weight of an organic liquid selected from the group consisting of an alcohol having from 1 to 4 carbon atoms, acetone and dimethylformamide, and, about 20 to 5 parts by weight of an organic liquid having the following formula:
wherein R represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 4 carbon atoms; R represents a member selected from the group consisting of a hydrogen atom and a methyl group; R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 3 carbon atoms, a hydroxyalkyl group of from 1 to 3 carbon atoms and an acetoxymethyl group; and, R represents a divalent alkylene group containing from 1 to 4 carbon atoms, the sum of the carbon atoms in said R R and R being from 1 to 4; and, incorporating said dispersion into a liquid photographic silver halide emulsion to spectrally sensitize the silver halide.
10. A process as defined in claim 9 wherein said organic liquid mixture comprises about 80 to 95 parts by weight methanol and about 20 to 5 parts by weight glycerol.
11. A process for spectrally sensitizing silver halide which comprises: dispersing, in about 5 cc. of an organic liquid mixture comprising 9 parts by weight methanol and 1 part by weight glycerol, about .5 gram of 3-ethyl-5-[(3- ethyl 2(3H) benzothiazolylidene)isopropylidene] 2- thio-2,4-oxazolidinedione.
12. A mixture comprising a hydrophilic colloid and a dispersion of a photographic spectral sensitizing dye in a water-soluble organic liquid in which the dye is insoluble, said organic liquid having the following formula:
wherein R represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 4 carbon atoms; R represents a member selected from the group consisting of a hydrogen atom and a methyl group; R represents a member selected from the group consisting of a hydrogen atom, an alkyl group containing from 1 to 3 carbon atoms, a hydroxyalkyl group of from 1 to 3 carbon atoms and an acetoxymethyl group; and R represents a divalent alkylene group containing from 1 to 4 carbon atoms, the sum of the carbon atoms in said R R and R being from 1 to 4.
13. A mixture comprising a hydrophilic colloid and a dispersion as defined in claim 12 wherein said organic liquid is selected from the group consisting of glycerol, monoacetin, ethylene glycol, methylglycol, ethyl glycol ether propyl glycol ether, butyl glycol ether, 1,3-propylene glycol, 1,3-butylene glycol, 1,4 butylene glycol, 2,3-butylene glycol, isobutylene glycol, 2-methyl-2,3-butanediol, 3- methyl 1,3-butanediol, 1,2-pentanediol, 1,4-pentanediol, 2,3-pentanediol and 1,5-pentanediol.
References Cited UNITED STATES PATENTS 3,469,987 9/1969 Owens ct a1. 96l32 I. TRAVIS BROWN, Primary Examiner U.S. Cl. X.R.
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Also Published As

Publication number Publication date
FR1602224A (en) 1970-10-26
DE1964169A1 (en) 1970-07-09
BR6915565D0 (en) 1973-01-18
CA942565A (en) 1974-02-26
GB1271329A (en) 1972-04-19
BE742612A (en) 1970-05-14

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