Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
  • G03C1/00—Photosensitive materials
  • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
  • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
  • G03C1/08—Sensitivity-increasing substances
  • G03C1/10—Organic substances

Definitions

• This invention concerns photographic silver halide emulsions, and more particularly, photographic silver halide emulsions containing novel sensitizing addenda.
• silver halide emulsions can be chemically sensitized with a variety of materials in order to increase their speed.
• Certain chemical sensitizers are believed to react with the silver halide to form on the surface of the silver halide minute amounts of silver sulfide, or of silver, or of other noble metals.
• other classes of compounds can be utilized to increase the sensitivity of photographic silver halide emulsions that apparently do not enter into chemical combination with the silver halide. Such sensitization reaches a limit beyond which further addition of sensitizer merely increases the fog of the photographic emulsion with constant or decreasing speed.
• the 1,1-dimethylhydrazinium salts of the invention are 1 alkyl-1,l-dimethylhydrazinium salts and a,w-alkylene bis(1,1-dimethylhydrazinium salts) having the formulas H a a wherein R is an alkyl radical generally having 2 to 20 carbon atoms and preferably 5 to 20 carbon atoms, R is an alkylene radical generally having 2 to 20 carbon atoms and preferably 2 to 12 carbon atoms, and X is an anion.
• Typical alkyl substituents for R include ethyl, isopropyl, n-butyl, isobutyl, n-hexyl, Z-ethylhexyl, n-decyl, n-dodecyl, n-hexadecyl, n-octadecyl, eicosyl, and the like.
• Typical alkylene substituents for R include ethylene, trimethylene, tert.-butylene, tetramethylene, hexamethylene, decamethylene, tetradecamethylene, hexadecamethylene, octadecamethylene, and the like.
• Typical anion substituents for X include p-toluene sulfonate, perchlorate, chloride, and the like ions.
• hydrazinium salts including such la-lkyl-1,1-dimethyll1ydraziniuin salts as;
• the present 1,1-dimethylhydrazinium salts are added to photographic silver halide emulsions in conventional sensitizing amounts in accordance with usual practice. Generally, however, about .01 to 10 and preferably about .1 to 5 grams per mole of silver halide in the emulsion of the 1,1-dimethylhydrazinium salts are utilized.
• the preparation of photographic silver halide emulsions such as are used with the addenda of this invention involves three separate operations: (1) emulsification and digestion of silver halide, (2) the freeing of the emulsion of excess water-soluble salts, suitably by washing with water, and (3) the second digestion or afterripening to obtain increased emulsion speed or sensitivity.
• the addenda of the invention can be added to the emulsion before the final digestion or after-ripening, or they can be added immediately prior to the coatmg.
• the addenda or" the invention can be added to photographic emulsions using any of the well-known techniques in emulsion making. For example, they can be dissolved in a suitable solvent and added to the silver halide emulsion, or they can be added to the emulsion in the form of a dispersion similar to the technique used to incorporate certain types of color-forming compounds (couplers) in a photographic emulsion. Techniques of this type are described in Jelley et al. U.S. Patent 2,322,- 027, issued June 15, 1943, and Fierke et al. US. Patent 2,801,171, issued July 30, 1957.
• the solvent should be selected so that it has no harmful effect upon the emulsion in accordance with usual practice, and generally solvents or diluents which are miscible with water are to be preferred.
• the emulsions can be digested with naturally active gelatin, or sulfur compounds can be added, such as those described in Sheppard U.S. Patent 1,574,944, issued March 2, 1926, and Sheppard et al. 1,623,499, issued April 5, 1927, and Sheppard and Brigham US. Patent 2,410,689, issued November 5, 1946.
• the emulsions can also be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium and platinum.
• Representative compounds are ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladite, which are used in arnountsbelow that which produces any substantial fog inhibition, as described in Smith and Trivelli US.
• Patent 2,448,060 issued August 31, 1948, and as antifoggants in higher amounts, as described in Trivelli and Smith US. Patents 2,566,245, issued August 28, 1951 and 2,566,263, issued August 28, 1951.
• the emulsions can also contain small amounts of gold salts as described in Waller et al. US. Patent 2,399,083, issued April 23, 1946, or in Damschroder US. Patent 2,597,856, issued May 27, 1952, and Yutzy and Leermakers US. Patent 2,597,915, issued May 27, 1952.
• Suitable compounds are potassium ehloroaurite, potassium aurithiocyanate, potassium chloroaurate, auric trichloride and 2-aurosulfobenzothiazole methochloride.
• the emulsions can also contain small amounts of reducing agents such as stannous salts (Carroll US. Patent 2,487,850, issued November 15, 1949), polyamines, such as diethylene triamine (Lowe and Jones US. Patent 2,518,698, issued August 15, 1950), polyamines, such as spermine (Lowe and Allen US. l-atent 2,521,925, issued September 12, 1950), or bis(fi-aminoethyl)sulfide and its water-soluble salts (Lowe and Jones US. Patent 2,521,926, issued September 12, 1950).
• reducing agents such as stannous salts (Carroll US. Patent 2,487,850, issued November 15, 1949), polyamines, such as diethylene triamine (Lowe and Jones US. Patent 2,518,698, issued August 15, 1950), polyamines, such as spermine (Lowe and Allen US. l-atent 2,521,925, issued September 12, 1950), or bis(fi-aminoethyl)sulfide and its
• the emulsions can also be optically sensitized with cyanine and merocyanine dyes, such as those described in Brooker US. Patents 1,846,301, issued February 23, 1932; 1,846,302 issued February 23, 1932; and 1,942,854, issued January 9, 1934; White US. Patent 1,990,507, issued February 12, 1935; Brooker and White US. Patents 2,112,140, issued March 22, 1938; 2,165,338, issued July 11, 1939; 2,493,747, issued January 10, 1950; and 2,739,964, issued March 27, 1956; Brooker and Keyes US. Patent 2,493,748, issued January 10, 1950; Sprague US. Patents 2,503,776, issued April 11, 1950 and 2,519,- 001, issued August 15, 1950; Heseltine and Brooker US. Patent 2,666,761, issued January 19, 1954; Heseltine US. Patent 2,734,900, issued February 14, 1956; Van
• the emulsions can contain a suitable gelatin plasticizer such as glycerin; a dihydroxy alkane such as 1,5- pentanediol as described in Milton and Murray US.
• a suitable gelatin plasticizer such as glycerin
• a dihydroxy alkane such as 1,5- pentanediol as described in Milton and Murray US.
• the emulsions can be hardened with any suitable hardener for gelatin such as formaldehyde; a halogensubstituted aliphatic acid such as mucobromic acid as described in White US. Patent 2,080,019, issued May 11, 1937; a compound having a plurality of acid anhydride groups such as 7,8-diphenylbicyclo(2,2,2)-7-octene- 2,3,5,6-tetracarboxylic dianhydride, or a dicarboxylic or a disulfonic acid chloride such as terephthaloyl chloride or naphthalene1,5-disulfonyl chloride as described in Allen and Carroll U.S.
• any suitable hardener for gelatin such as formaldehyde
• a halogensubstituted aliphatic acid such as mucobromic acid as described in White US. Patent 2,080,019, issued May 11, 1937
• Patent 2,732,316 issued Janumy 24, 1956; a dialdehyde or a sodium bisulfite derivative thereof, the aldehyde groups of which are separated by 23 carbon atoms, such as fl-methylglutaraldehyde t halide emulsion layer.
• the emulsions can contain a coating aid such as saponin; a lauryl or oleoyl monoether of polyethylene glycol as described in Knox and Davis US. Patent 2,831,- 766, issued April 22, 1958; a salt of a sulfated and alkylated polyethylene glycol ether as described in Knox and Davis US. Patent 2,719,087, issued September 27, 1955; an acylated alkyl taurine such as the sodium salt of N-oleoyl-N-methyl taurine as described in Knox, Twardokus and Davis US.
• a coating aid such as saponin
• a lauryl or oleoyl monoether of polyethylene glycol as described in Knox and Davis US. Patent 2,831,- 766, issued April 22, 1958
• a salt of a sulfated and alkylated polyethylene glycol ether as described in Knox and Davis US. Patent 2,719,087, issued September 27, 1955
• an acylated alkyl taurine such as the
• Patent 2,739,891 issued March 27, 1956; the reaction product of a dianhydride of tetracarboxybutane with an alcohol or an aliphatic amine containing from 8 to 18 carbon atoms which is treated with a base, for example, the sodium salt of the monoester of tetracarboxybutane as described in Knox, Stenberg and Wilson US. Patent 2,843,487, issued July 15, 1958; a water-soluble maleopimarate or a mixture of a water-soluble maleopimarate and a substituted glutamate salt as described in Knox and Fowler US. Patent 2,823,- 123, issued February 11, 1958; an alkali metal salt of a substituted amino acid such as disodium N-(carbo-p-tert.
• octylphenoxypentaethoxy) glutamate or a sulfosuccinamate such as tetrasodium N-(1,2-dicarboxyethyl-N-octadecyl sulfosuccinamate, or N-lauryl disodium sulfosuccinamate.
• the sensitizing addenda of the invention can be used in various kinds of photographic emulsions. In addition to being useful in orthochromatic, panchromatic, and infrared sensitive emulsions, they are also useful in X-ray and other non-optically sensitized emulsions. They can be added to the emulsion before or after any optical sensitizing dyes which may be used.
• Various silver salts can be used as the sensitive salt such as silver bromide, silver iodide, silver chloride, or mixed silver halides such as silver chlorobromide or silver brornoiodide.
• the subject addenda can be used in emulsions intended for color photography, for example, emulsions containing color-forming couplers or emulsions to be developed by solutions containing couplers or other colorgenerating materials, emulsions of the mixed-packet type, such as described in Godowsky US. Patent 2,698,794, issued January 4, 1955, or emulsions of the mixed-grain type, such as described in Carroll and Hanson US. Patent 2,592,243, issued April 8, 1952.
• Suitable color couplers usually belong to three widely known types, i.e., pyrazolone couplers, phenol couplers and open-chain ketornethylene couplers which combine with the oxidation products of aromatic primary amine silver halide developing agents to produce magenta, cyan and yellow images respectively.
• Development accelerators can be utilized in developing such color emulsions including polyethylene glycols, their ester derivatives, their ether derivatives typically having the formula wherein R is an alkyl radical having 1 to 5 carbon atoms and wherein n is 15l00, and related derivatives.
• the subject addenda can also be used in emulsions which form latent images predominantly on the surface of the silver halide crystal or in emulsions which form latent images predominantly insidethe silver halide crystal, such as those described in Davey and Knott US. Patent 2,592,250, issued April 8, 1952. V
• the subject addenda can also be used in emulsions intended for use in diiTusion transfer processes which utilize the undeveloped silver halide in the non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver
• diiTusion transfer processes which utilize the undeveloped silver halide in the non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a receiving layer in close proximity to the original silver
• Such processes are described in Rott U.S. Patent 2,352,014, issued June 20, 1944, and Land US. Patents 2,584,029, issued January 29, 1952; 2,608,236, issued December 28, 1954 and 2,543,181, is sued February 27, 1951.
• They can also be used in color transfer processes which utilize the diffusion transfer of an imagewise distribution of developer, coupler or dye, from a light-sensitive layer to a second layer, while the two layers are in close proximity to one another.
• gelatin In the preparation of the silver halide dispersions employed for preparing silver halide emulsions, there can be employed as the dispersing agent for the silver halide in its preparation, gelatin or some other colloidal material such as colloidal albumin, a cellulose derivative, or a synthetic resin, for instance, a polyvinyl compound, although gelatin is preferred.
• colloids which can be used are polyvinyl alcohol or a hydrolyzed polyvinyl acetate as described in Lowe US. Patent 2,286,215, issued June 16, 1942; a far hydrolyzed cellulose ester such as cellulose acetate hydrolyzed to an acetyl content of 19-26% as described in US.
• Patent 2,768,154 issued October 23, 1956; or containing cyanoacetyl groups such as the vinyl alcohol-vinyl cyanoacetate copolymer as described in Unruh, Smith and Priest US. Patent 2,808,331, issued October 1, 1957; or a polymeric material which results from polymerizing a protein or a saturated acylated protein with a monomer having a vinyl group as described Illingsworth, Dann and Gates U.S. Patent 2,852,382, issued September 19, 1958. If desired, compatible mixtures of two or more of these colloids can be employed for dispersing the silver halide in its preparation.
• Typical supports for photographic elements of the invention include cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethyleneterephthalate film and related films of resinous materials, as Well as glass, paper, wood, metals and others.
• EXAMPLE 1 Typical 1,1-dirnethylhydrazinium salts were incorpo rated into a high speed negative-type gelatino-silver bromoiodide emulsion which was panchromatically sensitized with cyanine dye. The emulsion was coated on cellulose acetate film supports at a coverage of about 435 mg. of silver and about 1050 mg. of gelatin per square foot. The prepared photographic elements were exposed in the form of film strips in an Eastman lb sensitometer, developed for 5 minutes at 68 F., and then fixed, washed and dried in the usual manner. Test samples containing no 1,1-dimethylhydrazinium salt were also included in the tests for purposes of comparison.
• the developer had the following formula: 1
• the subject 1,1-dimethylhydrazinium salts substantially increase the speed of photographic silver halide emulsions without accompanying undesirable amounts of fog.
• EXAMPLE 2 described for the data in Table A.
• the developer used to obtain the data in Table B (Developer I) is described in Example 1
• the developer used to obtain the data in Table C (Developer 11) has the following formula:
• EXAMPLE 3 To illustrate the unexpectedly high sensitizing properties of the l, l-dimethylhydrazinium salts of the invention, a typical sensitized addendum of the invention was compared with several known sensitizing hydrazine salts.
• the various addenda were incorporated into the photographic gelatino-silver bromoiodide emulsion described in Example 1, coated on a cellulose acetate film base at a coverage of 725 mg. of silver and 1330 mg. of gelatin per square foot and exposed in an Eastman Ib sensitometer, developed for 6.5 minutes at 68 F. in a developer of essentially the same composition as described in Example 1, and then fixed, washed and dried in the usual manner.
• R is an alkyl group. More specifically, 37.5 g. of 1,1-dimethylhydrazine is dissolved in 400 ml. of diethyl ether and a 0.5 mole of the alkyl bromide is added to the solution. After 4 days at 25-30 C., 1-all 1yl-1,1-dirnethylhydraziniurn bromide is separated from the reaction mixture and converted to the perchlorate salt by dissolving in warm water and mixed with an aqueous solution of sodium perchlorate. A 10% molar excess of the sodium perchlorate is used to insure a complete reaction.
• EXAMPLE 5 The a,w-alkylene bis(1,l-dimethylhydraziniuin salts) used to obtain the test data set out in the above tables can be prepared by the procedure illustrated by the following equations:
• the present invention provides a neW class of useful chemical sensitizers 'for photographic silver halide emulsions.
• a photographic gelati-no-silver halide emulsion containing about .01 to 10 grams per mole of silver halide of l-n-dodecyll,l dimethylhydrazinium perchlorate.
• a photographic geiatino-silver halide emulsion containing about .01 to 10 grams per mole of silver halide of 1-n-tetradecyl-1,l-dirnethylhydrazinium perchlorate.
• a photographic gelatino-silver halide emulsion containing about .01 to 10 grams per mole of silver halide ot' l-n-hexadecyl-l,l-dimethylhydrazinium perchlorate.
• a photographic gelatino-silver halide emulsion containing about .0 1 to 10 grams per mole of silver halide of l-n-octadccyl- 1 l-dimethylhydrazinium perchlorate.
• a photographic gelatino-silver halide emulsion having incorporated therein a sensitizing amount of a sensitizer selected from the group consisting of l-n-decyl-1,l-dimethylhydrazinium perchlorate,

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