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
  • G03C1/30—Hardeners
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C315/00—Preparation of sulfones; Preparation of sulfoxides
  • C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C317/00—Sulfones; Sulfoxides
  • C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C317/18—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to acyclic carbon atoms of the carbon skeleton
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
  • C07C323/10—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton
  • C07C323/11—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
  • C07C323/12—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and singly-bound oxygen atoms bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L101/00—Compositions of unspecified macromolecular compounds

Definitions

• This invention relatesto gelatin compositions in which a hardener has been incorporated, which hardener contains two or more vinylsulfonylalkyl groups. These groups can be attached to a plurality of tertiary or quaternary nitrogen atoms or to a plurality of ether oxygen atoms or a combination thereof.
• One object of our invention is to provide effective hardeners for photographic gelatin and for gelatin-containing photographic emulsions. Another object of our invention is to provide gelatin hardeners which are free from undesirable photographic properties and have good water solubility, low volatility and low physiological activity. Other objects of our invention will appear herein.
• photographic gelatin is interpreted as including gelatin derivatives and physical mixtures of gelatin and other colloids, such as mixtures of gelatin with compatible synthetic polymers exemplified by copolymers of methyl acrylate and acrylic acid or butyl acrylate and acrylic acid and the like.
• n is an integer from 2 to 6;
• A is each R is an alkyl group of 1 to 4 carbon atoms,
• X is an anion, such as for example C l-I SO ClO CH OSO and the like;
• m is 1 or 2;
• Z is a polyvalent radical of n valences such as for example alkylene radicals of from 1 to 10 carbon atoms which can contain unsaturation or which can be interrupted by an arylene in which R and R are lower alkyl groups of 1-4 carbon atoms, each m is 1 or 2 and R represents an alkylene chain of from 1-10 carbon atoms which can contain unsaturation or which can be interrupted by an arylene radical, a cycloalkylene radical or by simple functional groups such as ether, sulfur or amide linkages.
• R and both R s together with the two nitrogen atoms can constitute a heterccyclic ring such as piperazine, alkyl substituted piperazines and the like, and X is any suitable anion, such as C l-I SO ClO CH OSO and the like.
• the hardeners in accordance with our invention when present in the gelatin composition, exert hardening action, however, for practical purposes ordinarily the amount of hardener used would be in the range of 05-15%, based on the weight of the gelatin in the compositions.
• the compounds described in this application can be used effectively in combination with hardenable materials in general but they are most advantageously used with natural or synthetic polymers used as vehicles or binders in preparing photographic elements.
• Specific materials which can be hardened according to the practice of this invention include hardenable materials such as polymers, for example, gelatin, colloidal albumin, acid or watersoluble vinyl polymers, cellulose derivatives, proteins, various polyacrylamides, dispersed polymerized vinyl compounds, particularly those which increase the dimensional stability of photographic materials as exemplified by amine-containing polymers of alkyl acrylates, methacrylates, acrylic acid, sulfoalkyl acrylates or methacrylates, maleic acid, and the like.
• the hardening agents described herein can be used in various kinds of photographic emulsions. In addition to being useful in orthochromatic, panchromatic, and infrared emulsions, they are also useful in X-ray and other nonoptically sensitized emulsions. They can be added to the emulsions before or after the addition of any optically sensitizing dyes which may be used. They are effective in sulfur and gold sensitized silver halide emulsions.
• Typical supports include those generally employed for photographic elements as exemplified by cellulose nitrate film, cellulose acetate film, polystyrene film, polyethylene terephthalate film, and related films or resinous materials as well as glass, paper, metal, wood, and the like.
• Supports such as paper that are coated with u-olefin polymers, particularly polymers of wolefins containing 2-10 carbon atoms, as for example, polyethylene, polypropylene, ethylene butene copolymers, and the like, can also be employed.
• photographic emulsions and elements can also contain additional additives, particularly those known to be beneficial in photographic emulsions, as exemplified by optical sensitizers, speed increasing materials, other hardeners, plasticizers, and the like, such as those described in Henn and Goife US. Patent 3,128,180 issued Apr. 7, 1964.
• the emulsions hardened by new compounds can be used in photographic elements intended for color photography and thus may contain color-forming couplers or used as emulsions to be developed by solutions containing couplers or other color-generating materials or emulsions of the mixed-packet type.
• the silver halides employed in the photographic emulsions include any of the photographic silver halides as exemplified by silver bromide, silver iodide, silver chloride, silver chlorobromide, silver chloroiodide, and the like.
• the silver halides used can be those which form latent images predominantly on the surface of the silver to limit the scope of the invention unless otherwise spev cifically indicated.
• Examples 1-10 illustrate methods of preparing these hardening compounds and the tables following Examples 5 and 12 supply data indicating desirable photographic effects unexpectedly obtained using the various hardeners described herein.
• N,N-bis 2-vinylsulfonylethyl) piperazine-bis- (methoperchlorate) A solution of 9.7 parts of N,N'-bis(2-vinylsulfonylethyl)piperazine and 16.7 parts of methyl p-toluenesulfonate in 50 parts of acetonitrile is stirred at room temperature for two hours and then refluxed overnight. The solution is treated with charcoal and the filtrate is evaporated at reduced pressure on a water bath to /2 volume and poured into ether. An oily precipitate is obtained.
• This precipitate is washed with ether, dissolved in a minimum amount of water and then treated with a concentrated solution of about 20 parts of sodium perchlorate in 10 parts of water.
• the product is induced to crystallize, is filtered, and then recrystallized from a minimum amount of water.
• the colorless product obtained melts at 191-192 C.
• the metho-toluene sulfonate is prepared in essentially the same manner as in the preceding example but using instead of N,N' bis(2 vinylsulfonylethyl) piperazine, N,N bis(2 vinylsulfonylethyl) N,N dimethyl 2 butene 1,4 diamine.
• the colorless product designated (A) melts at 235-236 C.
• Some of the product is converted to the fiuoborate by using aqueous fiuoboric acid producing a colorless product designated (B) having a melting point of approximately 288 C. at which temperature decomposition occurs.
• EXAMPLE 5 1,2-bis (vinylsulfonylmethoxy) ethane 5,8-dioxa-3,10-dithiadodecane-1,12-diol is prepared by 6
• EXAMPLE 8 Bis [2-(2-vinylsulfonylethoxy)ethyl]sulfone The procedure described is repeated using 25 parts of divinyl sulfone and 15.4 parts of bis(2-hydroxyethyl) sulthe reaction of two molar proportions of sodium 2-hy- 5 droxyethylmercaptide with l,2-bis(.chloromethoxy)ethane fone i 20 parts of q .hmethyl slllfoxlde.
• 1,2 bis(2 chloroethylsulfonylmethoxy)ethane is preblsm (zvmylsulfonylethoxy)ethyl] urea pared by adding the disulfone diol to a large excess of 25 parts of divinyl sulfone and 14.8 parts of N,N- thionyl chloride containing a catalytic amount of N,N- b1s(2-hydroxyethyl)urea are reacted in 25 Parts Of y dimethylformamide, at room temperature. Evaporation acetonitrile and parts of dimethyl sulfoxide using of the excess thionyl chloride furnishes the crude chloride 15 sodium ethoxide catalyst. A product is obtained having which is dissolved in tetrahydrofuran and treated with an ge lar Weight of approximately 384. two molar proportions of triethylamine at 0 to 5 C.
• EXAMPLE 6 0.1 gram of hydroquinone yields an amine adduct which 1,2-bis (2-vinylsulfonylethoxy)ethane A few drops of a solution made by reacting sodium with excess ethylene glycol are added to a stirred solution of 6.2 parts of ethylene glycol in 23.6 parts of freshly distilled divinyl sulfone stabilized with less than 0.1% of hydroquinone. A rapid temperature rise indicates reaction is occurring. The reaction temperature is kept below 35 C. and a few crystals of hydroquinone are added. After 48 hours, the reaction mixture is neutralized with glacial acetic acid and any volatile compounds are removed under vacuum (0.5 mm, 30 C., five hours) and the mass is filtered. A product is obtained having an average molecular weight of approximately 293.
• EXAMPLE 7 1,4-bis(2-vinylsulfonylethoxy)butane A procedure is effected in the same .manner as the preceding example but using 24 parts of divinyl sulfone and 9 parts 1,4-butanediol in 20 parts of dry dichloromethane as the reaction medium. A liquid product is obtained having an average molecular weight of approximately 227.
• Samples of the compounds prepared in Examples 6-12 are added to separate portions of a high-speed silver bromoiodide emulsion which are panchromatically sensitized with a cyanine dye. Each emulsion sample is coated on a cellulose acetate film support at a coverage of 459 mg. of silver and 1040 mg. of gelatin per square foot. Samples of the various films are exposed on an Eastman 1B sensitometer, processed for five minutes in Kodak Developer DK-50, fixed, washed, and dried. The proportions of hardener used, the example from which the hardener was derived, the photographic tests on the fresh Fresh Tests Example Hardener Cone. Rel. Percent No. (g./mle Ag) Speed Gamma Fog Swell 100 1.
• Layer 5-Red-sensitive silver chlorobromide gelatin consisting of 90 mole percent bromide and a phenolic cyan coupler of the type described in U.S. Patent 2,423,730.
• Layer 3Gr een-sensitive silver chlorobromide gelatin emulsion consisting of 80 mole percent chloride and a pyrazolone magenta coupler of the types described in U.S. Patent 2,600,788.
• Layer 1-Blue-sensitive silver chlorobromide gelatin emulsion consisting of 98 mole percent bromide and an acyl acetanilide yellow coupler of the type described in U.S. Patent 2,875,057.
• the hardeners in accordance with our invention can be used in all six of the layers of the product or they can be used in the emulsion compositions with other hardeners being used in the gelatin layers if desired. In such use improvement in stain is obtained as compared with the use of a hardener such as formaldehyde or mucochloric acid.
• Silver halide emulsions containing the hardeners of the invention can be used in diffusion transfer processes which utilize the undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a silver layer in close proximity to the original silver halide emulsion layer.
• diffusion transfer processes which utilize the undeveloped silver halide in non-image areas of the negative to form a positive by dissolving the undeveloped silver halide and precipitating it on a silver layer in close proximity to the original silver halide emulsion layer.
• the emulsions can also be used in diffusion transfer color processes which utilize a diffusion transfer of an imagewise distribution of developer, coupler or dye, from a lightsensitive layer to a second layer, while the two layers are in close proximity to one another.
• diffusion transfer color processes which utilize a diffusion transfer of an imagewise distribution of developer, coupler or dye, from a lightsensitive layer to a second layer, while the two layers are in close proximity to one another.
• Such processes are described in Rogers U.S. Patent 2,983,606 issued May 9, 1961; Weyerts et al. U.S. Patent 3,253,915 issued May 31, 1966; and Whitmore U.S. Patent 3,227,552 issued Jan. 4, 1966.
• Silver halide emulsions containing the hardeners of the invention can be processed in stabilization processes such as the ones described in U.S. Patent 2,614,927 of Broughton and Woodward issued Oct. 21,
• the hardeners of this invention can be used to harden silver halide emulsion and other photographic layers containing silver halide developing agents such as polyhydroxy benzene, amino phenol and 3-pyrazolidone developing agents.
• composition of matter comprising a hydrophilic colloid and a hardener of the formula:
• composition of matter comprising a hydrophilic colloid and a hardener of the following formula:
• each R is a lower alkyl group
• R represents an alkylene chain which can contain unsaturation or which can be interrupted by an arylene or cycloalkylene radical or by simple functional groups, or R and both Rfs together with the two nitrogen atoms constitute a heterocyclic ring and m is 1 or 2.
• composition comprising a hydrophilic colloid and a hardener having the following formula:
• each R and R are lower alkyl groups, in is 1 or 2
• X is an acid anion
• R represents an alkylene chain which can contain unsaturation or can be interrupted by an arylene radical, a cycloalkylene radical or simple functional groups, or R and both R s together with the two nitrogen atoms constitute a heterocyclic ring.
• composition of matter comprising gelatin and N,N'-bis(2Pvinylsulfonylethyl)piperazine.
• composition of matter comprising gelatin and N,N-bis(2 vinylsulfonylethyl)piperazine bis (methoperchlorate).
• a composition of matter comprising gelatin and N,N'-bis(2 vinylsulfonylethyl)-N,N-dimethyl-2-butene- 1,4-diamine bis (metho-p-toluenesulfonate).
• a composition of matter comprising gelatin and N,N'-bis(2 vinylsulfonylethyl)-N,N'-dimethylethylene dia-mine bis (metho-p-toluenesulfonate 8.
• a composition of matter comprising gelatin and N,N'-bis[2 (-2 vinylsulfonylethoxy)ethyl]dimethylammonium p-tosylate.
• composition of matter comprising gelatin and N,N-bis[2 (2 vinylsulfonylethoxy)ethylJdimethylammonium perchlorate.
• a gelatin-silver halide photographic emulsion for use in color photography containing a coupler and, as a hardener therein, a compound having the following structural formula:
• each R is a lower alkyl group of 1 to 4 carbon atoms
• R represents an alkylene chain of from 1 to 10 carbon atoms which can contain unsaturation or is interrupted by an arylene or cycloalkylene radical or by simple functional groups
• R and both Rfs together with the two nitrogen atoms constitute a heterocyclic ring.
• composition of matter comprising a hydrophilic colloid and a hardener of the following formula:
• each R and R are lower alkyl groups, m is 1 or 2, X is an acid anion, and R represents an alkylene chain.
• a gelatin-silver halide photographic emulsion for use in color photography containing a coupler and as a hardener therein a compound having the following structural formula:
• each R is a lower alkyl group of 1-4 carbon atoms and R represents an alkylene chain.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Physics & Mathematics (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Health & Medical Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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Citations (3)

• 1966
  • 1966-09-05 BE BE686440D patent/BE686440A/xx unknown
  • 1966-09-20 GB GB41851/66A patent/GB1158263A/en not_active Expired
• 1967
  • 1967-11-13 US US682641A patent/US3490911A/en not_active Expired - Lifetime
• 1968
  • 1968-11-08 GB GB1256709D patent/GB1256709A/en not_active Expired
  • 1968-11-12 BR BR203921/68A patent/BR6803921D0/pt unknown
  • 1968-11-13 FR FR1591428D patent/FR1591428A/fr not_active Expired
  • 1968-11-13 BE BE723807D patent/BE723807A/xx unknown
  • 1968-11-13 DE DE19681808684 patent/DE1808684A1/de active Pending
• 1969
  • 1969-08-22 US US862144A patent/US3642908A/en not_active Expired - Lifetime

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