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
  • 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

Definitions

• compositions of matter comprising certain compounds containing two vinylsulfonylalkyl groups attached to a single heteroatom are disclosed as effective hardening agents for hardenable material. Photographic elements comprising said compounds are also disclosed.
• This invention relates to a class of new hardeners and more particularly to hardening compounds containing two vinylsulfonylalkyl groups attached to a single heteroatom.
• this invention relates to the rendering of compositions of proteins and proteinaceous substances, such as hydrophilic colloids, resistant to the effects of swelling from aqueous solutions.
• it relates to the use of said hardeners in photography and more particularly to photographic elements comprising a layer hardened by said hardeners and exhibiting reduced staining characteristics.
• improvements in photographic elements comprising color couplers.
• Yet another object of this invention is to provide certain vinylsulfonyl compounds possessing increased hardening activity as compared to known hardening compounds.
• single linking heteroatom is meant an atom chosen from non-metals in Groups VA and VI-A of the Periodic Table, which atoms include, for example, oxygen and nitrogen and which atoms can be substituted or unsubstituted, for example, alkyl nitrogen and dialkyl nitrogen linking atoms and more particularly,
• these hardening compounds are conveniently incorporated into photographic gelatin emulsions and layers thereof in order to provide needed hardening without substantially affecting photographic sensitivity adversely.
• These new hardening compounds can be effectively used in various concentrations for hardening purposes although a preferred suitable hardening concentration is generally in the range of from about 0.1 to 10% and more preferably about 0.5 to 6% by weight, based on the hardenable material such as the hydrophilic colloid.
• the hardeners described herein are particularly effective in color photography when combined with color couplers. Their use results in reducing the staining characteristics usually exhibited by multiple layer photographic silver halide systems containing a color coupler and hydrophilic colloid layers.
• Such layers generally comprise hardenable carboxyl-containing polymers, for example, gelatin, vinyl polymers, or mixtures thereof.
• Suitable carboxyl-containing polymers are film-forming and suitable vinyl polymers are exemplified by methyl acrylate-acrylic acid polymer, butyl-acrylate-acrylic acid polymer and the like.
• One embodiment of this invention relates to hardening compounds having two vinylsulfonylalkyl groups linked to a single linking heteroatom or radical.
• composition of matter comprising a hardenable substance and a hardener having the formula in which in is an integer of from 1 to 4, Z is a single heteroatom, and R is hydrogen or lower alkyl groups such as methyl, ethyl, isopropyl and the like which groups in turn can be further substituted.
• compositions of matter comprising a hydrophilic colloid and a hardener having as the heteroatom, a single nitrogen atom, or ether oxygen.
• Still another embodiment relates to a photographic element comprising a support and an emulsion layer comprised of hardenable carboxyl-containing polymer, said emulsion being hardened by an effective concentration of a bis vinylsulfonylalkyl-type compound disclosed herein.
• the bis vinylsulfonylalkyl type compounds disclosed herein are effectively used in combination with hardenable materials generally, but find particular use in photography for hardening various proteins, like hydrophilic colloid coating compositions, binders, vehicles and the like, including photographic gelatin emulsions and layers. These layers can take the form of interlayers, overcoats, antihalation layers, silver halide emulsion layers and the like.
• photographic gelatin emulsions is meant various gelatin derivatives and physical mixtures of gel atin and other colloids. These include gelatin mixtures of synthetic polymers exemplified by copolymers of methyl acrylate and acrylic acid or butyl acrylate and acrylic acid and the like.
• the compounds disclosed herein can be conveniently added either in solution or as addition salts to the emulsion or other substance to be hardened.
• the reactions for preparing the compounds of this invention are conducted in the presence of the desired organic solvents at moderate temperatures and the reactions are not solely pressure dependent, and consequently, super-atmospheric or subatmospheric pressures can be employed.
• the specific reaction conditions for example, temperature, pressure, and the like depend upon the particular reactants used.
• 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 eifective in sulfur and gold sensitized silver halide emulsions.
• Typical supports include those generally employed for photo graphic elements, as exemplified by cellulose nitrate film, cellulose acetate film, polyvinyl acetal film, polystyrene film, polyethylene terephthalate film, and related films.
• a-olefin polymers particularly polymers of u-olefins containing 210 carbon atoms, as for example, polyethylene, polypropylene, ethylene butene copolymers, and the like can also be employed.
• photographic emulsions and elements can also contain ad ditional 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. Pat. 3,128,180 issued Apr. 7, 1964.
• the emulsions hardened by our new compounds can be used in photographic elements intended for color photography and thus can 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 chloroiodine, and the like.
• the silver halides used can be those which form latent images predominantly on the surface of the silver halide grains or those which form latent images inside the silver halide emulsion.
• Hardened emulsions obtained in accordance with this invention and with gelatin or other hardenable hydrophilic colloids can be used in diffusion transfer materials.
• the disulfide is oxidized to the disulfone by hydrogen peroxide according to the method of H. S. Schultz et al., J. Org. Chem., 28, 1140 (1963).
• the resulting diol is converted to 2,2-bis(Z-chloroethylsulfonyl) ethyl ether by adding two molar proportions of thionyl chloride to a refluxing solution of the diol in acetonitrile containing a catalytic amount of N,N,-dimethylformamide.
• removal of the solvent and recrystallization from ethanol-acetone gives a high yield of a colorless chloride having a melting point of 70- 71 C.
• Dehydrohalogenation is effected in tetrahydrofuran solution at about 0-5" C. with two molar proportions of triethylamine. After 24 hours, the solvent is removed and the product recrystallized from methanol giving colorless crystals having a melting point of 47.5-48.5 C.
• bis vinylsulfones exhibiting good hardening include N,N bis(2 vinylsulfonylethyl) N ethyl-N- propylammonium tetrafiuoroborate, and bis(l vinylsulfonylethyl) ether.
• EXAMPLE V As previously indicated, the hardening compounds described herein give very good results when used to harden hydrophilic colloids, for example, gelatin compositions and more particularly photographic silver halide gelatin emulsions. To illustrate this, the compound prepared in the above Example I is added to separate sample portions of a high-speed silver bromoiodide emulsion which is panchromatically sensitized with a cyanine dye.
• Each emulsion sample is coated on a cellulose acetate film support at a coverage of 459 milligrams of silver and 1040 milligrams of gelatin per square foot.
• a sample of each film coating is then exposed on an Eastman 1B Sensitometer, processed for five minutes in Kodak DK-SO Developer, fixed, washed and dried. Results are recorded for sensitometric efiect of these compounds as compared to a control and to a prior art hardening compound l,2-bis(2-vinylsulfonyleth0xy) ethane. Similar good results are obtained with the other hardening compounds of this invention including those of Example IV.
• the coatings are tested for hardness after 1 day, 5 days after coating and upon heating with a p-phenylenediamine color developing solution at 10 C. intervals from 30 C. to 80 C., then immersing each test strip in the solution during the entire heating cycle and holding the bath temperature for 2 minutes at each interval. This is followed by rubbing or scratching through a rubber glove after each interval.
• Silver halide emulsions containing the hardners 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 ditfusion 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.
• diffusion transfer color processes which utilize a ditfusion 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.
• Such processes are described in Rogers US. Pat. 2,983,606 issued May 9, 1961; Weyerts et al. US. Pat. 3,253,915 issued May 31, 1966; and Whitmore US. Pat. 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 US. Pat. 2,614,927 of Broughton and Woodward issued Oct. 21, 1952, and as described in the article Stabilization Processing of Films and Papers, by H.
• 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.

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

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Cited By (18)

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Citations (1)

• 1967
  • 1967-11-13 US US682525A patent/US3539644A/en not_active Expired - Lifetime
• 1968
  • 1968-11-08 GB GB53119/68A patent/GB1255786A/en not_active Expired
  • 1968-11-08 GB GB28504/71A patent/GB1255787A/en not_active Expired
  • 1968-11-12 BR BR203926/68A patent/BR6803926D0/pt unknown
  • 1968-11-13 FR FR1599038D patent/FR1599038A/fr not_active Expired
  • 1968-11-13 BE BE723806D patent/BE723806A/xx not_active IP Right Cessation
  • 1968-11-13 DE DE19681808685 patent/DE1808685A1/de active Granted

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