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

Definitions

• This invention relates to organic materials which are particularly useful in the photographic field and to gelatin compositions containing therein a compound useful for hardening gelatin under alkaline conditions, but having little or substantially no hardening action under neutral or acidic conditions.
• compositions comprising a hardenable material such as a proteinaceous material, for example, gelatin and more particularly gelatin silver halide emulsions, are satisfactorily hardened by activating certain blocked-hardeners during processing.
• hardeners are aliphatic polyoxymethylene diesters which are particularly effective under alkaline conditions to harden protein and, in photographic binders, are capable of delivering rapid image formation.
• Our invention is accomplished by adding an aliphatic polyoxymethylene glycol aliphatic carboxylic acid diester to a hardenable material, for example, proteinaceous materials such as gelatin, gelatin derivatives and the like.
• a hardenable material for example, proteinaceous materials such as gelatin, gelatin derivatives and the like.
• gelatin as used in our invention includes not only gelatin, per se, but gelatin mixtures and derivatives as hereinafter described.
• aliphatic polyoxymethylene glycol-carboxylic acid diesters of our invention include those having the following formula:
• R is lower alkyl (e.g. alkyl of 1 to 3 carbon atoms), or haloalkyl and n is in integer of from 2 to 20.
• Typical alkyl groups include methyl, ethyl, n-propyl, isopropyl, and haloalkyl groups such as chloromethyl, chlo roethyl, trichloromethyl, etc.
• our diesters can be used to treat hardenable materials such as hydrophilic colloids as exemplified by gelatin.
• hardenable materials such as hydrophilic colloids as exemplified by gelatin.
• the binding agents in photographic materials are hardened by the compounds of this invention.
• the hardening, or crosslinking, effect occurs between the hardenable material and an aliphatic polyoxymethylene glycol aliphatic carboxylic acid diester of the invention.
• a method of hardening a hardenable material which comprises treating said material with a compound having the formula disclosed above.
• This hardenable material can comprise a layer on a support in a photographic element, for example, the layer can comprise a photographic silver halide emulsion.
• a useful range of blocked hardener is from 0.5 to 10 percent, based on the weight of the gelatin. Activation of the blocked hardener occurs preferably at a pH of about 10, a useful range being about 7 to 14.
• the pH can be adjusted prior to, during or after the addition of the hardening compounds to the hardenable material.
• the compounds of the invention can be fractionally distilled in many cases into substantially pure esters and used as such.
• Example I A preparation of dioxymethylene diacetate is effected following the procedure described by Tomiska and Spousta, Angew. Chem. 74, 248 (1962) for reacting s-trioxane with acetic anhydride.
• the dioxymethylene diacetate was recovered having a boiling point of approximately 54-56 C. (0.7 mm.).
• Example II In the same procedure as shown in Example I, there is also recovered trioxymethylene diacetate, possessing a boiling point of approximately 62-63" C. (0.07 mm).
• Example IV Mono-oxymethylene diacetate is obtained by fractionation of the forerun obtained in Example III; B.P. 65 mm.).
• Example V Dodeca(oxymethylene)diacetate is ob- 4 semi-solid extracted with ether. Fractionation of the ether extracts produce several fractions, one of which proves to be his (chloroacetoxy)rnethane with a boiling point of 66-68 C. (1 n 1.4662.
• the structure is confirmed by elementary analysis and by the nuclear magnetic resonance spectrum.
• Example VIII A higher boiling fraction from the ether extracts of Example VII which solidifies, is recrystallized from ether. This fractions structure is shown by elementary analysis and by nuclear magnetic resonance to be that of octa(oxyrnethylene)-bis-(chloroacetate).
• the compounds prepared in the preceding examples were added to separate portions of a high-speed silver bromoiodide emulsion panchromatically sensitized with a cyanine dye.
• Each emulsion sample was coated on a cellulose acetate film support at a coverage of 432 mg. of silver and 980 mg. of gelatin per square foot.
• a sample of each film coating was exposed on an Eastman IB sensitomere, processed for five minutes in Kodak D-l9 developer, and dried with the following results:
• Sensitometric data fresh Percent swell Rel. Wash Compound used Percent 1 speed Gamma Fog Dev. Fix water Control 100 1. 18 13 600 390 650 Dioxymet-hylene diaeetate 6 102 1. 12 380 260 410 Trioxymethylene diacetate 6 112 1. 23 11 350 240 360 Mono-oxymethylene diaeetate 6 112 1. 11 540 350 590 Control. 100 1. 57 16 460 320 510 Mixed trl-tet-ra and pentaoxymethyleno d1- acetates 6 89 1. 43 13 360 260 410 Mixed pentaand hexaoxy-methylene diacetates 6 89 l.
• Sensitometric data fresh Percent swell Wash Compound used Percent 1 Speed Gamma Fog Dev Fix water Control 100 1. 22 l4 1, 400 580 910 1 147 1. 3O 14 1, 100 490 790 Dioxymethylene diacetate. 3 297 1. 27 14 960 440 670 6 95 l. 23 l4 1, 510 710 Trioxy-methylene diacetate 3 94 1. 23 13 830 360 570 6 97 1. 23 14 900 420 620 Monooxymethylene diacetate 3 1. 32 14 1, 300 540 880 6 102 1. 32 14 1, 200 490 800 1 Based on weight of dried gelatin.
• Example Vl From the ether extraction of Example V, a residue is extracted with chloroform at 25 C. Upon evaporation and recrystallization from the chloroform, a colorless solid extract is produced having a melting point of 98100 C. This solid is heptadeca(oxymethylene)diacetate (Staudinger et a1. reports 98.599.5 C. for this compound.)
• Example VII.Bis(chloroacetoxy)methane is produced as folows: A mixture of 300 parts of chloroacetic anhydride and 265 parts of paraformaldehyde is heated at C. for 1 hour in a stirred autoclave. The reaction The silver halides employed in the photographic emul- 65 sions include any of the photographic silver halides, as
• Photographic emulsions of the present invention can contain antifogging and stabilizing agents and can be product is washed with petroleum ether and the residual 75 sensitized using any of the well-known techniques in emulsion making, for example, by digesting with naturally active gelatin or various sulfur compounds and/or gold compounds.
• the emulsions may be sensitized with salts of novel metals of Group VIII of the Periodic Table which have an atomic weight greater than 100.
• the emulsions can also be sensitized with labile selenium and noble metals as disclosed in US. Pat. 3,297,446 of Dunn issued Jan. 10, 1967.
• the emulsions may also contain speed-increasing addenda such as quaternary ammonium salts, polyethylene glycols, or thioether sensitizers.
• the emulsions of the invention may also contain conventional additives such as gelatin plasticizers, additional hardeners and coating aids. These emulsions may be used in X-ray and other non-optically sensitized emulsions, and may also be used in ortho-chromatic, panchromatic and infrared sensitive emulsions. The additives may be added to the emulsion before or after sensitizing dyes, if any, are used.
• the emulsions may 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 colorgenerating materials, or emulsions of the mixed-packet type, as disclosed in US. Pat. 2,698,794 of Godowsky issued Jan. 4, 19 55, or emulsions of the mixed-grain type, such as disclosed in US. Pat. 2,592,243 of Carroll and Hanson issued Apr. 8, 1952.
• the emulsions obtained in accordance with this invention may 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.
• Such processes are described in US. Pats. 2,352,014 of Rott issued June 20, 1944; 2,543,181 of Land issued Feb. 27, 1951; and 3,020,155 of Yackel et al. issued Feb. 6, 1962.
• the emulsions may also be used in diffusion transfer color processes which utilize a 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
• emulsion vehicles and dispersing agents for silver halide grains may be employed singly or in combination with each other, for example, gelatin, colloidal albumin, cellulose derivatives and synthetic resins, such as polyvinyl compounds.
• the blocked hardeners of this invention are effective with polymeric substances used in combination with gelatin in photographic emulsions, or otherwise as noted in Smith application U.S. Ser. No. 525,272, filed Dec. 20, 1965 US. Pat. 3,459,790.
• our blocked hardeners can be used with gelatin derivatives, such as those described in Yutzy and Frame US. Pat. 2,614,928, issued Oct. 21, 1952.
• colloids examples include poly(vinyl alcohol), hydrolyzed poly(vinyl acetate), hydrolyzed cellulose ester, water-soluble ethanolamine cellulose acetate, polyacrylamide, copolymers having a combined acrylamide content of 3-60 percent, copolymers of alkyl acrylate and acrylic acid, a vinyl alcohol copolymer containing urethane carboxylic acid groups or containing cyanoacetyl groups, or polymeric material which results from polymerizing a protein or saturated acrylated protein with a monomer having a vinyl group such as disclosed in US. Pat. 2,852,382 of Jones issued Sept. 16, 1958.
• Such polymeric additives may be employed as latices or hydrosols in the preparation of the photographic emulsions of our invention.
• the photographic emulsions can be coated on a wide variety of supports, preferably supports which are transparent and/or flexible.
• Typical supports include metals such as aluminum, paper, cellulose acetate film, polyvinyl acetate film, polystyrene film, polypropylene film and other polyolefin film, polycarbonate film, polyethylene terephthalate or other polyester film and other related materials.
• Supports such as paper which are partially acetylated or coated with an alpha-olefin polymer particularly a polymer of an alpha-olefin containing 2-10 carbon atoms, as exemplified by polyethylene, polypropylene, ethylenebutene copolymers and the like, give good results.
• these agents can be used in the preparation of various subbing layers for silver halide emulsions, interlayers, filter layers or in overcoat layers.
• a gelatin containing composition comprising a hardening concentration of an aliphatic polyoxy-methylene glycol aliphatic carboxylic acid diester.
• R is lower alkyl being unsubstituted or containing a halogen substituent
• n is an integer of from 2 to 20.
• a gelatin silver halide photographic emulsion comprising therein a hardening concentration of a polyoxymethylene diester having the structure:
• R is lower alkyl being unsubstituted or containing a halogen substituent
• n is an integer of from 2 to 20.
• R is Ris in which R is lower alkyl being unsubstituted or containing a halogen substituent, and n is an integer of from 2 to 20.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Citations (3)

• 1967
  • 1967-09-01 US US664924A patent/US3539351A/en not_active Expired - Lifetime
• 1968
  • 1968-08-29 GB GB41242/68A patent/GB1222024A/en not_active Expired
  • 1968-08-29 BE BE720147D patent/BE720147A/xx unknown
  • 1968-08-30 FR FR1577860D patent/FR1577860A/fr not_active Expired

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