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 the hardening of gelatin either when applied as an emulsion layer on a support, such as film, plate or paper, or when applied in the form of a solution as a simple coating or sizing for paper'or the like.
• gelatin emulsion layers or gelatin layers in general are capable of resisting ject of our invention is to provide a process of hardening gelatin coatings or layers generally whether in the form of a photographic emulsion or merely in the form of a layer or coating on paper or some other support therefor.
• Other objects of our invention will appear herein.
• the above objects may be ac complished by incorporating into an aqueous solution of gelatin or into a gelatin photographic emulsion a small proportion of a bis-ester of methane sulfonic acid.
• the composition which also forms a part of our invention, has been coated out onto a support, it is then subjected either to an elevated temperature or to long standing, which treatment increases the hardening efiect.
• any amount of one of these compounds has a hardening effect upon the gelatin, but it is usually 'desirable that at least 0.025 part of the hardenerper 15.5 parts of gelatin be present to give an effective hardening, it being preferable to use approximately 0.25 part of the hardener per..15.5 parts of gelatin.
• the hardener can be employed in proportions up to as much as M by weight of the gelatin, but as the preferred proportion given is ice
• Example 1.-1,2-di-(methanesulfonoxy)-etharie 310 parts of dry ethylene glycol was dissolved in 1500 7 parts of dry pyridine, and 1150 parts of methanesulfonyl chloride was slowly added to this solution with vigorous stirring.
• the temperature of the system was maintained between 5 and 15 C. After the reaction was completed the mass was stirred into three times its volume of finely crushed ice. The crystalline product which separated was I washed with ice water and then dried. The product was obtained in the form of white crystals having a melting point of 45-47 C. and a yield of 77% of theoretical.
• Example 2.--1,3-di-(methanesulfonoxy)-pr0pane 152 parts of trimethylene glycol was dissolved in 600 parts of dry pyridine, and 460 parts of methanesulfonyl chloride was slowly added thereto while vigorously agitating and maintaining the temperature between 5 and 15 C. After the reaction was completed the mass was stirred into three times its volume of. finely crushed ice. The crystals obtained were washed with ice water and dried. These crystals were recrystallized from ethyl alcohol.
• the crystals obtained had a melting point of 41942 C.
• Example 3.-1,5-di-(methanesulfonoxy)-pentane ride was added to this solution with vigorous stirring while the temperature was maintained between 5 and 15 C. After the reaction was completed, the mass was stirred into three times its volume of finely crushed ice. The crystalline product which separated was washed with ice water and dried. White crystals were obtained having a melting point of 3536 C.
• Example 4.fl,p-di-(methanesulfonoxy)-diethyl ether 212 parts of dry diethylene glycol was dissolved in 1200 parts of dry pyridine, and 460 parts of methanesulfonyl chloride was slowly added to the solution with vigorous agitating while maintaining the temperature between 5 and 15 C. After completion of the reaction the mass was stirred into three times its volume of finely crushed ice and the crystalline product was purified as in the preceding examples. White crystals were obtained having a melting point of 57-58" C.
• the various compounds prepared as above were used for hardening gelatin by adding to 200 cc. portions of a photographic emulsion containing approximately 15 /2 grams of gelatin, 0.025 gram and 0.25 gram respectively of p the compound in solution in methanol. Also, a control coating was made with the same batch of emulsion, but 1 without hardener. After coating the emulsion upon a support therefor, the coated support was incubated one day at F. and 50% R. H. to complete the hardening process. The degree of hardening was then determined by immersing the coatings in water at 70 F. and gradually raising the temperature to the point at which the coating disappeared from the support, the rate of increase in temperature being the same in all tests, and the water being stirred during the process.
• the reaction mixture was stirred into 3 times its volume of crushed ice.
• the crystalline product obtained was washed with ice water and dried. It was purified by recrystallization from ethyl alcohol.
• the product obtained had a melting point of 57-58 C.
• the above-prepared 1,6-di-(methanesulfonoxy)-hexane was employed as a hardener in photographic emulsions in the following manner: To 200 cc. portions of a silver halide-gelatin photographic emulsion containing about 8% gelatin was added methyl alcohol solutions of 1,6-di- (methanesulfonoxy)-hexane containing respectively 0.1, 0.2 and 0.4 gram thereof. The emulsions so prepared were coated onto glass plates, dried and were then conditioned by treating at 72 F. and 50% relative humidity, followed by heat sealing in foil bags and heating for 24 hours at 100 F.
• the melting points of these emulsion coatings were then determined in a water bath by bringing the temperature to 212 F. and holding for a maximum of 20 minutes, unless, of course, melting occurs sooner.
• the melting points of the coatings were as follows, a coating containing no hardener being included as a check:
• the gelatin coating may be allowed to stand for some time at ordinary temperature, whereupon it becomes resistant to the effects of boiling water.
• 0.05 gram of 1,5-di-(methanesulfonoxy)-pentane was added to 200 cc. of emulsion as described above, and was coated out on a support, and the emulsion layer was kept for at least 14 days at 70 F., whereupon the resulting layer was found to resist the melting effect of boiling water.
• the rate at which the hardening is effected is influenced by the temperature and the relative humidity. Therefore, if the coatings are allowed to stand under normal conditions, the time for curing is longer than when an elevated temperature is used. Also, if the curing is carried out at an elevated temperature, a decrease in relative humidity will necessitate either a higher temperature or a longer time than for a given relative humidity to obtain the equivalent degree of hardening. For instance, it has been found that maintaining at 100 F. and 50% R. H. for -1 day will give the maximum degree of hardening in accordance with our invention. However, if the relative humidity is lower, a higher temperature will be necessary to give the same effect in the given time and vice versa. The use of the combination of temperature, relative humidity and time which will give the ultimate degree of hardening in accordance with the proportion of hardener used will be referred to herein as curing.
• our invention is applicable not only to the manufacture of photographic emulsions of satisfactory hardening properties, but may likewise be applied to the manufacture of gelatin solutions which are to be used for producing coatings on paper, cloth, film or other surfaces. Also, if desired, these hardening agents may be used in conjunction with other hardening agents, for example, aldehydes or alum.
• a composition comprising an aqueous solution of gelatin containing therein at least 0.025 part, per 15% parts of gelatin, of a hardening agent having the following formula:
• a composition comprising an aqueous solution of gelatin containing therein approximately 0.25 part, per 15% parts of gelatin, of a hardening agent having the formula l-BChCHs wherein X is selected from the group of (CH:)o-4 and CaH4O-CaH4-.
• a composition comprising an aqueous solution of gelatin containing therein at least 0.025 part, per 15% parts of gelatin, of 1,2-di-(methanesulfonoxy)-ethane.
• a composition comprising an aqueous solution of gelatin containing therein at least 0.025 part, per 15% parts of gelatin, of 1,3-di-(methanesulfonoxy)-propane.
• a composition comprising an aqueous solution of gelatin containing therein at least 0.025 part, per 15% parts of gelatin, of 1,5-di-(methanesulfonoxy)-pentane.
• a composition comprising an aqueous solution of gelatin containing therein at least 0.025 part, per 15% parts of gelatin, of p,p-di-(methanesulfonoxy)-diethyl ether.
• a photographic product comprising a gelatin layer upon a support therefor, which gelatin layer contains therein at least 0.025 part, per 15% parts of gelatin, of a hardener having the formula in which X is selected from the group (CH:)e-4 and C2H40C2H4.
• a photographic product comprising a gelatin layer upon a support therefor, which gelatin layer contains therein approximately 0.25 part, per 15% parts of gelatin, of a hardener having the formula x -SO1CH3 in which X is selected from the group (CHa)o-4 and -C2H4O-C2H4.
• a photographic product comprising a gelatin layer upon a support therefor, which gelatin layer contains therein at least 0.025 part of 1,2-di-(methancsulfonoxy)- ethane per 15% parts of gelatin.
• a photographic product comprising a gelatin layer upon a support therefor, which gelatin layer contains therein at least 0.025 part of 1,3-di-(methanesulfonoxy)- propane per 15% parts of gelatin.
• a photographic product comprising a gelatin layer upon a support therefor, which gelatin layer contains therein at least 0.025 part of l,S-di-(methanesulfonoxy)- pentane per 15 /2 parts of gelatin.
• a photographic product comprising a gelatin layer (E-SOxCH:
• X is selected from the group (CHz)o-4 and CzH4-O--C2H4.
• a method of hardening gelatin the step which comprises adding to an aqueous gelatin solution, prior to coating out upon a surface, approximately 0.25 part, per 15 parts of gelatin, of a hardener having the formula (f-BOaCH;

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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)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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Citations (2)

• 0
  • BE BE515924D patent/BE515924A/xx unknown
• 1951
  • 1951-12-01 US US259511A patent/US2726162A/en not_active Expired - Lifetime
• 1952
  • 1952-11-25 DE DEE6370A patent/DE935706C/de not_active Expired
  • 1952-12-01 GB GB30402/52A patent/GB729345A/en not_active Expired
  • 1952-12-01 FR FR1078393D patent/FR1078393A/fr not_active Expired

Patent Citations (2)

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