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

• the present invention relates to hardeners for photographic gelatin and a method for hardening a gelatincontaining photographic layer.
• a number of compounds have been proposed for gelatin hardeners; Among them, the following compounds have been known to be especially effective; i.e., formalin, mucochloric acid, addition products of formalin, nitrogencontaining heterocyclic six membered ring compounds having two or more of active halogens in the molecule for instance, 2,4-dichrolo-6-B-hydroxyethylaminel,3,5.-triazine, compounds having active vinyl groups such as divinyl sulfone, divinyl ketone, N,N,N- triacryloylhexahydro-1,3,5-triazine, compounds containing two or more of aziridine groups or epoxy groups in the molecule and high molecular hardeners such as dialdehyde starch, polyvinyl alcohol and maleic acid half esters of starch, etc.
• formalin i.e., mucochloric acid, addition products of formalin, nitrogencontaining heterocyclic six membered ring compounds having two or more of active halogen
• German Pat. No. 872,153 (1949) discloses use of divinyl sulfone, but this compound has strong irritating property and toxicity to human body.
• German Patent Publication No. 1,100,942 (1961) has proposed aromatic compounds having two or more of vinylsulfonyl groups in the molecule and US. Pat. No. 3,490,911 (1970) has proposed compounds having vinylsulfonylethyl groups.
• vinyl sulfone type hardeners have rapid hardening action and the so-called posthardening occurs with difficulty, the so-called over-hardening phenomenon (hardening proceeds to much and photographic emulsion film hecomes keratin (becomes brittle) to damage the permeability of processing solution) occurs in low frequency; photographically undesirable actions such as fog, stain or ground, etc., less occur; and the suppression of color development or discoloration caused by reactions with color couplers are not caused.
• the vinyl sulfone type hardeners are excellent in these points, but most of them are too much expensive and moreover some of them require a large amount of organic so
• One object of the present invention is to provide effective hardeners for photographic gelatin and for gelatin-containing photographic emulsions. Another object of the present invention is to provide a method for effectively hardening a gelatin-containing photographic layer. Other object ofthe present invention will appear herein.
• the change of viscosity of the photographic emulsion during preparation is surprisingly minor as compared with that of the case of other vinyl sulfonyl compounds being used and this is the important characteristic of the compounds used as hardeners of the present invention.
• These compounds have further characteristics that they are excellent in affinity with water and require no special organic solvent in their application, being different from the other conventional vinyl sulfonyl compounds.
• the compounds of the present-invention are also superior to the conventional vinyl sulfonyl compounds in that they have substantially no bad effect on human body due to gasification and cause less physiological action to the skin.
• the B-chloroethyl sulfonyl groups can be introduced as follows:
• B-Unsaturated fatty acid derivatives and B-chrolo ethane sulfinic acid are reacted to produced compounds having the said group, or hydroxyl groups of B-(B-hydroxylethylthio) fatty acid derivatives produced by reactions of B-mercaptoethanol and B-unsaturated fatty acid derivatives are firstly converted to the chrologroups and then its thioether bond is oxihydroxyl group is chlorinated into above mentioned minutes.
• the temperature was decreased to C and stirring was carried out for 1 hour and thereafter the separated crystal was filtered off. To the filtrate while stirring at 5 C was added a solution of 7.1 g of acrylamide in 50 ml of water and they were preserved at cold state for 48 hours.
• Table 1 stand for cooling, water was added thereto and insoluble matter was filtered and, recrystallized from water to obtain 2.4 g. of colorless crystalline powder having a melting point of 2l3.0 214.0C.
• Preparation 3 N.Nmethylene bis-91HB-chlorocthylsulfonyl) propionamide) was dispersed in 250 ml of dimethylformamide and added thereto with stirring was 4.44 g. of triethylamine at room temperature. The stirring was continued for 5 hours and then the undissolved matter was filtered off.
• EXAMPLE 1 by polyethylene coating and which contained no From the above Table 1, it is clearly recognized that a gelatin-containing photographic emulsion layer which was hardened in a short period of time after coating and showed no over-hardening under acceleration conditions was obtained without causing any undesirable effect on sensitivity and fog density.
• the rapid hardening action of the hardener of the present invention is comparable to that of the compound (c) and superior to the compound (b) as well as the compound (d).
• Compound (a) can be used as a 1 percent aqueous solution, but compound (c) must be added to emulsion as 1 percent DMF solution or 1 percent dioxane solution.
• Example I was repeated except that the compound obtained in Preparation 3 was replaced by compound (lV) listed before to obtain the same results as Example I.
• Example 1 was repeated except that the compound obtained in Preparation 3 was replaced by compound (Vll) listed before to obtain the same results as those of Example 1.
• EXAMPLE 5 ca ca so CH CHCONH ⁇ X en CH S0 CH (IZHCONH (Wherein R is a member selected from the group consisting of hydrogen and methyl group and X is a lower alkylene group 1 to 6 carbon atoms).
• composition according to claim 1 wherein the amount of the hardener is 0.1 20 percent by weight of gelatin based on the dry weight.
• a method for hardening a gelatin-silver halide photographic emulsion characterized in that a hardener having the general formula:
• R is a member selected from the group consisting of hydrogen and methyl group and X is a lower alkylene group of l to 6 carbon atoms

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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)
• Silver Salt Photography Or Processing Solution Therefor (AREA)

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Cited By (10)

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Citations (2)

• 1971
  • 1971-12-30 JP JP47002346A patent/JPS5035807B2/ja not_active Expired
• 1972
  • 1972-12-27 US US319025A patent/US3868257A/en not_active Expired - Lifetime

Patent Citations (2)

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