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
  • G03C1/305—Hardeners containing a diazine or triazine ring
• • 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

• Photographic materials are composed of a photosensitive emulsion layer containing silver halide, which is the main constituent for photosensitiveness, and hydrophilic organic macromolecular binders applied supplementarily thereon, for example the protective layer, intermediate layer, underlayer and backing layer whose composition is almost the same as silver halide emulsion layer.
• photographic materials are composed of a layer or layers of hydrophilic film applied on one side or both sides of a water resistant support. It is essential for these film layers, whether or not they are photosensitive, that upon photographic treatment after exposure to light, the developing solutions for photographic treatment should be allowed to sufiiciently penetrate and diffuse inthese layers.
• binders whose main constituent is gelatin have been widely used.
• natural substances such as starch and gum arabic were mainly used.
• artifiicial'substances such as polyvinyl alcohol, polyacrylic acid, polyacrylamide, and various water soluble derivatives of cellulose, polyvinyl alcohol and starch have widely come into use, solely or in mixture with gelatin.
• photographic layers comprising these water soluble binders are generally poor in water resistance, and therefore swell in excess during treatments of developing, fixing and washing. As a result, troubles such as reticulation, blister, and frilling are apt to cause. Therefore, it is usual to prevent the softening 3,717,467 Patented Feb.
• binders are also mixed as a plasticizer for the purpose of preventing the contraction of the film layer and increasing its softness. Also in this case, the water resistance generally decreases. In order to reinforce this, stronger hardeners are required. While powerful hadeners comprising dialdehyde compounds, polyfunctional epoxy compounds or active vinyl compounds such as vinyl sulfones and vinyl ketones are developed, macromolecular hardeners such as a copolymer of polyvinyl methyl ether with maleic anhydride, or of styrene with maleic anhydride, a monomaleic ester of polyvinyl alcohol or starch, or dialdehyde starch are also on the market.
• Macromolecular hardeners have in their long molecules many bonding points, where not only the molecules are crosslinked to each other but also they are crosslinked to molecules of other binders mixed therein to form a network structure. Although a great amount of water is coordinated and absorbed in this network, the film layer does not dissolve even when heated at a high temperature. This is a characteristic of high polymer hardening agents. This offers a striking contrast with the char acteristic of low molecular hardeners which, when the more powerful they are, make the film layer the more horny, decreasing the water absorption and swelling property. In the case of high polymer hardeners, they do not ditfuse or migrate from one layer to another which are superposed upon each other. Therefore, it is a further advantage of polymer hardeners that a given film layer could be hardened to a desired extent without hardening other layers at all.
• X is N: or CH R is H, CH or C H preferably or N--& CH;CONHNHC% ⁇ N 2 (Racetamino) phenylamine-4,6-dlcl1loro-1,3,5triazine is made to react in water with a Water soluble organic macromolecular colloidal binder for photographic use. Said compound is dissolved with a least possible amount of a Water miscible organic solvent which is a comparatively good solvent for both said compound and, said binder. After they have reacted homogeneously a great amount of a water miscible organic solvent which is com-- paratively poor solvent for both is added to precipitate the reaction product.
• the reaction product is separated and added to the main protective colloidal binders to constitute the photographic layer as a hardener.
• Said good solvents include formamide, dimethylformamide, dimethylformarnide, dimethylsulfoxide and tetrahydrofuran
• said poor solvents include methanol, ethanol; n-propanol, iso-propanol, butanol, acetone, and methyl ethyl ketone.
• necessary amount of a hardener to be added to gelatin is at least about 0.5 to 1% based on the weight of the dry weight of gelatin.
• the hardener dissolves in alcohol only to an extent of 0.1%. Accordingly, if silver halide emulsion, whose binder is for example gelatin, is desired to be hardened by this method, necessary amount of the hardener is 0.05 to 0.1 g. for ml. of the emulsion containing 10% of gelatin. This necessitates to add 50 to 100 ml. of alcohol, thus allowing to precipitate and separate out the emulsion at once.
• the inventors after repeating many experiments, have succeeded in: making it possible to add to the photographic layer the hardener that is made soluble in water to a desired extent using a proper combination of two orgarn'c solvents miscible with water, avoiding their unfavorable eifects. If these powerful solvents are used, it is easy to add a necessary amount of hardener to the binder.
• the hardener is added to the solution'of a hydrophilic' binder such as gelatin, polyvinyl alcohol, starch, etc. together with such a solvent. In an appro priate step of 'the reaction.
• the desired binder combined with the hardener is separated in a purified form as a hardener of the macromolecular type. Even if about 0.5 to 10% of the above-mentioned hardener based on the dry weight of the binder are made to react and combined, the reaction product does not usually lose the characteristic water solubility of the binder. Therefore, the reaction product precipitated with alcohol or acetone and dried may be dissolved in water again to use.
• this hardener of the high polymer type can be used as a part of the binder which forms the photographic layer. If, for example gelatin containing 5% of hardener is obtained, and is substituted for to 20% of the whole binder, the percentage of the hardener in the whole binder is equivalent to 0.5 to 1% of the hardener added to the whole binder. Thus a photographic layer having a sufiicient hardening property and yet having excellent water absorption is obtained.
• the solubility in ethanol or methanol was both less than O.-1%, and 2 to 3% in formamide, dimethylformamide, etc. Since this substance has dichlorotriazine group, it naturally reacts and combines in a neutral or alkaline condition with various substances having 'NH, NH or OH groups such as gelatin, polyacrylamide, polyvinyl alcohol or cellulose, etc., while liberating hydrochloric acid. Usually one chlorine atom reacts at first, and two chlorine atoms do not react in water if not in a severe condition. It is aimed in this invention when the dried film layer is cured, two chlorine atoms react to form crosslinkage between the molecules. I
• gelatin is most widely used. Besides gelatin, the following substances may be used: casein, polyacrylamide, poly-alanin, a copolymer of -a1anin with acrylamide, polyethylene iniide, polyvinylamine, polyvinyl alcohol, vinyl polymers, copolymerized with these polymers, or derivatives of these compounds, etc.
• Polyvinyl alcohol is well known as a substitute for gelatin, and reacts and combines with this dichloro-s-triazine compound like cellulose. But it is difficult to mix polyvinyl alcohol itself with gelatin.
• a derivative of this compound of which a part of OH groups is changed to monoester of a dibasic acid may be mixed with gelatin easily.
• a copolymer of vinyl ethyl ether with maleic anhydride, or a copolymer of styrol with maleic anhydride does not react but becomes more reactive when they are changed to half-amide with the use of ammonia or an amine group, and can be used for this purpose. Accordingly, every binder mentioned above should also be considered as a kind of a water soluble organic high polymer colloidal binder capable of reacting and combining with dichloro-s-triazine nucleus.
• the supernatant was removed, and the precipitate was washed with one liter of ethanol.
• the mother liquid was removed, one liter of distilled water was added, and the water was warmed to dissolve the precipitate. After cooling, two liters of acetone were added to precipitate again. Then, after distilled water was added to make up to one liter and the whole solution was warmed, it was again cooled to set. The coagulum was shredded into small noodles.
• the resulting jelly was used without being dried. During such operation, the loss of gelatin is usually about 15 to 20%. Therefore, 120 g. of the jelly are considered to correspond to 10 g. of gelatin and 0.5 g. of the hardener. Upon adding the jelly to the emulsion etc., this was taken into account.
• the precipitate was dissolved in 500 ml. of distilled water and was precipitated again with 3 liters of methanol. After being washed with methanol, the precipitate was dissolved in distilled water to make up to 500 ml., thus obtaining about a 10% solution of the hardener of this invention.
• a concentrated emulsion produced by forming a precipitate from a high sensitive bromide emulsion according to an ordinary method using phthalic monoester of polyvinyl alcohol was prepared. (This method of precipitation Was filed for another Japanese patent application, and therefore a brief explanation is made here.)
• One liter of a 10% solution (pH 6.5) of polyvinyl monophthalate (the substitution ratio being about 53%) was added to 3.5 liters of an emulsion prepared from 100 g. of silver halide and 300 g. of gelatin, and at pH 3 a concentrated emulsion was obtained as a precipitate in the form of mass. This was washed twice with 1% acetic acid, and 1.6 kg. of a concentrated emulsion was obtained.
• 160 g. of this concentrated emulsion contains 30 g. of gelatin and 10 g. of polyvinyl alcohol monophthalate, and this constitutes a part of the final binder.
• color photographic paper for silver dye bleaching method was prepared as follows: At first 100 g. of the hardener solution of this invention was added to 160 g. of the above concentrated emulsion. Then, optical sensitizing dyestuffs for red and blue were added respectively to the emulsions in order to form cyan and magenta layers. Further, emulsions added with about 3 g. of Direct Blue (CI 24410), and Diamine Rose (CI 15080), and about 6 g. of Brilliant Yellow (CI 124890) were respectively prepared. To these emulsions were added the ordinary additives before applying including stabilizers for each emulsion and saponin, and the total weight of the liquid was made up to 600 g. with water.
• CI 24410 Direct Blue
• CI 15080 Diamine Rose
• Brilliant Yellow CI 124890
• the ratio of polyvinyl alcohol monomaleate to the whole binder was 20% and the ratio of the monochloro-s-triazine hardener added thereto was 1%
• the hydrophilic binder except gelatin goes up to 40% based on the weight of the total binder. Therefore although this photographic layer has good water absorption and swelling property and low development inhibiting power, the whole hardening property is excellent and completely withstands the treatment of strong hydrochloric acid bleaching solution of the silver dye bleaching method. Moreover, since this hardener acts as a good mordant for acid dyes there was no necessity for further mordant treatment.
• said hardener is 2 (p-acetamino)-phenylamino-4,6-dichloro-1,3,5-triazine.

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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)
• Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Processes Of Treating Macromolecular Substances (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=13950839

Family Applications (1)

Country Status (3)

Cited By (2)

• 1969
  • 1969-11-07 JP JP44088724A patent/JPS4910688B1/ja active Pending
• 1970
  • 1970-11-03 US US00086617A patent/US3717467A/en not_active Expired - Lifetime
  • 1970-11-06 DE DE19702054787 patent/DE2054787A1/de active Pending

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