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
  • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
  • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
  • G03C7/388—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor
  • G03C7/3882—Processes for the incorporation in the emulsion of substances liberating photographically active agents or colour-coupling substances; Solvents therefor characterised by the use of a specific polymer or latex
• • 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
  • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
  • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers

Definitions

• ABSTRACT [30] Foreign Application Priority Data in color photographic photosensitive materials, coum dpdn pler can be stably and finely dispersed in a silver hal- 152 US. Cl. 96/100- 96/84 96/1 14 ide Phomgmphic emulsion by addition of Poly 151 lm. c1. oosc 1/40- oosc 1/72 which Side chains in one [58] Field of Search 96/1 14 100 carboxyl group imidazo'e group and amide gmuP N-(1,l-dimethyl-3-oxobutyl)aminocarbonyl group be- [56] References Cited side said three groups.
• the present invention relates to a color photographic photosensitive material. More particularly, it relates to an inner type color photographic photosensitive material in which a color coupler which couples an oxidation product of N,N-dialkyl-para-phenylenediamine developing agent to form a dye image is stably dispersed in a silver halide photographic emulsion layer.
• a coupler into a silver halide photographic emulsion there are two methods for introducing a coupler into a silver halide photographic emulsion, namely, one method which comprises introducing it by adding water soluble or alkali soluble group thereto and the other method which comprises mechanically dispersing a solution of an oil soluble coupler in solvent of high boiling point in gelatin with a surface active agent and redispersing thus obtained dispersed solution in a silver halide emulsion.
• both of these methods have various defects.
• the coupler which carries carboxyl group and (or) sulfon group is incorporated into silver halide gelatin emulsion
• said coupler is dissolved in a solution of alkali metal hydroxide such as aqueous sodium hydroxide, alcoholic potassium hydroxide, etc. and then is added to the silver halide gelatin emulsion.
• alkali metal hydroxide such as aqueous sodium hydroxide, alcoholic potassium hydroxide, etc.
• coagulation may occur.
• addition of a coupler which is soluble in only a highly alkaline solution causes excessive increase in pH of the photographic emulsion and therefore, it must be made acidic again, due to which coagulation may also be caused.
• solvents of low boiling point such as ethyl acetate, methylethyl ketone, toluene, benzene, cyclohexane, etc. are jointly used as assistant solvent, but unless the coupler is such one as substantially improved in solubility, recrystallization occurs and coloration often becomes insufficient.
• dispersed particles of such coupler are preferably as fine as possible.
• N-( l, 1 -dimethyl-3- oxobutyl)aminocarbonyl group can be accomplished by adding N-( l,l-dimethyl-3-oxobutyl)acrylamide (the so-called diacetone acrylamide) to the monomers before polymerization and copolymerizing them in accordance with usual method.
• N-( l,l-dimethyl-3-oxobutyl)acrylamide the so-called diacetone acrylamide
• Optimum proportion of the monomers in the synthetic resin namely, vinylimidazole derivative, acrylic acid, acrylamide and diacetone acrylamide varies depending upon kinds of coupler to be dispersed, solvent for the coupler and surface active agent.
• the stability of the dispersed particles depends on various complicated factors and optimum conditions must be obtained in each case, but usually vinylimidazole is 1-20 mol acrylic acid is 1-20 mol acrylamide is 10-98 mol and diacetone acrylamide 0-50 mol Furthermore, isoelectric point of the polymer used in the present invention may be freely controlled within the range of 3-8.5 by proportion of each monomer.
• the polymer used in the present invention may be applied to any kind of couplers. Furthermore, it is also effective for dispersing the agents usually employed in the color photographic photosensitive materials such as ultraviolet absorbing agents, e.g., Tinuvin ps, Tinuvin 320 and Tinuvin 328 (Tradenames for the products of Ciba-Geigy Co., Switzerland); stain-inhibitors, e.g., 2,5- di-tert-butylhydroquinone, 2,o-di-tert-butyl-p-cresol, etc.; and scavenger, e.g., 2,5-di-tert-octylhydroquinone. Furthermore, the layer to which the polymer is added is not limited to the photosensitive emulsion layer.
• the vinylimidazole derivative used in the present invention is such as having the following general formula:
• R, R, R" and R' are vinyl group and others are hydrogen, alkyl or hydroxyalkyl.
• vinylimidazole examples include l-vinylimidazole, vinylimidazole, l-vinyl-2-methyl-imidazole, l-vinyl-2- ethyl-imidazole, l-vinyl-2,4-dimethyl-imidazole, lvinyl-2-ethyl-4-methyl-imidazole, l-vinyl-4(or 5)-62 -hydroxyethyl-imidazole, l-vinyl-2-B-hydroxyethylimidazole, etc.
• the polymer used in the present invention can be added to the emulsion at any stage of dispersing the coupler, blending the emulsion and coating of the emulsion and most preferably it can be added at dispersing of the coupler.
• the amount of the polymer added to the photosensitive emulsion addition of about 50-60 by weight of gelatin can provide the maximum effect, but it may be added in an amount of less than said range.
• the polymer may also be added to a silver halide emulsion containing no gelatin as disclosed in Japanese Patent Publication No. 756/68.
• the preferable weight ratio of silver halide/polymer is l/0.ll/l0.
• the polymer used in the present invention is effective for any couplers used in the inner type color photographic photosensitive materials. Furthermore, the polymer has no troubles such as dye absorption, etc. when the photosensitive materials contain halation inhibiting dyes and irradiation inhibiting dyes (such as food red dye No. 2 or food blue dye No. 2 as disclosed in US. Pat. No. 2,956,879 or those disclosed in Japanese Patent Publication No. 13,168/68) and has no adverse effects on photographic characteristics such as sensitivity, fog, preservability, etc.
• halation inhibiting dyes and irradiation inhibiting dyes such as food red dye No. 2 or food blue dye No. 2 as disclosed in US. Pat. No. 2,956,879 or those disclosed in Japanese Patent Publication No. 13,168/68
• Any supports to be coated with emulsion such as films, baryta paper, etc. may be used and have no limitation.
• the coupler dispersion may be prepared from only the polymer used in the present invention without using gelatin to inhibit deviation in quality caused by lot of gelatin and to always obtain coupler dispersions of a constant quality. Furthermore, since there occur no deteriorations such as putrefaction and change of quality caused by bacteria, a large amount of coupler dispersion can be produced at one time it can be stored in a form of solution. Therefore, a necessary amount of thus stored coupler dispersion can be doled out and incorporated into silver halide photographic emulsion. This is markedly advantageous for producing color photographic photosensitive materials.
• PREPARATION EXAMPLE 1 Liquid (1) 99% Acrylamide 1-Vinyl-2-methylimidazole Nitric acid lsopropyl alcohol Water Liquid 2 Water To the liquid (2) through which nitrogen was previously and sufficiently passed and which was kept at 70C was added the liquid (1) dropwise in minutes and thereafter this was kept at 70C for another 30 minutes. Then, this was treated with 4 ml of 30 methanolic solution of N-dihydroxyethylaniline at 70C for 30 minutes to decompose the remaining potassium pe'rsulfate.
• PREPARATION EXAMPLE 2 99% Acrylamide V l-Vinyl-2-B.hydroxyethylimidazole Acrylic acid lsopropyl alcohol Water 2 Potassium persulfate
• the above monomer mixed liquid was subjected to polymerization reaction at 70C for 2 hours while passing nitrogen therethrough and stirring. After completion of the reaction, 4 ml of 3 methanolic solution of N-dihydroxyethylaniline was added thereto and this was heated at 70C for further 30 minutes and then cooled. The resin in the resultant resin solution was precipitated with methanol or acetone and the precipitate was vacuum dried.
• Liquid 1 Liquid 2 Potassium persulfate Water Polymerization was carried out under the same conditions as in Preparation Example 1. To the product was added 4.5 g of sodium hydroxide and 100 ml of water and this was heated at 70C for 30 minutes to hydrolyze a part of amide group and then was neutralized by adding 14 g of 7O 7( nitric acid and 130 g of water and cooled.
• the resultant polymer had the compositions of about 8 mol of 2methylimidazole group, about 7 mol of carboxyl group, about 20 mol of diacetone acrylamide and about 65 mol (remainder) of acrylamide group.
• PREPARATlON EXAMPLE 4 99: Acrylamide LVinyl-Z-ethylimidazole Diacetone acrylamide Acrylic acid lsopropyl alcohol Water Potassium pcrsulfate EXAMPLE 1 Synthetic resin of Preparation Example I 6 kg Water 5% Aqueous solution of di-Z-ethyl-hexyl sulfo succinate l Magenta c0up
• Liquid A Liquid 8 Tricresyl phosphate Ethyl acetate 2 l-( 2-4.6-trichluruphenyl)3-l A (3-n-pcniadecylphcnoxy )butyl Iamide-SpyraZolOne
• the above liquid A was kept at 50C and the liquid B was at 60C to sufficiently dissolve the coupler and then they were mixed and the coupler was dispersed with a homoblender for 1 hour.
• a coupler dispersion was prepared under the same conditions as mentioned above except that 6 kg of photographic inert bone gelatin was substituted for the synthetic resin of Preparation Example 1.
• Emulsion of the present invention The comparative emulsion l l of each emulsion was left at 40C for 3 days and then was filtered with a filter fabric of Amilan. in case of the comparative emulsion, the filter fabric was clogged because the coupler was recrystallized and the filtration was impossible while in case of the present emulsion no such troubles were caused.
• photosensitive materials were exposed and subjected to the usual color development treatment comprising color developing, water washing, bleaching with potassium ferricyanide-bromide, fixation, etc.
• the photosensitive material having the present emulsion produced a brighter magenta image than the photosensitive material having the comparative emulsion.
• Example 1 was repeated except that 6 kg of the synthetic resin of Preparation Example 1 was replaced by combination of4 kg of inert gelatin and 2 kg of the synthetic resin of Preparation Example 2 and by combina tion of 5 kg of inert gelatin and 1 kg of synthetic resin of Preparation Example 4.
• 6 kg of the synthetic resin of Preparation Example 1 was replaced by combination of4 kg of inert gelatin and 2 kg of the synthetic resin of Preparation Example 2 and by combina tion of 5 kg of inert gelatin and 1 kg of synthetic resin of Preparation Example 4.
• EXAMPLE 3 Synthetic resin of Preparation Liquid A was kept at 50C and liquid B was at C to sufficiently dissolve the ultraviolet ray absorbing agent and then the absorbing agent was dispersed for 1 hour by a homoblender.
• a dispersion was prepared in the same manner as mentioned above except that the synthetic resin of Preparation Example 2 was replaced with 86 g of a photographic bone gelatin and the solvent of high boiling point was increased to 2 times. After these dispersions were kept at 40C for 24 hours, the state of the dispersions was observed with a microscope to find that in the comparative dispersion, innumerable crystals of the ultraviolet ray absorbing agent were produced while in the present dispersion the dispersed particles of about 0.1 ,u. were stably maintained.
• ultraviolet ray absorbing agent dispersion may be coated on a coupler containing emulsion layer and this can be applied to a color photographic photosensitive material.
• a color photographic silver halide emulsion which comprises silver halide and a coupler, the improvement of additionally including in said emulsion a polymer which contains as side chain groups (a) carboxyl groups, (b) imidazole groups, and (c) amide groups or side chain groups (a), (b) and (c) and also ((1) N-(1,1-dimethyl-3-oxobutyl) aminocarbonyl groups, the proportions of said groups being (a) 1-20 mo] (b) 1-20 mol (c) lO-98 mol and ((1) -50 mol said polymer being a terpolymer of l) acrylic acid, (2) acrylamide and (3) a vinyl imidazole or being a tetrapolymer of l (2), (3) and also (4) diacetone acrylamide.
• a polymer which contains as side chain groups (a) carboxyl groups, (b) imidazole groups, and (c) amide groups or side chain groups (a), (b)
• a color photographic material which comprises a support and the emulsion as defined in claim 2 coated thereon.
• An emulsion according to claim 1 wherein the polymer is a terpolymer of acrylamide, l-vinyl-2-,B- hydroxyethyl-imidazole and acrylic acid.
• polymer is a terpolymer prepared by hydrolyzing a copolymer of acrylamide and l-vinyl-2-methylimidazole to form a terpolymer of l-vinyl-2- methylimidazole and acrylic acid.
• polymer is a tetrapolymer prepared by hydrolyzing a terpolymer of acrylamide, 1-vinyl-2-methylimidazole and diacetone acrylamide.
• a coupler dispersion which comprises a coupler and the polymer as defined in claim I.

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

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Citations (6)

• 1973
  • 1973-01-30 JP JP48012306A patent/JPS49102339A/ja active Pending
• 1974
  • 1974-01-25 US US436790A patent/US3907572A/en not_active Expired - Lifetime
  • 1974-01-28 GB GB389374A patent/GB1456278A/en not_active Expired
  • 1974-01-29 DE DE2404193A patent/DE2404193A1/de active Pending

Patent Citations (6)

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