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
  • G03C1/38—Dispersants; Agents facilitating spreading
• • 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
  • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
  • G03C1/825—Photosensitive materials characterised by the base or auxiliary layers characterised by antireflection means or visible-light filtering means, e.g. antihalation

Definitions

• a photographic element comprising a support having thereon at least one light-sensitive silver halide emulsion layer and at least one gelatin layer containing R. R;-+l ⁇ I-CH( JH ,.Coo
• R R and R which may be the same or different, each represents an aliphatic hydrocarbon radical, R and R which may be the same or different, each represents a hydrogen atom or an aliphatic hydrocarbon radical, and the total of the carbon atoms in R to R is from 8 to 21, and n is 0 or 1.
• This invention relates to a silver halide photographic light-sensitive element containing as its constituent photographic coatings composed mainly of a mordant, a dye and a betaine type surfactant which is employed as coating aids.
• the purposes of the present invention are to improve the wetting property of a photographic coating composition; to provide uniformity to a film after the application of the coating composition; and to present a silver halide photographic light-sensitive element in which the diffusion of the dye from the photographic coatings thus obtained to its adjacent photographic emulsion layer is prevented in the formation of the photographic coatings containing the dye which serves as light filtering layer such as yellow filter layer and light absorbing layer such as antihalation layer.
• a photographic light-sensitive element is generally constituted of a support, such as one of cellulose triacetate, polycarbonates, polyesters, other synthetic polymers, glass or paper; a subbing layer, an antihalation layer, a photographic emulsion layer, an intermediate layer, a filter layer and a protecting layer etc., which are provided in order on the support.
• the photographic light-sensitive element is generally composed of a number of layers. These layers can not be applied uniformly where the coating composition is not employed along with a surfactant which serves to spread the coating composition uniformly and to improve its wetting characteristics. The surfactant also ice has the effect of suppressing the formation of foams and the repellency of the coating composition.
• a coating composition containing a photographic emulsion having a different composition or a polymer material, such as gelatin may be continuously coated in some cases in a multilayered manner on a support in the production of a color photographic light-sensitive element.
• a coating composition or a photographic emulsion containing gelatin on a gelatin layer more difiiculties are encountered in obtaining the required wetting characteristic in comparison with that encountered in the direct application of a gelatin coating composition to the support.
• Saponin has been widely employed as coating aids for many years in the photographic industry and more widely utilized than a number of other surfactants.
• saponin has such disadvantages that it is liable to foam and there is large variation in its quality between batches due to the fact that it is natural product.
• synthetic surfactants turn out to be employed in the photographic industry in recent years and a number of patents concerning this have been already published.
• the synthetic surfactants disclosed in these patents are not only employed as coating aids but also have the effects of static charge prevention, an increase in the solubility of color couplers, the permeability of a treating composition, a decrease in difiiculties due to a waterdrop, a disappearance of bubbles on the application of a gelatin sol to an emulsion layer which is set on cooling, development acceleration, and on prevention of stain due to the antihalation dye on a support.
• An example of the difficulties encountered in the coating process in the production of photographic light-sensitive element is to coat uniformly a mordant-dye type colloid dispersion in which the mordant and the dye are dispersed in a considerably diluted gelatin solution. Coating of this colloid dispersion has been usually employed as antihalation layer or filter layer in the photographic light-sensitive element. However, in this case, it was almost impossible to obtain a homogenous mordant-dye type dispersion and to apply it to a coating surface without foam formation or repellency.
• the diffusion of the dye is attributable to formation of a binding between the mordant and the anionic surfactant, which leads to isolation of the dye, due to the fact that the binding strength of the mordant and the anionic surfactant is stronger than that of the mordant and the dye.
• non-ionic surfactants such as saponin or polyalkylene-oxide derivatives
• diffusion of the dye and cohesion of the mordant with the dye can be surpressed whereas wettability with a subbing layer is found to be bad, thereby causing repellency of a coating composition to occur. This phenomenon is especially remarkable under high speed coating operations.
• Cationic surfactants such as N-alkyl-N,N-dimethyl-N- benzylammonium chloride, have similar antidiifusion effeet on the dye but striking cohesion of the dye and formation of fog, etc., are accompanied therewith, thus causing photogrpahic properties to be worse and hence there is little practical importance.
• an N-alkylaminopropionic acid type amphoteric surfactant can be employed as coating aids for a coating composition forming a decolorizing filtering layer, comprising benzoxazolepyrazolonemelocyanine dye having a sulfonyl-, a sulfoalkylsulfophenyl-, a carboxylor a carboxylalkyl radical in its aromatic nucleus, and a basic high molecular weight mordant, such as a poly-alpha-methylalkyl-N-guanidylketoimine, to prevent diffusion of the dye and consequently to give a uniform mottleless film.
• a basic high molecular weight mordant such as a poly-alpha-methylalkyl-N-guanidylketoimine
• a coating aid such as sodium coco-beta-aminopropionate, described in the above British patent, is employed for a coating composition forming a decolorizating filtering layer, comprising a poly-Z-methyl-l-vinylimidazole type high molecular weight mordant and a dye, described, for example, in the specification of US. Pat. No. 3,445,231.
• the present invention relates to application of a gelatin solution containing a mordant and a dye, which is diflicult to coat.
• the primary object of the present invention is to provide a photographic light-sensitive element having improved wetting and anti-repellent characteristics on the application of a gelatin solution comprising a basic high molecular weight mordant and an acidic dye, containing a betaine type surfactant, on a support or on other photographic layers.
• Another object of the present invention is to apply a photographic composition without formation of any bubbles and other difiiculties on its application.
• Another object of the present invention is to facilitate application where a photographic gelatin or emulsion layer is coated simultaneously or in order with another or still another gelatin or emulsion layer or layers.
• Another object of the present invention is to prevent diffusion of the dye, thereby the sensitivity of this adjacent.
• photographic emulsion layer is prevented from lowering.
• Still another object of the present invention is to prevent cohesion of the mordant with the dye so as to give a stable coating composition.
• R R and R which may be the same or different, each represents an aliphatic hydrocarbon radical, R and R which may be the same or different, each represents a hydrogen atom or an aliphatic hydrocarbon radical, and the total of the carbon atoms in R to R is from 8 to 21, and n is 0 to 1, to a gelatin composition containing a high molecular weight mordant having basic radicals, such as a polymer comprising more than 50% of Z-methyl-l-vinyl-imidazole units or the quaternary salts thereof, a polymer comprising more than 50% of 2-(or 4-) vinylpyridine units or the quaternary salts thereof, or a polymer comprising more than 50% of alkylaminoalkylacrylate units or alkylaminoalkylmethacrylate units or the quaternary salts thereof, and an acid dye, i.e., an oxanol or a pyrazolonestyryl type dye containing an acidic radical in its aromatic nu
• betaine compounds may be converted to its carboxylate in an aqueous alkali solution.
• betaine type surfactants which are employed in the present invention show peculiar effects in view of the same amphoteric type surfactant as described in the above British patent specification of No. 1,124,490. Accordingly, the betaine type surfactants represented by the above general formula are employed in the present invention to form a uniform film without having any undesirable properties, e.g., diffusion of the dye, cohesion (precipitation) of the mordant with the dye, and repellency etc. There is also no adverse influence on the photographic properties.
• R to R in the above betaine type surfactant generally will contain an aliphatic chain of from 1 to 18 carbon atoms, for example, alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, oleyl and the like.
• mordants and dyes are illustrative of those which can be used in the present invention, but it should be understood that these compounds are not a limitation thereof, i.e., preferably employing any of an oxanol or pyrazolone-styryl type dye containing an acidic radical, such as a sulfo or a carboxyl radical, etc., and capable of being decolorized during the course of the treatment, or a basic high molecular weight mordant having a basic group in its main or branched chain, such as a poly-Z-methyl-l-vinylimidazole, a polyalkylaminoalkylacrylate or a polyalkylaminoalkylmethacrylate, or a poly- 2(or 4)-vinyl-pyridine group.
• the high molecular weight mordants which can be used in this invention generally have a polymerization degree of above about 50, although this is not a critical consideration. Examples of such mordants are given as follows:
• betaine type surfactants which may be employed in the present invention are illustrated as follows:
• Betaine compound (1) C Hz5- NC H: C O 0" Betaine compound 2) e 1o :1 IIICH;O O O- H:
• These betaine compounds which are employed in the present invention can be easily synthesized by a method, such as that described in the Journal of the American Chemical Society, 69, 2095 (1947). For example, one mol of dodecylamine is dissolved in 300 ml. of ethyl alcohol, and 260 ml.
• This betaine compound may be employed alone as a coating aid, or may be employed together with a nonionic surfactant, such as saponin or a polyalkylene oxide derivative, or an amphoteric surfactant, such as alanine.
• a nonionic surfactant such as saponin or a polyalkylene oxide derivative
• an amphoteric surfactant such as alanine.
• the betaine type compounds which are employed in the present invention are employed in a ratio of from 0.2 to 5% by weight based on the amount of gelatin in a photographic coating composition, capable of being'coated at a coating velocity of 100 meters/min.
• the proportion of mordant, dye and colloidal binder may be varied over a wide range and will depend on the specific requirements of the photographic element being produced.
• the present invention is applicable to a photographic light-sensitive element con taining at least one layer selected from a decolorizing antihalation layer, a filter layer and intermediate layers, composed of the mordant, the dye and the betaine type surfactant.
• These layers are especially necessary to obtain a color photographic light-sensitive element having high resolving power and sharpness, serving as an effective antihalation layer when the base is not colorized, affecting little irradiation between the layers and capable of being applied to an emulsion layer on a support.
• These layers are also effective to control spectral sensitivity of the emulsion layer on which the layers are coated, thereby improving the properties of the color photographic lightsensitive element.
• the following examples are presented to illustrate the present invention.
• EXAMPLE 1 -5 ml. of a 4% aqueous solution of saponin is added as a coating aid to one kg. of a silver halide iodobromide emulsion containing a color coupler to give a photographic emulsion which is then applied to a cellulose triacetate support subjected to subbing so as to be 3 microns in thickness in the dried condition.
• a solution containing 50 parts by weight of gelatin, 6 parts by weight of Dye (1) and 5 parts by weight of Mordant (l) is diluted with water so that 1.6% by weight of gelatin is contained in the diluted solution.
• the degree of repellency and the wetting characteristics in this case are shown in Table 1.
• the wetting width represents the relative value of the wetting width. When a. photographic support is wet-ted fully over its width, the wetting width is designated as 100.
• Coating aids C 2508 OsNa R represents a hydrocarbon radical obtained from coco-oil.
• EXAMPLE 2 In the same manner as described in Example 1, a silver halide photographic emulsion containing a color coupler is applied to a cellulose triacetatc support subjected to subbing so as to be 3 microns inthickness in the dried condition. Independently, solutions containing 50 parts by weight of gelatin, 2.5 parts by'weight of a mordant and 5 parts by weight of each of Dyes (2) to (6) are diluted separately with water so that 1.6% by weight of gelatin is contained in each of the diluted solutions. To each of these solutions are added separately Betaine compound (1) as coating assistant so as to be 2.5% by weight based on the amount of the gelatin to give coating compositions. These coating compositions are applied to the silver halide photographic emulsion.
• the Betaine compounds in the present invention show excellent coating characteristics, essentially regardless of the dyes, i.e., x0- 1101 type dyes having a sulfonyl or a carboxyl radical and pyrazol type dyes.
• EXAMPLE 3 A silver halide photographic emulsion containing a color coupler is applied to a cellulose triacetate support, subjected to subbing so as to be 3 microns in thickness in the dried condition.
• solutions containing 50 parts by weight of gelatin, 6 parts by weight of Dye (1) and parts by weight of each of Mordants (1) to (5) are diluted separately with water so that 1.6% by weight of gelatin is contained in each of the diluted solutions.
• Betaine compound (4) as coating aids so as to be 2.5% by weight based on the amount of the gelatin to give coating compositions which are then applied to the silver halide photographic emulsion layer. Also in this case, no repellency is observed and an excellent coated surface is obtained in all of the samples, regardless of the dyes.
• EXAMPLE 4 The applicability of the Betaine compound as coating aidsto anti-halation composition to which Dye (1), Dye (4) and Dye (6) are added is examined.
• a solution containing 50 parts by weight of gelatin 2, parts by weight of Dye (l), 2 parts by weight of Dye (4), 2 parts by weight of Dye (6) and 5 parts by weight of Mordant (2) is diluted 'with water so that 1.6% by weight of gelatin is contained in the diluted solution.
• Betaine compound 1) as coating aids so as to be 2.5% by weight based on the amount of the gelatin, after which the mixture thus obtained is supplied to a support subjected to subbing. Consequently, no repellency is observed and an excellent film is obtained.
• EXAMPLE 5 Preparation of a red-sensitive emulsion To a silver iodobromide photographic emulsion which is prepared by a conventional method is added a methanol solution containing 0.2 millimol of anhydro-5-, 5'-dichloro-3', 9-diethyl-3-(8-sulfobutyl)-selenacarbocyaninehydoxide per one millimol of the silver halide. Independently, one gram of N-n-dodecyl-l-hydroxy-4-chloro-2- naphthoamide is dissolved as a cyan coupler in 2.0 ml.
• This emulsified dispersion is then added to the silver halide emulsion containing the photosensitive coloring matter so that 0.15 gram of the coupler is contained per one mol of the silver halide.
• To the emulsion thus prepared are also added the stabilizer, the hardening agent, the coating assistant, the pH adjusting agent and the ant-turbidity agent, which are the same as described in the preparation of the red-sensitive emulsion to give a green-sensitive emulsion.
• the stabilizer Further to the emulsion thus prepared are also added the stabilizer, the hardening agent, the coating aid, the pH-adjusting agent and the anti-turbidity agent, which are the same as described in the preparation of the red-sensitive emulsion to give the blue-sensitive emulsion.
• a coating composition for an intermediate layer A solution containing 50 parts by weight of gelatin, 3 parts by weight of Dye (5) and 5 parts by weight of Mordant (2) is diluted with water so that 1.6% by weight of gelatin is contained in the diluted solution. To the solution thus obtained is added as a coating aid Betaine compound (1) so as to be 2.5% by weight based on the amount of the gelatin, after which a hardening agent is further added thereto to give the coating composition for the intermediate layer.
• a coating composition for a yellow filter A solution containing 50 parts by weight of gelatin, 5 parts by weight of Dye (1) and 5 part by weight of Mordant (2) is diluted with water so that 1.6% by Weight of gelatin is contained in the diluted solution. To this so lution is added Betaine compound (4) as a coating aid so as to be 2.5% by weight based on the amount of the gelatin to give the coating composition for the yellow filter.
• the photographic coating compositions thus prepared are applied successively in layers to a cellulose triacetate support as the anti-halation layer (Example 4), red-sensitive emulsion layer, intermediate layer, green-sensitive emulsion layer, yellow filter layer, blue-sensitive emulsion layer and protecting gelatin layer separately.
• the color photographic light-sensitive element is sub jected to an exposure treatment for a period of & second by the use of NSG-III type sensitometer having a light source of 4,800 K.
• the color photographic lightsensitive element thus treated is then subjected to developing treatment by the use of a developer having the following composition for a period of 10 minutes at 24 C. followed by washing with water, hardening, washing with water and reversal exposure treatment.
• the color photographic light-sensitive element thus treated is subjected to color developing treatment for a period of 15 minutes at 24 C. by the use of a color developer having the following composition followed by wasing with water, bleaching, washing with water, fixation and washing with water to give a transparent color positive image.
• Color developer composition :
• the positive image thus developed on the cyan, magenta and yellow layers shows no color turbidity due to poor silver removal and stains, etc., to give a sharp color photograph having no undesirable effects on its other photographic characteristics.
• EXAMPLE 6 This example illustrates that the betaine compound is rather employed to improve the mordanting eificiency of the mordant and not decrease it.
• a solution containing 50 parts by weight of gelatin, 6 parts by weight of Dye (2) and 5 parts by weight of Mordant (2) is diluted with water so that 1.6% by Weight of gelatin is contained in the diluted solution.
• Each of these coating compositions is then applied to a cellulose triacetate support on which anti-halation and gelatin layers comprising colloidal silver are previously coated, so as to provide a 2 microns dry thickness, and dried.
• a blue-sensitive emulsion layer containing a yellow coupler prepared by the same method as described in Example 5 is further applied thereto so as to be 5 microns in thickness in the dried condition followed by drying. Independently, the blue-sensitive emulsion layer is applied to the support and dried to give samples without applying a yellow filter layer thereto. Each of the samples thus prepared is then subjected to exposure and developing treatments similar to that described in Example 5 to give a yellow positive image.
• a relative value of the degree of exposure to 1.0 of the concentration of the yellow positive image is determined as the relative speed, and results to 100 of the relative speed of coating aids (2) and number of repellencies are shown in Table 2.
• the sensitivity of the blue-sensitive emulsion layer is found essentially to not be lowered when Coating aid (2) is employed, but repellency occurs in a large amount and an excellent film is not obtained.
• lowering in the sensitivity is hardly observed when Betaine compounds (1), (2) and (4) are employed, separately, as understood in comparison with the sensitivity of blue-sensitive emulsion layer having no yellow filter layer, and also no repellency is observed to give an excellent film.
• a photographic element comprising a support having thereon at least one light-sensitive silver halide emulsion layer and at least one gelatin layer containing (1) a polymeric basic mordant having more than 50% recurring units selected from the group consisting of Z-methyl-l-vinylimidazole units and the quaternary salts thereof, 2- or 4-vinylpyridine units and the quaternary salts thereof, alkylaminoalkylacrylate units and the quaternary salts thereof, and alkylaminoalkylmethacrylate units and the quaternary salts thereof,
• R R and R which may be the same or different, each represents an aliphatic hydrocarbon radical, R and R which may be the same or dilferent, each represents a hydrogen atom or an aliphatic hydrocarbon radical, and the total of the carbon atoms in R and R is from 8 to 21, and n 0 or 1.
• said gelatin layer is a light filtering layer.
• gelatin layer is a light absorbing layer.

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• Physics & Mathematics (AREA)
• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• General Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Silver Salt Photography Or Processing Solution Therefor (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

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• 1970
  • 1970-10-07 JP JP45088132A patent/JPS4916051B1/ja active Pending
• 1971
  • 1971-10-01 GB GB4590971A patent/GB1339297A/en not_active Expired
  • 1971-10-04 BE BE773459A patent/BE773459A/xx unknown
  • 1971-10-06 FR FR7135931A patent/FR2111042A5/fr not_active Expired
  • 1971-10-07 US US00187553A patent/US3726683A/en not_active Expired - Lifetime
  • 1971-10-07 DE DE2150136A patent/DE2150136C3/de not_active Expired

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