Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
  • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
  • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
  • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
  • B41M5/132—Chemical colour-forming components; Additives or binders therefor
• • 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
  • G03C1/815—Photosensitive materials characterised by the base or auxiliary layers characterised by means for filtering or absorbing ultraviolet light, e.g. optical bleaching
• • 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
  • G03C7/28—Silver dye bleach processes; Materials therefor; Preparing or processing such materials
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
  • Y10S430/134—Brightener containing

Definitions

• the present invention relates generally to a dispersion of an oleophilic material in an aqueous medium and more specifically the invention relates to a novel dispersion useful for incorporating an oleophilic material such as oleophilic couplers for color photography,
• the refractive index of the coupler particles or ultraviolet absorbent particles not only in a gelatin layer wetted by a processing solution but also in a dry gelatin layer is not, in general, equivalent to that of the gelatin in that layer, the particles of the coupler or the ultraviolet absorbent cause light scattering and make the gelatin layer opaque to some extent. Accordingly, in order that the emulsion layer containing the dye images has high transparency, it is necessary to reduce the size of the particles inthe emulsion.
• An oleophilic coupler or-an oleophilic ultraviolet absorbent has, hitherto, been dispersed as fine droplets in an aqueous medium using an aqueous solution of gelatin as the aqueous medium and an anionic surface active agent as the emulsifying agent.
• Gardinol WA trade name of a sulfated coconut fatty alcohol, made by the E. I. Du Pont de Nernours Co.
• triisopropylnapthalene sulfate described in the specification of US. Pat. No. 2,332,027 and Alkanol B (sodium triisopropylnapthalene sulfate made by the E. I. Du Pont de Nernours Co.) in the specifications of US. Pat. No. 2,801,170 and US. Pat. No. 2,801,171.
• a method of using as an emulsifying agent a water soluble coupler having a sulfo group or a carboxyl group together with an aliphatic group having the same chain length is described.
• aqueous gelatin solution containing an anionic surface active agent tends to foam quite readily to such an extent that the entire solution can be foamed by stirring the solution vigorously.
• a readily foamable solution is stirred to achieve dispersion by emulsification, a large amount' of foam is formed in the solution.
• the shearing stress provided by the means used for emulsification is lost due to the foam cushioning thereby disturbing the effective transmission of the shearing stress to the oil droplets containing the coupler. This results in greatly reducing the emulsification efficiency.
• the fine foam formed in the emulsified liquid in the emulsification step partially remain in the coating solution, which causes pin holes in the emulsion layer thus coated using such a coating solution.
• the photographic properties are reduced due to the occurrence of fogs in the photographic emulsion and weak bleaching and also the mechanical strength of the emulsion layer constituting the multilayer system used for color photographic lightsensitive materials is reduced.
• An object of this invention is, therefore, to provide a dispersion having improved physical and photographic properties, such as a dispersion in which an oleophilic material has been dispersed finely in an aqueous medium and in which the resulting dispersion is stable.
• a further object of the present invention is to provide a photographic material having excellent properties prepared by using the above-described dispersion (for instance, a color photographic material which is stable for a long period of time and shows a high coupling activity SUMMARY OF THE INVENTION
• the above objects of the present invention can be attained by dispersing an oleophilic material in an aqueous medium in the presence of (1) at least one nonionic surface active agent containing in the molecule thereof polyoxypropylene units and polyoxyethylene units in which a molecular weight of the polyoxypropylene units is greater than 500, the molar ratio of the polyoxyethylene units to the polyoxypropylene units being from 0.1 to 0.6 and (2) at least one anionic surface active agent having in the molecule thereof a hydrophobic hydrocarbon group and containing an SO M group or an --OSO M group, wherein M represents a monovalent cation.
• a photographic light-sensitive material can also be produced by adding the dispersion prepared in the manner as described above in a silver halide photographic emulsion and coating the emulsion on a support using techniques well known in the photographic field.
• the anionic surface active agents which are suitable for the practice of this invention are an amphiphilic substance having an appropriate hydrophilic group and a hydrophobic group in the molecule and can be se lected from a wide range of compounds, each having an SO M group or -OSO M group, where M is a monovalent cation, for example, a hydrogen atom, an alkali metal such as Na, K and Li, or an ammonium group such as NH. and a hydrophobic hydrocarbon group, preferably having about 8 to about 30 carbon atoms.
• Those anionic surface active agents are illustrated in Ryohei Oda and Kazuhiro Teramura Synthesis and Application of Surface Active Agent and A. W. Schwartz and J. W. Perry Surface Active Agents (Intersciencc Publication).
• anionic surface active agent used in the present invention includes not only commonly used socalled anionic surface active agents as described above but also a water-soluble coupler which has a hydrophobic group, preferably hydrocarbon radical of about 8 to about 30 carbon atoms and an SO M group, where OSON, 0 a
• the nonionic surface active agent which can be used in this invention is composed of a polyoxypropylene fragment with a molecular weight of greater than 500 and a polyoxyethylene fragment, in which a molar ratio of the entire polyoxyethylene units to the entire poly- 5 oxypropylene units ranges from 0.1 to 0.6.
• the term, fragment used hereinafter has the same meaning as units.
• any nonionic surface active agent having a wide range of a molecularweight can be used.
• a polyoxypropylene fragment of a nonionic surface active agent has a molecular weight of less than 500 is used, the resulting dispersion is unstable.
• the nonionic surface active agent has the entire molecular weight, preferably up to about 8,000 and more preferably having a molecular weight of from 1,000 to 5,000.
• nonionic surface active agents particularly suitable for the practice of this invention are illustrated below, although the nonionic surface active agent used in this invention are not limited to these examples only.
• nonionic surface active agents of this type can be prepared by methods described in various known literature and by changing the ratio of polyoxypropylene and polyoxyethylene, the compound having a suitable l-lLB (hydrophile lypophile balance) value for use can be readily obtained.
• the oleophilic coupler to be incorporated in a photographic emulsion utilizing the dispersion of this invention is a colorless or colored compound having a coupling unit capable of giving a colored compound having a spectral absorption in a visible wave length region by the coupling reaction with the oxidation product of an N,N-di-substituted p-phenylenediamine compound together with a hydrophobic group having from 9 to 28 carbon atoms as an oil solubilizing group.
• This coupler has no group such as sulfonate group or a sulfuric acid ester group which is excessively hydrophilic.
• the coupling unit of the aforesaid oleophilic coupler can be selected from the phenols and compounds having aromatic groups, amines, pyrroles, or active methylene groups.
• a phenol derivative, a napthol derivative, an acylaceta'nilide derivative, and a 5- pyrazolone derivative are useful as such a coupling unit.
• oleophilic ultraviolet absorbents suitable for the practice of this invention are described, for example, in US. Pat. Nos. 2,739,888, 2,784,087 and 3,352,681; (a thiazolidone derivative): US. Pat. Nos. 3,253,921 and 3,533,794, German Offenlegungsschrift (OLS) No. 2,151,098 (corresponding to US. Pat. application Ser. No. 189,013 filed on Oct. 13, 1971) and Japanese Patent Publication OPI No. 1026/1972 (a 2-phenyl benzotriazole derivative); German Offenlegungsschrift (OLS) No. 2,049,289 (corresponding to US. Pat. application-Sen No. 78,710 filed on Oct. 7, 1970) (an a-cyanocinnamic acid ester); German Patent Publication (DAS) No. 1,087,902; and US. Pat. Nos. 2,685,512 and 3,250,617.
• oleophilic materials used in the dispersion system of the present invention are antioxidants, dye image stabilizing agents, fluorescent brightening agents, dyes for silver dye bleaching process, leuco dyes or color formers for pressure sensitive copying sheet which are all oil-soluble or oleophilic as commonly used in the photographic field. Specific examples of these oleophilic materials are described, for example, in the following specifications:
• antioxidants U.S. Pat. Nos. 2,336,327 and 2,360,290; German Offenlegungsschrift (OLS) Nos. 2,110,521 (corresponding to U.S. Pat. application Ser. No. 17,730 filed on Mar. 6, 1970 and 2,149,789; ii. dye image stabilizing agents: U.S. Pat. Nos. 3,432,300, 3,573,050 and 3,574,627; OLS Nos. 2,126,187; 2,126,954, 2,140,309 (corresponding to U.S. Pat. application Ser. No. 63,270 filed on Aug. 12, 1970) and 2,146,668 (corresponding to U.S. Pat. application Ser. No. 182,558 filed on Sept. 21, 1971); U.S. Pat.
• a liquid oleophilic material can directly be dispersed into an aqueous medium
• a solid oleophilic material can preferably be dissolved prior to the dispersion with heating or in an organic solvent to render it liquid.
• an oleophilic material having a melting point below that of water is dissolved with heating, it is expedient to conduct this dissolution under a mild condition.
• the organic solvent for oleophilic materials used for dispersing finely the oleophilic materialin an aqueous medium is advantageously such a solvent as conventionally used for dissolving couplers in a gelatin containing medium, which is illustrated, e.g., in U.S. Pat. Pat. Nos. 2,322,027 and 3,253,921.
• the organic solvent of the above type which is substantially water-immiscible and has a boiling point of higher than about 175C at normal pressure can be selected from carboxylic acid esters, phosphoric acid esters, carboxylic amides, ethers, carbonates, ketones, sulfonamides and substituted hydrocarbons.
• organic solvents are dim-butyl phthalate, di-iso-octyl phthalate, dimethoxyethyl phthalate, tricresyl phthalate, benzyl phthalate, di-n-butyl adipate, di-iso-octyl azelate, tri-nbutyl citrate, butyl laurate, di-n-butyl sebacate, tricresyl phosphate, tri-n-butyl phosphate, tri-iso-octyl phosphate, triphenyl phosphate, diphenyl mono-ptertbutyl phenyl phosphate, mono-o-chlorophenyl phosphate, N, N-diethylcaprylic amide, N, N-dimethylpalmitic amide, n-butyl m-pentadecylphenyl ether, ethyl 2,4-tertbutylphen
• hydrophobic liquid which is mixed with an oleophilic material and is dispersed in an aqueous medium
• hydrophobic liquid includes, castor oils, arachic oil, whale oil, turpentine oil, lard, dynamo oil, spindle oil, silicone oil, etc.
• di-n-butyl phthalate di-n-butyl phthalate, tri-cresyl phthalate, tricresyl phosphate, dichlorodiphenyl and chlorinated paraffin are particularly preferred.
• a low-boiling solvent or a water-miscible solvent with or in addition to the above-described organic solvents for dissolving the oloephilic materials.
• the organic solvents are disclosed in U.S. Pat. Nos. 3,253,921 and 3,574,627. Examples of such solvents includei l.
• Low-boiling solvents such as propylene carbon ate, methyl, ethyl, propyl, isopropyl and butyl acetates, ethyl propionate, nitromethane, nitroethane, chloroform, carbon tetrachloride, sec-butyl alcohol, etc. and
• Water-miscible solvents such as tetrahydrofuran, cyclohexanone, dimethylformamide, diethyl sulfoxide, methyl cellosolve, methyl isobutyl ketone, diethylene glycol monoacetate, acetonyl acetone, ethylene glycol, acetone, methanol, ethanol, and the like.
• the aqueous medium which can be used in this invention can be selected from aqueous solutions containing hydrophilic colloid materials, such as gelatin, albumin, collodion, gum arabic, agar-agar, alginic acid, cellulose derivatives (e.g., the alkyl esters of carboxylated cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, etc.), synthetic resins (e.g., polyvinyl alcohol, polyvinyl pyrrolidone, etc.) and others well known in the art.
• hydrophilic colloid materials such as gelatin, albumin, collodion, gum arabic, agar-agar, alginic acid, cellulose derivatives (e.g., the alkyl esters of carboxylated cellulose, hydroxyethyl cellulose, carboxymethyl hydroxyethyl cellulose, etc.), synthetic resins (e.g., polyvinyl alcohol, polyvinyl
• gelatin used in the present invention in- I cludes an acid-treated gelatin, a lime-treated gelatin, an enzyme-treated gelatin and gelatin derivatives modified with an agent such as an acylating agent, e.g., acety-' lated gelatin, phthalated gelatin, succinated gelatin, etc.
• the hydrophilic colloid materials having higher molecular weight are suitable especially for preparing a finer dispersion, since such a property as a protective layer is enhanced as a molecular weight increases.
• a gelatin having an average molecular weight more than 30,000 is particularly effective. 1
• hydrophilic colloid materials can be used either alone or in combination.
• the dispersing means used for practicing the present invention suitably there can be used any means which is capable of giving a large shearing force to the liquid to be treated or giving rise to high ultrasonic energy.
• a colloid mill, a homogenizer, a capillary-type emulsifying means, a liquid siren, an electromagnetic striction type sonic wave generator, an emulsifying means equipped with a Pohleman whistle, etc. give better results.
• the amounts added of the anionic active agent and the nonionic surface active agent used in the practice of this invention depend upon the nature of the oleophilic materials used, the kind and amount of the solvent for dispersion, and the type of color photographic light-sensitive material prepared, but an especially effective amount of them ranges from 0.5 to 50 wt.% based on the weight of the oleophilic materials used, and preferably from 5 to 40 wt.% to give the most effective result.
• the amounts added of the anionic surface active agent and the nonionic surface active agent are preferably equivalent.
• the anionic surface active agent was found to have a tendency of im proving finely dispersing an oleophilic material when added in a small amount such as 0.2 wt.
• nonionic surface active agent was found to have a tendency to improve the storage stability of the resulting dispersion when added in an amount more than 1 wt.%. Both of these anionic surface active agent and nonionic surface active agent give a synergistic effect when used in combination and the amounts described above are not critical.
• the present invention has the following effects and advantages.
• the oleophilic materials can be dispersed finely by emulsification in a photographic emulsion without reducing the photographic properties and, further, by using the emulsified dispersion thus prepared, excellent photographic light-sensitive materials can be obtained.
• the nonionic surfaceactive agent used in this invention contributes to minimize remarkably the formation of bubbles and foam in the dispersion and an anionic surface active agent and to facilitate the dispersion process. This fact will be clearly confirmed by the experimental results of Example 3 described hereinafter.-
• nonionic surface active agent of this type By using the nonionic surface active agent of this type, it becomes possible to disperse oleophilic materials as finer particles. This is believed to be due to, in addition to the above-described increase in the efficiency of dispersion by the reduction in the formation of foam, the reduction in the surface tension between the oil phase and aqueous phase to a quite low level by the cooperation of the hydrophilic material, the anionic surface active agent, and the nonionic surface active agent. The fact that fine dispersed particles are formed by the use of the nonionic surface active agent of this type will become clear from the results of the examples of this invention shown hereinafter.
• the amount of the anionic surface active agent used in the dispersion of these materials can be reduced. If a large proportion of an anionic surface active agent is present in a photographic emulsion at the coating thereof, the surface tension of the coating liquid is extremely reduced and thus when two or more photographic emulsions are coated simultaneously, the coatings tend to become uneven in thickness. On the other hand, because the amount of the anionic surface active agent in the present invention is less, the multilayer coating for color photographic light-sensitive materials can be uniformly and easily practiced.
• the nonionic surface active agent used in this invention is slightly soluble in water and has a low HLB value, the photographic emulsion containing the surface active agent has less foaming tendency and the stability of the emulsified dispersion is improved.
• the nonionic surface active agent is incorporated alone in a photographic emulsion and the photographic emulsion is coated on a support, the coating liquid tends to be repelled on the support, is not easily spread over the surface of the support, and thus uneven coatings are obtained.
• the advantage of using the nonionic surface active agent and the anionic surface active agent in accordance with the present invention would not have been expected or anticipated from the nature or the effect of each of the surface active agents alone.
• EXAMPLE 1 A solution prepared in heating to about 50C a mixture of 10 g of the above-described ultraviolet absorbent U-l 0.5 g of the above-described nonionic surface active agent N-l, 20 ml of dibutyl phthalate, and i5 ml of ethyl acetate was poured in ml of an aqueous 10% gelatin solution containing 0.4 g of sodium dodecylsulfate (A-l) with stirring and dispersed by stirring for about 5 minutes in a high speed rotary mixer at 10,000 r.p.m.
• A-l sodium dodecylsulfate
• the mean particle size of the ultraviolet absorbent in the dispersion was confirmed to be about 0.28 micron and the ultraviolet absorbent was confirmed to be dispersed thereinas fine oil drops.
• the mean particle size of the ultraviolet absorbent in the dispersion prepared in the same manner as described above was about 0.8 micron.
• EXAMPLE 2 Two parts of a solution each containing 3 g of the above-described ultraviolet absorbent U-l, 3g of the ultraviolet absorbent U-5, 6 g of the ultraviolet absorbent U-7, 20 ml of dibutyl phthalate, and 10 ml of ethyl acetate were prepared and after adding 0.5 g of the nonionic surface active agent N-2 described above and 0.5 g of a known or conventional oil-soluble nonionic surface active agent, sorbitan monolaurate, respectively, to each solution, each solution was heated to about 50C and allowed to stand for 30 minutes.
• the mean particle size of each of the dispersion prepared above was measured using an electron microscope, coarse particles of 50 microns were observed among particles of 0.65 micron in the dispersion containing the conventional nonionic sur face active agent, sorbitan monolaurate, while the mean particle size of the dispersion containing the nonionic surface active agent of this invention was about 0.3 micron, there were no particles of greater than one micron, and the ultraviolet absorbents in the dispersion were dispersed very finely. Also when the dispersion containing the nonionic surface active agent of this invention was allowed to stand in a cooling box for 20 days at 7C, the mean particle size was observed to be 0.3 micron, which showed the maintenance of stable dispersed condition.
• the dispersion containing more than 0.8 g of the nonionic surface active agent showed almostno foaming and thus when the dispersion immediately after dispersing was added to a photographic emulsion and the latter was coated on a support, an emulsion layer having no pin holes could be obtained.
• the aqueous gelatin solution as the second coating could be coated uniformly over the sur-' face of the silver halide emulsion containing the dispersion (vii), while the aqueous gelatin solution was par tially repelled on the surface of the silver halide emulsion layer containing the dispersion (xiii) and could not be uniformly coated on the layer.
• the coupler be finely dispersed but also the coating of a silver halide emulsion containing the emulsified dispersion of the coupler could be facilitated.
• the entire amount of the dispersion (a) prepared as described above was added to 360 g of a red-sensitive emulsion containing 0.11 mole of silver iodobromide and 18 g of gelatin; the entire amount of the dispersion (b) was added to 540 g of a green-sensitive emulsion containing 0.22 mole of silver iodobromide and 45 g of gelatin; and further the entire amount of the dispersion (c) was added to 500 g of a blue-sensitive emulsion containing 0.18 mole of silver iodobromide and 50 g of gelatin.
• An aqueous gelatin solution containing black colloidal silver was coated on a triacetyl cellulose film base in the dry thickness of 3 microns, the above-described red-sensitive emulsion was coated on the gelatin layer in a dry thickness of 4 microns, an aqueous gelatin solution containing low-sensitive silver chlorobromide particles was coated on the red-sensitive emulsion layer in a thickness of 1.5 microns as an intermediate layer, the above-described green-sensitive emulsion wasv further coated on the intermediate layer in a thickness of 4 microns, an aqueous gelatin solution containingyellow colloidal silver was further coated on the greensensitive layer in a thickness of 2 microns as a yellow filter layer, the above described blue-sensitive emulsion was coated on the filter layer in a thickness of 6 microns, and finally an aqueous gelatin solution was coated on the blue-sensitive layer in a thickness of 1 micron to give a color photographic negative film.
• composition for the color developing solution used in the above color development was as follows:
• an acid aqueous solution containing sodium thiosuflate and sodium sulfite was used as the fixing solution and a neutral aqueous solution containing potassium ferricyanide was used as the bleaching solution in the above procedures.
• EXAMPLE 5 The following three kinds of coupler solutions were prepared. Dispersion d g of the above-described yellow-forming coupler Y-4 was melted by heating in boiling water. After adding 0.8 ml of a 30% ethanol solution of the abovedescribed nonionic surface active agent N-7 to an aqueous solution containing 0.6 g of the abovedescribed anionic surface active agent A-9 and 30 g of gelatin at 75C, the coupler melted above was added to the mixture; The resultant mixture was treated six times using a small-scale colloid mill preheated to a temperature above 80C by passing it through hot water. (Dispersion e) the above-described magenta-forming coupler M-l, 1.0
• the entire amount of the dispersion (d) prepared above was added to 1 kg of a blue-sensitive emulsion containing g of gelatin and 0.25 mole of silver chlorobromide; the entire amount of the dispersion (e) was added to 800 g of a green-sensitive emulsion containing g of gelatin and 0.22 mole of silver chlorobromide; and 500 g of the dispersion (f) was added to 1 kg of a red-sensitive emulsion containing 70 g of gelatin and 0.27 mole of silver chlorobromide.
• the blue-sensitive emulsion prepared above was coated on a photographic baryta-coated paper in a dry thickness of 5 microns, an aqueous solution was coated on the blue-sensitive emulsion layer in a thickness of 1 micron as a first intermediate layer, the green-sensitive emulsion prepared above was coated on the intermediate layer in a thickness of 4 microns, an aqueous gelatin A solution prepared by heating a mixture of 15 g of solution was coated on the green-sensitive emulsion layer as a second intermediate layer in a thickness of 1 micron, the red-sensitive emulsion prepared above was coated on the second intermediate layer in a thickness of 4 microns, and further an aqueous gelatin solution 5 having dispersed therein the same ultraviolet absorbent as described in Example 1 was coated on the redsensitive emulsion layer in a thickness of 1 micron as a protective layer to give a color photographic paper.
• triethylene phosphamide was used as a hardening agent for gelatin.
• the entire amount of the dispersion thus prepared was added to 100 g of a red-sensitive emulsion containing 7.0 g of gelatin and 3.3 X 10" mole of silver chlorobromide.
• the resultant emulsion was coated on a triacetyl cellulose film base having an antihalation layer in a dry thickness of 5 microns and dried to give a sample film.
• the light-sensitive film thus prepared was exposed to a figure formed by writing on a white paper with a black ink and processed as described in Example 4, a slide for display having sharp lines and characters on a blue background and having high transparency was obtained.
• EXAMPLE 7 A solution prepared by heating to about 50C, a mixture of 10 g of an antioxidant, 2,5-di-tert-butyl hydroquinone, 0.5 g of the above-described nonionic surface active agent N-l, 15 ml of dibutyl phthalate and 15 ml of ethyl acetate was poured in 100 ml of an aqueous l0 gelatin solution containing 0.4 g of sodium dodecylsulfate (A-l with stirring and dispersed by stirring for about 5 minutes in a high speed rotary mixer at 10,000 rpm.
• the mean particle size of the antioxidant in the dispersion was about 0.45 p. and the antioxidant was u niformly dispersed therein as fine oil drops. When the dispersion was allowed to stand in a cooling box for 2 weeks at 7C, the mean particle size was observed to be 0.48 ;1.
• a dispersion was prepared in the same manner as described above except using an azo dye of the following formula in place of the above nitro dye:
• the dispersion showed the maintenance of stable dispersed condition.
• the dispersion thus obtained can be incorporated in a light-sensitive silver halide emulsion to give a photographic emulsion for a silver dye bleaching process disclosed, for example, in US. Pat. No. 3,615,494.
• a multilayer photographic light-sensitive silver halide element containing a dispersion comprising an aqueous gelatin solution having dispersed therein at least one oleophilic material selected from the group consisting of an oleophilic dye for a silver dye bleaching process, an oleophilic coupler free of a water solubilizing group, an oleophilic ultraviolet absorbent, an oleophilic antioxidant, an oleophilic dye image stabilizing agent and an oleophilic fluorescent brightening agent, in the presence of (a) a nonionic surface active agent containing polyoxypropylene units having a molecular weight of greater than 500 and polyoxyethylene units and a molar ratio of said polyoxyethylene units to said polyoxypropylene units ranging from 0.5 to 0.6, and (b) an anionic surface active agent having an O- SO M group or an SO M group, wherein M represents a monovalent cation, and a hydrophobic group, said nonionic surface active agent being a slightly water
• gelatin is acid-treated gelatin, lime-treated gelatin or enzymetreated gelatin.
• said coupler is a coupler which couples with the oxidation product of an N,N-disubstituted p-phenylenediamine developing agent and which has a ballasting group of from 9 to 28 carbon atoms.
• Compound A l2 I C H 'S0 Na is incorporated.
• surface active agent has a molecular weight up to 11. The element of claim 1, wherein said aqueous 8,000.
• medium is an aqueous solution of gelatin oraderivative 14 h l t f l 13 h thereof, albumin, collodion, gum arabic, agar-agar, ale e emen o c alm w erem Sal non-Ionic ginic acid, an alkyl ester of carboxylated cellulose, hy- 3Q ggg g a agent has a molecular we'ght of from droxyethyl cellulose, carboxymethyl hydroxyethyl cel-- to lulose, polyvinyl alcohol or polyvinyl pyrrolidone, or 15.
• the element of claim 1, wherein said block polymixtures thereof. mer has free hydroxy groups at the terminals thereof.

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• General Chemical & Material Sciences (AREA)
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• 1971
  • 1971-08-25 JP JP46064991A patent/JPS5224412B2/ja not_active Expired
• 1972
  • 1972-08-23 US US283026A patent/US3860425A/en not_active Expired - Lifetime
  • 1972-08-24 DE DE2241567A patent/DE2241567C2/de not_active Expired
  • 1972-08-24 FR FR7230217A patent/FR2150505B1/fr not_active Expired
  • 1972-08-25 CA CA150,236A patent/CA988770A/en not_active Expired
  • 1972-08-25 GB GB3985172A patent/GB1359440A/en not_active Expired

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