JPH0554651B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to silver halide photographic paper with improved whiteness of the white background of printed photographic paper, and more particularly to blue tinting with oil-soluble fluorescent brighteners and dyes. The present invention relates to a method for improving whiteness by using a combination of PRIOR ART It is a well known technique to apply fluorescent brighteners to enhance the whiteness of the processed substrate of silver halide photographic paper. These fluorescent whitening agents absorb ultraviolet light and usually emit slightly bluish fluorescence, making objects appear whiter. Such fluorescent brightening methods have long been used to add a fluorescent brightener to the paper support or its polyethylene laminate layer, as well as to add a water-soluble brightener to the silver halide emulsion layer or other photographic coating layer. A method of adding a fluorescent brightener or an oil-soluble fluorescent brightener, and a method of adding a fluorescent brightener to a developing solution in advance are known. However, in the case of silver halide photographic paper made of a polyethylene laminated paper support, which is particularly suitable for rapid processing, it is difficult to incorporate a fluorescent brightener into the laminate layer due to the poor thermal stability of the fluorescent brightener. However, there are disadvantages such as the fact that the fluorescent brightener easily decomposes during the hot extrusion process during the formation of the laminate layer, and if a fluorescent brightener is applied during the development process, If you don't try to maintain a constant concentration at all times, there are inconveniences such as not being able to maintain a uniform finish.
Most preferably, a fluorescent brightener is included in the photographic layer in advance. In particular, in the method of adding a fluorescent brightener to the photographic layer, an oil-soluble fluorescent brightener is used rather than a water-soluble one to prevent the fluorescent brightener from being washed away during the development process. For this purpose, it is effective to incorporate an oil-soluble fluorescent brightener into the photographic layer as described in British Patent No. 1072915, in which an oil-soluble fluorescent brightener is dissolved in an organic solvent and an emulsified dispersion is prepared in the gelatin layer. There is a known method of adding On the other hand, although visual whiteness varies depending on individual preference, it is also known that, in general, a bluish white looks whiter than a neutral white. Furthermore, in silver halide photographic elements, undesirable light absorption on white backgrounds is caused by the yellowing of natural polymers such as gelatin used as binders, synthetic polymers such as polyvinylpyrrolidone and polyvinyl alcohol, and the yellowing of silver halide emulsions. Residual color due to silver and pigments due to fog, residual color due to sensitizing dyes and anti-irradiation dyes, dyeing of colored substances in the processing machine, yellowing caused by couplers, antioxidants, ultraviolet absorbers, etc., which is a problem especially in color photographic paper,
Examples include the formation of coloring dyes by couplers and developing agents that occur without the development of silver halide.
As a means of adjusting the hue of the white background by adding bluing to visually cancel out these so-called residual colors,
As seen in JP-A No. 53-19021, an inorganic coloring pigment is incorporated into polyolefin in a polyolefin coated paper to adjust the hue of the support surface, and as shown in JP-A-55-93150, a photographic layer is incorporated. There is known a method of controlling the hue in a photographic layer by using an oil-soluble dye therein. Hue adjustment on the surface of the support involves the complexity of preparing the support according to the optical properties of the various photographic layers, and extrusion coating of polyolefin is usually performed at high temperatures of 300°C or higher, and the colorant is It must satisfy requirements such as having heat resistance of 300℃ or more, no bleed-out, no sublimation, and good dispersibility in polyolefin, which narrows the range of colorant selection. In this respect, it is advantageous to incorporate the colorant in the photographic layer. In particular, in recent years, rapid processing using automatic processors has become widespread, and the above-mentioned residual color of sensitizing dyes and the like has become a more serious problem. However, when an oil-soluble fluorescent brightener emulsion dispersion and further dye are added in order to obtain higher whiteness by combining the fluorescent whitening effect and the hue adjustment effect, for some reason, the whiteness improves to some extent. However, it was not possible to obtain a satisfactory degree of whiteness. On the other hand, when a water-soluble fluorescent brightener is added, for example as described in Japanese Patent Publication No. 48-30495, good whiteness can be obtained by using it in combination with a blue dye. However, as mentioned above, there are some drawbacks such as the whiteness not being as high as expected due to the fluorescent brightener leaking out during the development process, and the whiteness fluctuating depending on the processing conditions. I can't escape it. (Objective of the Invention) Therefore, an object of the present invention is to provide a silver halide photographic paper which always has a white background with good whiteness regardless of development processing conditions. (Structure of the Invention) An object of the present invention is to include an emulsified dispersion of an oil-soluble fluorescent brightener and a dye in a photographic layer on a support, and to make the emulsified dispersion of an oil-soluble fluorescent brightener and the dye substantially different from each other. This is achieved by having the two layers present in different photographic layers. As a result of our investigation, we found that when an oil-soluble fluorescent brightener emulsion and a dye are used together in the same photographic layer, the whiteness does not improve as much as expected because the fluorescent white brightening emulsion is used alone. It has been found that the cause is a decrease in fluorescence intensity in some cases. Special Public Service 1977-
Publication No. 37376 describes that a cyan-forming phenolic coloring agent produces a dye that extinguishes fluorescence upon color development, but the mechanism by which the dye acts to extinguish fluorescence is completely unknown. do not have. Furthermore, it is not possible to predict which dyes will have this effect. This decrease in fluorescence intensity is thought to be caused by some kind of interaction between the fluorescent brightener and the dye, but in order to separate the two, the oil-soluble dye was dissolved in a high-boiling organic solvent and a separate solution was used. Even when it was added as an emulsified dispersion, the decrease in fluorescence intensity could not be completely prevented. However, it was surprising that it was possible to prevent a decrease in fluorescence intensity and obtain a satisfactory whiteness for the first time by making both of them exist in separate photographic layers. As for the method of adding the dye, simply adding it to a layer separate from the oil-soluble fluorescent brightener emulsion is not sufficient to achieve the effect of the present invention. It is necessary to use means to The most desirable method for this purpose is to dissolve an oil-soluble dye in a high-boiling organic solvent and use it as an emulsified dispersion. Specifically, it can be produced in the same manner as the oil-soluble brightener emulsion described below. Other methods include dissolving it in a monomer and then polymerizing it to form a latex dispersion, or impregnating it into a hydrophobic polymer with an auxiliary solvent to form a latex dispersion, which is separate from the fluorescent brightener emulsion. When using water-soluble dyes, use dyes with a molecular structure that makes them virtually resistant to diffusion, or when using diffusible dyes, use cationic polymers. A method such as mordant is advantageously used. When the dye is used as a latex dispersion, it can be carried out using a method similar to the latex dispersion method described in JP-A-50-126732. When mordanting a diffusible dye, specifically, those described in the following patents can be used. For example, UK number 685475, US number 2675316, number 2839401,
Same No. 2882156, No. 3048487, No. 3484309, Same No.
No. 3445231, West German Patent Application (OLS) No. 1914362,
Polymers described in JP-A-50-47624, JP-A-50-71332, etc. can be used. Any dye can be used in the present invention, and specifically, anthraquinone-based, azo-based, phthalocyanine-based, oxonol-based, and benzylidene-based dyes can be used. Among these, anthraquinone-based, azo-based and phthalocyanine-based dyes are particularly preferably used. Next, a typical example will be shown.

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[Table] The dye used in the present invention is used for the purpose of adjusting the white and other hues of photographic paper. It should be selected so that it looks white, and even if a blue dye is used alone, red dye, green dye, blue dye, etc. can be used as needed.
It is also possible to use more than one species in combination to adjust its absorption properties. The content of dye is actually determined by the type of photographic layer and the type of processing, and is not particularly limited, but it is usually preferably from 0.05 mg/m to 5 mg/m. In addition, as the additive photographic layer, it may be added to any layer of the photographic layer as long as it is a layer different from the fluorescent brightener emulsion used together, and it has the same effect for the purpose of improving whiteness. has. Specific examples of the photographic layer include an emulsion layer, an intermediate layer, a protective layer, and an undercoat layer. Examples of water-insoluble fluorescent brighteners used in the present invention include substituted stilbenes and substituted coumarins described in British Patent No. 786234 and U.S. Patent No. 3135762.
Substituted thiophenes such as those described in JP-B-45-37376 and JP-A-50-126732 can be used particularly advantageously. Typically useful fluorescent brighteners include those having one of the following structural formulas. () () () () Here, Y ₁ and Y ₂ are alkyl groups, Z ₁ and
Z ₂ is hydrogen or an alkyl group, n is 1 or 2,
R ₁ , R ₂ , R ₄ and R ₅ are aryl, alkyl, alkoxy, aryloxy, hydroxyl, amino, cycano, carboxyl, amide, ester,
It is an alkylcarbonyl, alkylsulfo or dialkylsulfonyl group or a hydrogen atom. R ₆
and R ₇ is a hydrogen atom, an alkyl group such as a methyl group, an ethyl group, or a cyano group. R ₁₆ is a phenyl group, a halogen atom, or an alkyl-substituted phenyl group. R ₁₅ is an amino group or an organic primary or secondary amine. Next, specific examples of water-insoluble fluorescent brighteners used in the present invention will be given. F-1 F-2 F-3 F-4 F-5 F-6 F-7 F-8 F-9 F-10 F-11 F-12 F-13 F-14 F-15 F-16 F-17 F-18 F-19 F-20 F-21 F-22 F-23 F-24 F-25 A method for preparing an emulsion of these water-insoluble fluorescent brighteners is as exemplified in British Patent No. 1072915, in which the fluorescent brightener is dissolved in a high-boiling organic solvent, and then this is dissolved in a hydrophilic colloid such as gelatin. There is a method of emulsifying and dispersing it together with a surfactant. Examples of high boiling point organic solvents include US Pat.
No. 3779765, West German Patent No. 1152610, British Patent No. 1272561,
JP-A-53-1520, JP-A-55-25057, JP-A-Sho
Phthalate esters and phosphate esters such as those described in 45-37376 can generally be used, but
Of course, the invention is not limited to these, but includes, for example, the amide compound disclosed in U.S. Pat. No. 3,416,923,
Benzoic acid esters and substituted paraffins can also be used advantageously. If the amount of the fluorescent brightener used is too small, the whiteness improving effect will not be sufficient, and if it is too large, so-called blooming will occur in areas of high image density, resulting in an apparent decrease in image density. The emission efficiency of fluorescent light depends on the type of fluorescent brightener, the type and concentration of oil used for emulsification, the coexistence of various quenching substances,
The amount of the fluorescent whitening agent used in the present invention is most preferably used within the range of 3 mg/200 m ² , although it cannot be expressed uniformly because it varies depending on the presence of other ultraviolet absorbing substances. The ratio of emulsifying oil to fluorescent brightener is selected and used at an optimal value from the viewpoint of solubility and concentration quenching of the fluorescent brightener. Further, the layer to which the fluorescent brightener emulsion is added is preferably on the same surface as the color-sensitized silver halide emulsion, and may be any layer as long as it is a photographic layer different from the dye mentioned above. However, in terms of making blooming less likely to occur, it is more preferable to select an emulsion layer or a layer closer to the support (for example, an intermediate layer, an undercoat layer, etc.). As the binder or protective colloid that can be used in the emulsion layer or hydrophilic colloid layer (e.g., protective layer, intermediate layer) of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic Colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose, and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol , polyvinyl alcohol partial acetal,
Poly-N-vinylpyrrolidone, polyacrylic acid,
A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, and the like. In addition to coal-processed gelatin, acid-processed gelatin and Bull.Soc.Phot.Jahan, No. 16, p30 are used as gelatin.
(1966) may be used, and gelatin hydrolysates and enzymatically decomposed products may also be used. Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. The preferred silver halide is silver iodobromide containing up to 15 mole percent silver iodide. Particularly preferable is 2
Silver iodobromide containing from mol% to 12 mol% silver iodide. The average grain size of silver halide grains in a photographic emulsion (the grain size is the grain diameter in the case of spherical or approximately spherical grains, the grain length in the case of cubic grains,
Expressed as an average based on projected area. ) is not particularly limited, but is preferably 3μ or less. The particle size may be narrow or wide. The silver halide grains may have different phases inside and on the surface. Further, the particles may be particles in which the latent image is mainly formed on the surface, or may be particles in which the latent image is mainly formed inside the particles. The photographic emulsion used in the present invention is P. Glafkides
Written by Climie et Physique Photographique (Paul
Montel Publishing, 1967), GFDlffin
Photographic Emulsion Chemistry (The Focal
Press, 1966), VL Zelikman et al.
Maknng and Coating Photographc Emulsion
(The Focal Press, 1964). That is, any of the acid method, neutral method, ammonia method, etc. may be used.
Further, as a method of reacting the soluble silver salt and the soluble halogen salt, any one of a one-sided mixing method, a simultaneous mixing method, a combination thereof, etc. may be used. It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).
As one of the simultaneous mixing methods, it is also possible to use a method in which the pAg in the liquid phase in which the formed silver halide is produced is kept constant, that is, a so-called controlled double jet method. According to this method, a silver halide emulsion having a regular crystal shape and a nearly uniform grain size can be obtained. Two or more types of silver halide emulsions formed separately may be mixed and used. In the process of silver halide grain formation or physical ripening, cadmium salts, zinc acid, lead acid, thallium salts, iridium salts or complex salts thereof, rhodium salts or complex acids thereof, iron salts or iron complex salts, etc. may be allowed to coexist. . Silver halide emulsions are usually chemically sensitized.
For chemical sensitization, see for example “Die
Grundlagender Photographischen Prozesse
mit Silber−halogeniden” (Akademische
Verlagesellschaft, 1968) pages 675-734 can be used. Namely, sulfur sensitization using sulfur-containing compounds that can react with active gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); reducing substances (e.g., stannous salts); , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds) reduction sensitization method:
Noble metal compounds (e.g., gold complex salts, Pt, Ir,
A noble metal sensitization method using complex salts of metals in the periodic table group such as Pd can be used alone or in combination. The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroimidazole salts, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptoenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptoterazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxide linthion; azaindenes, For example, triazaindenes, tetraazaindenes (especially 4-hydroxy substituted (1,
3,3a,7) tetraazaindene), pentaazaindene, etc.; benzenethiosulfonic acid,
Many compounds known as antifoggants or stabilizers can be added, such as benzenesulfuric acid, benzenesulfonic acid amide, and the like. For more detailed examples of these and how to use them, see, for example, U.S. Pat. No. 3,954,474;
Those described in No. 3982947 and Japanese Patent Publication No. 52-28660 can be used. The photographic emulsion thickening layer or other hydrophilic colloid layer of the light-sensitive material produced using the present invention may be used as a coating aid, antistatic, smoothness improvement, emulsification dispersion, adhesion prevention, and improvement of photographic properties (e.g., development acceleration, contrast enhancement, etc.). , sensitization)
Various surfactants may be included for various purposes. For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols Nonionic interfaces such as alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: Alkyl carboxylate, alkyl sulfonate, alkylbenzene sulfonate, alkylnaphthalene sulfonate, alkyl sulfate, alkyl phosphate, N-acyl-N-alkyl taurine, sulfosuccinic acid Contains acidic groups such as carboxy groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc., such as esters, sulfoalkyl polyoxyethylene alkyl phenyl ethers, lolioxyethylene alkyl phosphate esters, etc. Anionic surfactants: Amino acids, aminoalkyl sulfonates, aminoalkyl sulfates or phosphates, alkylbentanes, amine oxides, etc. Ampholytic surfactants: Alkylamine hydrochloric acid, aliphatic or aromatic quaternary ammonium Cationic surfactants such as hydrochloric acid, subcyclic quaternary ammonium hydrochloric acids such as pyridinium and imidazolium, and phosphonium or sulfonium hydrochloric acids containing aliphatic or heterocycles can be used. The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholins, and quaternary ammonium for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain developing agents such as salt compounds, urethane derivatives, urea derivatives, imidazole derivatives, dihydroxybenzenes, and 3-pyrazolidones. Among them, dihydroxybenzenes (hydroquinone, 2-methylhydroquinone, catechol, etc.) and 3-pyrazolidones (1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, etc.) are preferred. , usually used at 5 g/m ² or less. For dihydroxybenzenes, 0.01 to 1
g/m ² is more preferable, and in the case of 3-pyrazolidones, 0.01 to 0.2 g/m ² is more preferable. The photographic light-sensitive material used in the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer in other hydrophilic colloid layers of the photographic emulsion layer for the purpose of improving dimensional stability. For example, alkyl (meth)acrylate, alkoxyalkyl (meth)
Acrylate, glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or together with acrylic acid, methacrylic acid, α, β-
A polymer containing a combination of unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, styrene sulfonic acid, etc. as a monomer component can be used. The photographic emulsions used in the present invention may be spectrally sensitized with methine dyes and others. The pigments used include cyanine pigments, merocyanine pigments,
Included are complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. That is, pyrroline nucleus, oxazoline nucleus, thiazoline nucleus, pyrrole nucleus, oxazole nucleus, thiazole nucleus, selenazole nucleus, imidazole nucleus, tetrazole nucleus, pyridine nucleus, etc.; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of Imidazole nuclei, quinoline nuclei, etc. can be applied.
These nuclei may be substituted on carbon atoms. The merocyanine dye or composite merocyanine dye includes a nucleus having a ketomethylene structure such as a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus, A 5- to 6-membered heteroartic ring nucleus such as a thiobarbituric acid nucleus can be applied. The invention is also applicable to multilayer, multicolor photographic materials having at least two different spectral sensitivities on the support. Multilayer natural color photographic materials usually have at least one each of a red-sensitive emulsion layer, an edge-sensitive emulsion layer and a blue-sensitive emulsion layer on a support. The order of these layers can be arbitrarily selected according to need. Usually, the red-sensitive emulsion layer contains a cyan-forming coupler, the edge-sensitive emulsion layer contains a magenta-forming coupler, and the blue-sensitive emulsion layer contains a yellow-forming coupler, but different combinations may be used depending on the case. The photographic emulsion layer of the photographic light-sensitive material prepared using the present invention contains a dye-forming coupler, that is, an aromatic primary amine developer (e.g., phenylene diamine derivative, aminophenol derivative, etc.) in the color development process. A compound capable of developing color by oxidation may also be used. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, closed acylacetonitrile couplers, and yellow couplers include acylacetamide couplers (e.g., benzoylacetonilides, pivaloylacetonilides). ), and cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible and have a hydrophobic group called a ballast group in their molecules, or are polymerized. The coupler may be either 4-equivalent or 2-equivalent to silver ions.
Also, colored couplers have a color correction effect, or release development inhibitors or development accelerators during development (so-called DIR couplers or
DAR coupler). The photographic material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer or other hydrophilic colloid layer. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.),
Dioxane derivatives (2,3-dihydroxydioxane, etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,3-dihydroxydioxane, etc.), (4-dichloro-6-hydroxy-s-triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxychloroic acid, etc.), and the like can be used alone or in combination. In the photosensitive material produced using the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a cationic polymer or the like. The light-sensitive material produced using the present invention may contain a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative, an ascorbic acid derivative, etc. as a color antifoggant. The photosensitive material produced using the present invention may contain a water-soluble dye in the hydrophilic colloid layer as a filter dye or for the purpose of preventing irradiation. Such dyes include oxonol dyes, hemioxonol dyes, styryl dyes,
Included are merocyanine dyes, cyanine dyes and azo dyes. Among them, oxonol dyes: hemioxonol dyes and merocyanine dyes are useful. In carrying out the present invention, the following known anti-fading agents may be used in combination, and the color image stabilizers used in the present invention may be used alone or in combination of two or more. Known antifading agents include hydroquinone derivatives, gallic acid derivatives, p-alkoxyphenols, p-oxyphenol derivatives, and bisphenols. The support used in the present invention may be paper, baryta coated paper, paper coated with an α-olefin polymer such as polyethylene, or the like. These supports may further contain titanium oxide, dyes, etc. in order to increase the whiteness. Preferably, a water-impermeable reflective support is used. Any known method can be used for the photographic processing of the light-sensitive material of the present invention. A known treatment liquid can be used. Processing temperature is usually 18
The temperature is selected between 18°C and 50°C, but the temperature may be lower than 18°C or above 50°C. Depending on the purpose, either a development process that forms a silver image (black photographic process) or a color photographic process that consists of a development process that forms a dye image can be applied. The developer used in black photographic processing can contain known developing agents. Examples of developing agents include dihydroxybenzenes (e.g. hydroquino), 3-pyrazolidones (e.g. 1-
phenyl-3-pyrazolidone), aminophenols (e.g. N-methyl-p-aminophenol), 1-fer-3-pyrazolines, ascorbic acid and the 1,2,
Heterocyclic compounds in which a 3,4-tetrahydroquinoline ring and an indolene ring are condensed can be used alone or in combination. The developing solution generally contains other well-known preservatives, alkaline agents, PH buffers, antifoggants, etc., and, if necessary, solubilizing agents, color toners, development accelerators, surfactants,
It may also contain antifoaming agents, water softeners, hardening agents, viscosity imparting agents, and the like. As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thioianates, organic sulfur compounds known to be effective as fixing agents can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent. The photosensitive material of the present invention is preferably processed using an automatic processor, which enables rapid processing. At this time, the developing process is 30~45℃, 5~
It is preferable to carry out the fixing step at 30 to 45 DEG C. for 5 to 30 seconds, and the washing step at 30 to 45 DEG C. for 5 to 30 seconds. Further, in this case, it is preferable to use an acidic hardening fixing bath containing a polyvalent metal as the fixing bath. Example 1 A spectral sensitizing dye having the following structural formula was added to an emulsion consisting of cubic AgRrI (I; 1.2 mol%) grains with an average grain size of 0.6 μm prepared by the double jet method. A coating solution was prepared by adding 0.30 mmol/mol AgX. 2.0g of silver and 4.5g of gelatin in 100g of this coating solution.
After adjusting the gelatin concentration so as to contain 1.5 g of gelatin, 1 mg of 1-phenyl-5-mercaptotetrazole was added as an antifoggant, and
A fluorescent brightener emulsion prepared by the method shown in
g and 2,4-dichloro-6- as a hardening agent.
110 μ thick polyethylene laminate paper with addition of 0.2 g of hydroxy-1,3,5 triazine and a protective layer consisting of 1.5 g/m ² of gelatin (containing 15 wt% titanium white in the surface laminate layer)
A coating was prepared on the support with a coating silver amount of 1.3 g/m ² .
In addition, Triton×-200 is used as a coating aid in the protective layer.
Rhom & Haas) at 30 mg/m ² and a dye emulsion prepared by the method shown in Table 2 at 0.5 g/m ² were added. For comparison, samples were also prepared with no fluorescent brightener emulsion or dye emulsion added, with only one added, and with dye emulsion added to the emulsion layer instead of the protective layer. . The coated samples were treated without exposure under the conditions shown in Table 3, and measured using a Hitachi Model 850 spectrofluorophotometer with a xenon lamp light source, excitation light of 400 nm, and a bandwidth of 5 nm. The light intensity was determined and the whiteness of the coated samples was visually evaluated, and the results are shown in Table 4. Samples 1-5, which are embodiments of the present invention, are
Fluorescence intensity was sufficiently strong, and satisfactory whiteness was obtained without yellowing.

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[Table] Example 2 In Example 1, 0.5 mg/m ² of Exemplified Compound D-19 was used as a water-soluble dye instead of the dye emulsion.
Table 5 shows the results of carrying out the same procedure as in Example 1 except that 0.3 mg/m ² of poly-N,N-diethylaminoethyl methacrylate hydrochloride was added as a mordant.

[Table] It is understood that even when a water-soluble dye subjected to migration prevention is used, samples 2-5, which are embodiments of the present invention, have extremely high whiteness. Example 3 In Example 1, exemplified compound D- was used as a substantially diffusion-resistant water-soluble dye instead of the dye emulsion.
Table 6 shows the results obtained in the same manner as in Example 1 except that 0.5 mg/m ² of 4 was added.

[Table] In this case as well, 3-5 which is an embodiment of the present invention
It is understood that the sample has outstanding whiteness. Example 4 In sample No. 1-5 of Example 1, instead of the emulsion consisting of cubic AgRrI (I: 1.2 mol%) grains with an average grain size of 0.6 μm, cubic grains with an average grain size of 0.5 μm were used.
A coating solution was similarly prepared using an emulsion consisting of AgRrI (I: 2 mol%) particles, and the antifoggant 1-phenyl-5-mercaptotetrazole 1 mg, the hardener 2,4-dichloro-6-hydroxy 1, 3,5-
Add 0.2g of triazine and then add hydroquinone.
300 mg was added, and the rest were Sample No. 1- of Example 1.
Sample No. 4-1 was prepared in the same manner as in Example 5. Sample No. 4-1 thus obtained showed good whiteness, similar to Sample No. 1-5.

Claims (1)

[Claims] 1. A photographic layer on a support having a hydrophilic colloid as a binder contains an oil-soluble optical brightener emulsified dispersion and a dye, and the oil-soluble optical brightener emulsified dispersion and the dye are substantially each other. A silver halide photographic paper characterized by the presence of different photographic layers.