JPS6370844A - Photographic sensitive material - Google Patents

Abstract

PURPOSE:To improve the whiteness of a substrate after development without deteriorating other characteristics of the substrate such as luminance, saturation, sharpness, etc., by incorporating a fluorescent whitening agent to at least one layer provided on the substrate. CONSTITUTION:In a photographic sensitive material provided with at least one photosensitive layer on a substrate having a surface capable of causing mirror reflection or the second kind diffusion reflection, a fluorescent whitening agent is incorporated in at least one layer formed on the substrate by dispersing it therein, thus the agent is incorporated in a specified layer, particularly in an undercoated layer, intermediate layer, protecting layer, etc. The fluorescent whitening agent is soluble in an org. solvent, and can be dispersed by emulsification, or by the aid of a polymer or coupler. Therefore, it is advantageous to incorporate it in a specified layer. Compds. expressed by the general formula II, III, IV, or V are preferred. Thus, the whiteness is enhanced, and the saturation of yellow and red color and the luminance which are distinct in the color photography can be improved.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a photographic material that has been dramatically improved in image brightness, tone reproducibility in dark areas, sharpness, and the like. More specifically, the present invention relates to a light-sensitive material using a reflective support having specular reflection or second type diffuse reflection that improves white reproduction and brightness of iz4 light.

[Conventional technology]

The applicant has proposed a photographic material that can improve image brightness, tone reproducibility and sharpness in dark areas, and especially in the case of color photosensitive materials, saturation of color images to a degree that cannot be achieved with conventional photographic reflective materials. An application has already been filed (Japanese Patent Application No. 168800-5 of 1981). These excellent performances are largely due to the use of a support having a specular reflective or second type diffuse reflective surface.

[Problem that the invention seeks to solve]

However, even on a support with a type 2 diffuse reflective surface or a support with a specular reflective surface, if an undercoat layer or photosensitive layer is coated, the length of approximately 4200 m after desilvering and fixing treatment is
There is a defect that gives highlights a pale yellowish tinge due to strong spectral absorption in the following areas.

An object of the present invention is to improve the whiteness in development processing using a support without deteriorating other characteristics such as brightness, chroma, sharpness, etc.

Preferably, it not only increases whiteness but also improves the saturation and brightness of yellow and red colors that are prominent in color photographs.

The present invention is achieved as follows.

[Means for solving problems]

The present invention relates to a photographic material in which at least one photosensitive layer is provided on a support having a specular reflective surface or a type 2 diffuse reflective surface. The present invention relates to a photographic material containing a fluorescent brightener.

Furthermore, the present invention provides a photographic light-sensitive material in which at least one photosensitive layer is provided on a support having a specular reflective surface or a type 2 diffuse reflective surface. The present invention relates to a photographic light-sensitive material characterized in that an intermediate layer or a protective layer adjacent to the layer contains a fluorescent brightener that reacts with an oxidized product of a developing agent to release fluorescent whitening residues.

The present invention will be explained below.

(Support) The support used in the present invention is a support having a specular reflective surface or a second type diffuse reflective surface.

In general, the reflection characteristics of an object's surface can be roughly divided into specular reflection and diffuse reflection. Furthermore, diffuse reflection can be divided into first type diffuse reflection and second type diffuse reflection. Specular reflection is reflection from a smooth surface and follows the normal rules of specular reflection. On the other hand, diffuse reflection refers to paper, painted surfaces,
Reflection from wood or walls causes parallel incident light to scatter not only in the specular direction but also in all directions.

Type 2 diffuse reflectance generally refers to reflection from rough surfaces with small slope boundaries, such as ground glass or polished metal surfaces. In the present invention, type 2 diffuse reflectance refers to reflectivity in which a smooth mirror-reflecting surface has small boundaries due to small irregularities. In this case, the diffusely reflected light can be considered to be a collection of specularly reflected lights from small reflecting surfaces. This is the second
This is why the species diffuse reflectance is called "small specular reflectance."

For example, Color Science Handbook (Japan Color Society, 1932)
Chapter 18, Chapter 1 of 05th edition, published by the University of Tokyo Press)
Defined by Section.

Type 1 diffuse reflectance and type 2 diffuse reflectance can be distinguished by the difference in reflectance on the mirror surface of the material. In general, a material with a first type of diffuse reflection property provides a reflectance lower than a reflectance R of a material with a second type of diffuse reflection property. In the present invention, the second type of diffusely reflective material preferably has a reflectance R° of 0.
It can be said that it is 5 or more. More preferably, the reflectance R is 0.7 to 1.0. This reflectance R can be determined using a goniole left meter.

The first type of diffuse reflection means that a solid with good light transmittance is made into a fine powder, and most of the irradiated light is first transmitted through the powder.
This refers to the reflectivity of diffused light due to surface reflection or total reflection.

The difference between specular reflectance and diffuse reflectance can be distinguished as follows based on the difference in spectral reflectance. Here, the spectral reflectance refers to, for example, 5
Measured with 50 nm monochromatic light, and removes the specular component by setting a trap at a viewing angle of 10 degrees centered on the specular reflection direction of the incident light, and components that are diffusely reflected in a viewing angle range of 90 degrees from the normal line. is calculated using an integrating sphere and calculated as a percentage of the incident light. The second type of diffuse reflectance in the present invention is the above-mentioned spectral reflectance (measured with monochromatic light of 550 nm) of 5% or more.The reason why monochromatic light of 55On+n was adopted here is because it has a wavelength close to relatively high visibility. This is because the wavelength is a typical wavelength in the green wavelength region, and dyes and pigments that intentionally interfere with the spectral absorption characteristics of the material on the surface of the support must be excluded in the measurement.Generally, the spectroscopy of the support according to the present invention The reflectance is represented by a flat curve.The spectral reflectance can be determined using a Color Analyzer Model 307 manufactured by Hitachi.

The material providing the specular reflective surface and the second type diffuse reflective surface according to the present invention is F, Benford.
et al. J, Opt, Soc, Amer, vol. 32, 174
184 (1942), such as silver, aluminum, gold, copper, chromium nickel, platinum,
For example, alloys thereof such as aluminum/magnesium alloy, aluminum/F4, aluminum/antimony, and scintillator are used.

In addition to metals, natural mica, fish and shellfish scales, and pearls are also materials that provide the second type of diffuse reflection.

For example, there is a description in a paper by Teizo Aida of "Optics" Vol. 15, No. 3 (published June 1986), pp. 207-212.

Specular reflective surfaces are typically rolled using a smooth rolling drum in an annealing process and then laminated with the smooth side to a substrate or used as a support itself.

It can also be obtained on a smooth substrate by vacuum evaporation, sputtering, ion blating, electrodeposition, electroless plating, or the like. A second type of diffusely reflective surface is provided by roughening the specularly reflective surface described above. For example, the metal may be annealed and then rolled using an appropriately textured rolling drum, or, for example, two metal sheets may be stacked and rolled at the same time, and then separated and rolled up. It is also possible to add unevenness. By making the surface of the substrate uneven in advance, it is also possible to walk on the uneven surface that provides the second type of diffuse reflection. Further, a second type of specular reflective surface can be created by mixing a powdered solid with a resin to form a filling layer. The number of concavities and convexities can be measured as the frequency of surface roughness, and can be actually measured using Elonics, a cross-sectional shape measuring device that uses electron beam irradiation. Preferably the average frequency is 0.1-2
000 pieces/mff1, more preferably 1 to 1000 pieces/mff1
It is mm. It is also possible to adopt a multiplexing concept in which one frequency is overlapped with, for example, four times as many high frequencies. Further, the average particle diameter of the solid that provides specular reflection is preferably 0.01 to 100 μ. Especially in the case of aluminum, it is 1 to 100μ.
Preferably it is 5 to 70μ. In the case of silver, it is preferably 0.1 to 100μ, and in the case of gold, it is preferably 0.01 to 100μ.

In addition, resins include water-soluble polymers (e.g., gelatin, etc.), aqueous latex (e.g., styrene-butadiene,
acrylonitrile-butadiene, acrylic, styrene-acrylic, vinylidene chloride, acetic acid-vinyl chloride, ethylene-vinyl acetate, etc.)a Organic solvent-based resin (e.g., acrylic, polyester, cellulose, polystyrene, polychloride) Thermoplastic resins such as vinyl and polyvinyl acetate (e.g. polyethylene propylene, phenolic resins, etc.)
etc. can be mentioned.

In the present invention, the above-mentioned resin and the above-mentioned solid powder are mixed, and then the mixture is coated on a substrate using a known method such as a knife coater, and if necessary, dried. A support can be obtained.

In addition, as a different method, photopolymerizable monomers or oligomers (for example, acroyl-based monomers having unsaturated double bonds,
A metaacroyl-based or acrylamide-based compound, a compound containing an allyl group, a vinyl ether group, a vinyl thioether group, etc., or an unsaturated polyester-based compound (molecular weight 1000 to 20,000)) and the solid powder are mixed, and the mixture is used as a substrate. The photographic support of the present invention can also be obtained by coating the film thereon and then irradiating it with an electron beam or the like to form a film. In the present invention, for example, pages 235 to 236 and A of the photosensitive resin data collection published by Sogo Kagaku Kenkyusho (1968).

Franken, Fatipec Congress, l
Compounds described in Vol. 1, No. 19 (1972) and the like can be suitably used as the photopolymerizable monomer or oligomer.

As the substrate of the support according to the present invention, those conventionally used can be used as they are without any problem. For example, plastic, film, paper, RC paper, synthetic paper, metal plate, etc. are used. Paper or RC-paper is preferable, and it can also be obtained by laminating metal foil using low-density polyethylene in combination with the polyethylene layer of RC-paper.

The support according to the present invention can be provided with a silver halide emulsion layer via an undercoat layer. The undercoat layer is obtained using a thermoplastic resin such as polyethylene or polypropylene, or an ionomer resin containing an epoxy adhesive. A gelatin or gelatin silver halide emulsion layer can be provided thereon, with or without corona discharge treatment.

In some cases, the present invention may contain fine particles that perform diffuse reflection of the first type in an upper layer such as an undercoat layer in a small amount, for example, 1 g/m1 or less, and finely dispersed particles of latex or a high boiling point organic solvent that perform diffuse reflection of the first type in the upper layer. It can also be included.

Other methods described in the specifications of Japanese Patent Application No. 61-168800-5 can be selected and used.

The photosensitive material used in the present invention can be made by the method described in the specification of the above-mentioned application. That is, a silver halide emulsion layer for black and white printing paper may be provided on the support via an undercoat layer if necessary, and the protection I may be provided thereon. Similarly, a color photographic paper light-sensitive material can be prepared by providing two or more light-sensitive silver halide emulsion layers each having a different spectral sensitivity and each containing a different color coupler for ordinary color photographic paper. It is also possible to produce color reversal photosensitive materials, direct positive color photographic papers, and direct positive color copy materials using a light fogging method. Further, on this support, red-, green-, and blue-sensitive silver halide emulsion layers containing silver halide grains having different spectral sensitivities and a dye used in the silver gouy bleach (SDB) method are formed. It is also possible to make SDB-type printed photosensitive materials by using this method.

It can also be used as an image-receiving sheet by a silver salt diffusion method or a dye diffusion method. It can also be used as a sheet for image transfer.

(Fluorescent Brightener-1) The feature of the present invention is that the fluorescent brightener is dispersed and contained in a specific layer. Especially undercoat layer, intermediate layer, protective layer,
This means that it should be included in, etc.

Generally, a fluorescent brightener is often added to a developing solution to dye the image. However, it may not dye stably. Furthermore, in this method, the stability of the optical brightener over time is poor. Rather than the whitening effect, the removal of dyeing substances may contribute to whitening.

What is the optical brightener used in the present invention? JP-A-60-154
This is a compound specifically shown in No. 251. This optical brightener is soluble in organic solvents, can be dispersed by emulsion dispersion, polymer dispersion, or coupler dispersion, and is advantageous for incorporating into a specific layer of a light-sensitive material, and has the following general formula (II) a.
Compounds represented by (I[I)a(I''/)a(V) are preferred.

In the formula, Y+, Y2: alkyl group, ZISZ2 is H1
Alkyl group, n is 1 or 2, R+, R2, R4, R
s is H1 aryl group, alkyl group, alkoxy group, aryloxy group, hydroxynopeamino, cyano, carboxynobeamide, ester, alkylcarbonyl, alkylsulfo or dialkylsulfonyl group, R6 and R7 are H1 methyl group, ethyl group, etc. R16: phenyl group, halogen atom, alkyl-substituted phenyl group, R1s niamino group, organic primary or secondary amine. Next, a specific example will be given.

These water-soluble optical brighteners are used by being dissolved in a high-boiling point organic solvent and dispersed in these hydrophilic colloids with a surfactant in the same way as color couplers.

For example, British Patent No. 1.072.915, JP-A-60-
The method shown in Japanese Patent Publication No. 134232, Japanese Patent Publication No. 51-30463, Japanese Patent Application Laid-Open No. 1520-1980, Japanese Patent Application Publication No. 25057-1987, Japanese Patent Publication No. 37376-1987, and U.S. Patent No. 341692
This method and organic solvents are described in No. 3 and other publications.

Further, these fluorescent brighteners can also be used by dissolving them in a low boiling point organic solvent such as acetone, methyl, ethyl ketone, methanol, etc. and mixing them into an undercoat coating solution such as an ionomer solution. These dispersions can be used by being mixed with a coating solution for a predetermined layer. Optical brighteners are usually 3+r
+g~200mg/m" is used. Also, JP-A-57-
Hydrophobic materials or color couplers can also be mixed with ionomer polyaddition or condensation products used in place of optical brighteners to form polymers that can be used as subbing layers, as described in US Pat. No. 87,429.

In addition, optical brighteners selected from ordinary stilbene derivatives and diphenyl derivatives can be used to make polyvinyl By incorporating it in combination with pyrrolidone, polyvinyl acetate, or a polymer of the following repeating unit, it is possible to fix the brightener and create a layer that exhibits strong fluorescence.

General formula (VI') -8-1i-: A knee COR in the formula
+ , -C'00Rz, ^ (ONHR3, -CONHCOR4 or -SO□R2
R+, R2, Rs, R4, and Rs each represent a monosubstituted or unsubstituted alkyl group, aryl group, or cycloalkyl group.

Next, specific compounds are shown.

ni:j7:m=23:50:27 Specific examples of optical brighteners used here are shown below.

For example, dissolve 0.1 g of WF-1 in 100 mf of water, add 0.25 g of P-1 polymer to it, make a dispersion, and make a protective layer with a coating amount of WF-1 of 50 mg/m''. It can be added to the undercoat layer.

(Fluorescent Whitening Agent-2) This is a device in which the whitening effect of a fluorescent whitening agent acts only on the highlight areas of an image and does not act on the image forming area. Generally, in the case of color light-sensitive materials, since an ultraviolet absorber is contained in the layer on the surface side of the image forming layer, the effect of the fluorescent brightener on the support side must be weakened. Therefore, it is preferable that the compound having a fluorescent whitening effect be present on the surface side, and more preferably only in the highlighted area. Therefore, in the present invention, a photosensitive layer containing silver halide or an intermediate layer adjacent thereto is provided with a fluorescent substance that reacts with an oxidized product of a developing agent to release a fluorescent whitening residue and release it into the developer. Use brightener.

Specifically, a compound represented by the following general formula CI) is used.

General formula [:I:l A-(L)a-Ff In the formula, FIl is a residue of a compound with fluorescent whitening property, L is a linking group, and a is 1
or 2. A represents a color coupler residue, a colorless coupler residue, a hydroquinone residue, etc., and is a residue of a compound capable of performing an exchange reaction with an oxidized form of a developing agent to release Ff. For example, JP-A-52-1099
27, British Patent No. 945.542, West German Publication No. 1800420, etc. Next, specific compounds are listed.

UUSimilar to color couplers, such compounds are dissolved in an organic solvent with a high boiling point, and dispersed in a hydrophilic colloid with the help of a surfactant to form a photosensitive layer, especially a photosensitive N or N containing photosensitive silver halide on the surface. This is added to the adjacent intermediate layer or protective layer. On the other hand, for example, Special Publication No. 48-30494
Such compounds can be dispersed using water-insoluble organic solvent-soluble polymers such as polyvinyl alcohol, polyvinyl acetate, polyacrylic acid esters, copolymers, etc., or the above-mentioned optical brightener-dispersed polymers and latexes, as described in No. You can also do it. By using these compounds, only the highlight portions of each image can be whitened relatively selectively.

(Silver Halide Emulsion) The silver halide grains used in the present invention may be obtained by any of the acid method, neutral method, ammonia method, or a combination of these methods. For example, the core particles may be made by an acid method and then grown by an ammonia method. This growth process is pi
(It is preferable to use a method such as SflAg in which a predetermined amount of silver ions or halogen ions are implanted under controlled conditions.

The diameter of the particles may be anywhere from 1μ to 0.05μ, especially 0.
．． The particles may have a particle diameter of 8 to 0.2μ, and may be monodisperse particles or polydisperse particles.

These silver halide grains may be pure silver chloride, silver chlorobromide, silver bromide or silver iodobromide emulsion. Any choice is fine.

The silver halide emulsion used in the present invention has an average grain size of 0.1 μm as expressed by the diameter of an equivalent circle in projection.
~2 μm is preferable, more preferably 0.2 μm ~1
．． It is 3 μm. Preferably, the emulsion is a monodisperse emulsion, and the grain size distribution representing the degree of monodispersion is 0 in terms of the ratio of the statistical standard deviation (S) to the average grain size (positive) (S/d).
．． It is preferably 2 or less, more preferably 0.15 or less.

The silver halide grains used in the present invention may have different phases inside and on the surface, may have a multiphase structure such as a bonded structure, or may consist of a uniform phase throughout the grain. Moreover, they may be mixed.

The shape of the silver halide grains used in the present invention is regular (cubic, octahedral, dodecahedral, dodecahedral, etc.).
), may have an irregular crystal shape such as a spherical shape, or may have a composite shape of these crystal shapes. Further, tabular grains may be used, and in particular, an emulsion may be used in which tabular grains having a length/thickness ratio of 5 or more, particularly 8 or more occupy 50% or more of the total projected area of the grains. An emulsion consisting of a mixture of these various crystal forms may also be used. These various emulsions may be either a surface latent image type in which a latent image is mainly formed on the surface or an internal latent image type in which a latent image is formed inside the grains. These silver halides can be sensitized using activated gelatin, chemical sensitizers such as allylthiocarbamide, cystine, thiosulfate, reduction sensitizers such as polyamines and stannous chloride, noble metal sensitizers, and rhodium or iridium complex salts. Chemical sensitization may be performed using a sensitizer such as a sensitizer.

Further, fog suppressants such as mercaptotriazoles, mercaptotetrazoles, and benzo)IJ azoles may be used in combination with the silver halide emulsion layer.

For rapid development processing, a silver chlorobromide emulsion or a silver chloride emulsion is preferred, and a fog suppressant or stabilizer strongly adsorbed to silver halide, such as a mercapto compound, a nitrobenzotriazole compound, or a benzotriazole compound, is used therein. Further, commonly used development accelerators, antihalation agents, antiirradiation agents, fluorescent whitening agents, and the like can also be used in combination.

The blue-sensitive, green-sensitive and red-sensitive emulsions of the present invention are spectrally sensitized with methine dyes and others so that they have color sensitivity. The dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopo-5-cyanine dyes, hemicyanine dyes,
Included are styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes, merocyanine dyes, and dyes belonging to complex merocyanine dyes.

Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus for these dyes. Namely, viroline 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 Nuclei, quinoline nuclei, etc. can be applied. These nuclei may be substituted on carbon atoms.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, and a 2-thioxazolidine-2 nucleus having a ketomethylene structure.
, 4-dione nucleus, thiazolidine-2,4-dione nucleus, rhodanine nucleus, thiobarbic acid nucleus, and the like can be applied.

These sensitizing dyes may be used alone or in combination, and combinations of sensitizing dyes are often used particularly for the purpose of supersensitization. Typical examples are U.S. Patent Nos. 2.688.545, 2.977.229, and
, No. 397.060, No. 3,522.052, No. 3,
No. 527,641, No. 3,617.293, No. 3,6
No. 28,964, No. 3,666.480, No. 3,67
No. 2.898, - No. 3,679.428, No. 3,70
3.377, 3.769.301, Dohada 814,
No. 609, No. 3.837.862, No. 4,026.7
07, British Patent No. 1.344,281, British Patent No. 1,50
No. 7,803, Special Publication No. 43-4936, No. 53-12
No. 375, JP-A-52-110618, JP-A No. 52-10
No. 9925.

Along with the sensitizing dye, it is a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light,
A substance exhibiting supersensitization may also be included in the emulsion.

(Coupler) The color coupler incorporated in the light-sensitive material is preferably diffusion-resistant by having a ballast group or being polymerized. A two-equivalent color coupler substituted with a leaving group can reduce the amount of silver coated than a four-equivalent color coupler in which the coupling active position is a hydrogen atom. Couplers in which the color-forming dye has adequate diffusivity, non-color-forming couplers, or DIR couplers that release a development inhibitor or couplers that release a development accelerator upon coupling reaction can also be used.

A representative example of the yellow coupler that can be used in the present invention is an oil-protected acylacetamide coupler. A specific example is U.S. Patent No. 2.40
7.210, 2.375.057 and 3.265.50
It is stated in issue 6 etc. The use of two-equivalent yellow couplers is preferred for the present invention, as described in U.S. Pat. No. 3,408.
No. 194, No. 3.447.928, No. 3,933
．． 501 and 4,022,620, Japanese Patent Publication No. 58-10739, and U.S. Patent No. 4,401.752.
No. 4,326.024, RD18053 (1
April 979) a British Patent No. 1.425.020, West German Published Application No. 2,219.917, West German Patent Application No. 2.261,361,
No. 2,329.587 and No. 2; 433.8
A typical example thereof is the nitrogen atom separation type yellow coupler described in No. 12. α-pivaloylacetanilide couplers provide excellent color fastness, especially light fastness, while α-benzoylacetanilide couplers provide high color density.

Magenta couplers that can be used in the present invention include oil-protected indacylon or cyanoacetyl couplers, preferably pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles. As for the 5-pyrazolone couplers, a coupler in which the 3-position is substituted with an arylamino group or an acylamino group is preferable from the viewpoint of the purple hue and color density, and a typical example thereof is as described in U.S. Pat. No. 2,311,082. , 2.3 of the same
No. 43,703, No. 2,600,788, No. 2.
No. 903,573, No. 3.062.653, No. 3,152.896, No. 3.936.015, etc. As a leaving group for a two-equivalent 5-pyrazolone coupler, the nitrogen atom leaving group described in U.S. Pat. No. 4,310.619 or U.S. Pat. No. 4,351
．． The arylthio group described in No. 897 is preferred. Further, the 5-pyrazolone coupler having a ballast group described in European Patent No. 73.636 provides a high color density.

As a pyrazoloazole coupler, US Patent No. 3.
369,879, preferably pyrazolo[5.1
-C] [”1.2.4]) Riazoles, research
Examples include pyrazolotetrazoles described in Disclosure 24220 (June 1984) and pyrazolopyrazoles described in Research Disclosure 24230 (June 1984). Imidazo["1.2-b] described in European Patent No. 119,741 in terms of low yellow side absorption of coloring dye and light fastness.
Pyrazoles are preferred, such as pyrazolo (1,5-b:] described in European Patent No. 119.860).
(1,2,4)) Riazoles are particularly preferred.

Cyan couplers that can be used in the present invention include oil-protected naphthol-based and phenolic couplers, such as the naphthol-based couplers described in U.S. Pat. No. 2,474,293, and preferably U.S. Pat. No. 4
．． Typical examples include the oxygen atom elimination type two-equivalent naphthol couplers described in No. 146.396, No. 4,228.233, and No. 4.296,200. Further, specific examples of phenolic couplers are described in U.S. Pat. There is. Cyan couplers that are stable against humidity and temperature are preferably used in the present invention, and a typical example thereof is as described in U.S. Pat. Phenolic cyan coupler with U.S. Patent No. 2
．． No. 772,162, No. 3.758,308, No. 4.126.396, No. 4.334,011, No. 4.327,173, West German Patent Publication No. 3.329.729 No. and patent application No. 58-42671
2,5-diacylamino-substituted phenolic couplers described in U.S. Pat. No. 3,446.622, U.S. Pat. ,427.7
These include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No. 67.

Granularity can be improved by using a coupler in which the coloring dye has an appropriate diffusibility. Such dye-diffusive couplers are described in US Pat. No. 4.366.237 and British Patent No. 2.125,
Specific examples of magenta couplers are given in European Patent No. 96,570 and German Published Application No. 3.234.5.
No. 33 describes specific examples of yellow, magenta or cyan couplers.

The dye-forming couplers and the special couplers described above may form dimers or more polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3.451.82.
0 and 4.080.211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and US Patent No. 4.367.
It is described in No. 282.

The various couplers used in the present invention can be used in combination in the same layer of the photosensitive layer in order to satisfy the characteristics required for the photosensitive material, or in two or more different layers using the same compound. It can also be introduced into

The coupler used in the present invention can be introduced into the light-sensitive material by an oil-in-water dispersion method. In the oil-in-water dispersion method, the boiling point is 1
After dissolving in either a high boiling point organic solvent of 75°C or higher and a low boiling point so-called auxiliary solvent alone or in a mixture of both, finely dispersed in an aqueous medium such as water or an aqueous gelatin solution in the presence of a surfactant. . Examples of high boiling point organic solvents are described in U.S. Pat. No. 2,322,027 and others. Dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, noodle washing, ultrafiltration, or the like before use for coating. Further, a technique of dispersing a water-insoluble organic solvent-soluble polymer or latex, similar to the method of dispersing a fluorescent brightener, can be used.

For example, compounds described in the specification of Japanese Patent Application No. 61-168800-5, such as anti-fading agents for coloring pigments, anti-color mixing agents,
Ultraviolet absorbers, filter dyes, antihalation dyes, colloidal silver, hardening agents to strengthen film quality, polymer latex particles, etc. can be used to improve the light printing durability of color images.

The black and white light-sensitive material used in the present invention has an antihalation layer (AHL) on the support, and the light-sensitive layer containing silver halide grains is spectrally sensitized using the above-mentioned sensitizing dyes depending on the purpose, in addition to regular, ortho, and panchromatic sensitization. Most of them are composed of a high-sensitivity layer (GL), a low-sensitivity layer (UL), an intermediate layer (ML), a protective layer (PCL), etc. In the case of color photosensitive materials, there are a red-sensitive layer (RL), a green-sensitive layer (GL), a blue-sensitive layer (BL), an intermediate layer (ML), and a yellow filter layer (
YFL) a, etc., if necessary, for example, on the support.
HL, BL, GL, RL, ML.

PCL; AHLSBLSRLSGL, ML.

PCL; AHL, RL, MLGL, MLSYFL.

BL, MLSPC, etc. can be used arbitrarily.

The silver halide photosensitive layer can be divided into two or more layers such as a high-sensitivity layer and a low-sensitivity layer. For these structures, the structure of a photosensitive material for printing using a normal film or photographic paper as a support can be applied.

In the case of black-and-white photosensitive materials, methods and processing agents commonly used for developing black-and-white photographic paper are used.

In the case of color photosensitive materials, the following methods and processing agents are used.

The color developing solution used in the development of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing crude drug as a main component. Aminophenol compounds are also useful as color developing agents, but p-phenylenediamine compounds are preferably used, representative examples of which are 3-methyl-4-amino-N, N-diethylaniline, 3-methyl -4-amino-N-ethyl-N-
β-hydroxylethylaniline, 3-ethyl-4-amino-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-methyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-)luenesulfonate. These diamines are generally more stable in their salt form than in their free state and are preferably used.

The color developer contains pH buffering agents such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazole or mercapto compounds. Generally, it includes such things as If necessary, derivatives such as hydroxylamine or dihydroxyalkylamine or preservatives such as sulfites, organic solvents such as triethanolamine and diethylene glycol, benzyl alcohol, polyethylene glycol, quaternary ammonium salts,
Development accelerators such as amines, dye-forming couplers, competitive couplers, nucleating agents such as sodium boron hydride, auxiliary developers such as 1-phenyl-3-pyrazolidone, tackifiers, aminopolycarboxylic acids, West German patent application (OL
S) Antioxidants such as those described in No. 2,622,950 may be added to the color developer.

In the development process for reversal color photosensitive materials, black and white development is usually performed followed by color development. This black and white developer contains dihydroxybenzenes such as hydroquinone, 1-phenyl-
3-pyrazolidone neck or N- such as 3-pyrazolidone
Known black and white developers such as aminophenol compounds such as methyl-p-aminophenol can be used alone or in combination.

After color development, the photographic emulsion layer is usually bleached.

The bleaching process may be performed simultaneously with the fixing process or may be performed separately. As a bleaching agent, for example, iron (■) a
Compounds of polyvalent metals such as cobalt (■), chromium (■), copper (II), peracids, quinones, nitrone compounds, and the like are used. Typical bleaching agents include ferricyanide; dichromate; iron, (III) or cobal) (II
f) organic complex salts such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1.3-
Aminopolycarboxylic acids such as diamino-2-propatoltetraacetic acid or complex salts of organic acids such as citric acid, tartaric acid and malic acid; persulfates; manganates; nitrophenols and the like can be used. Among these, ethylenediaminetetraacetic acid iron (III) salt and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Furthermore, the ethylenediaminetetraacetic acid iron(III) complexes are particularly useful both in stand-alone bleach solutions and in -bath bleach-fix solutions.

If necessary, various accelerators may be used in combination with the bleaching solution and bleach-fixing solution. For example, in addition to bromide ion and iodide ion, U.S. Pat.
Thiourea compounds as shown in No. 53-36233 and No. 53-37016; JP-A-53-1244
No. 24, No. 53-95631, No. 53-57831, No. 53-32736, No. 53-65732, No. 5
Thiol-based compounds as shown in JP-A-49-59644 and US Pat. No. 50-140, etc.;
No. 129, No. 53-28426, No. 53-14162
No. 3, No. 53-104232 and No. 54-3572
Heterocyclic compounds described in No. 7, etc.; JP-A-52-. 20
No. 832, No. 55-25064 and No. 55-265
Thioether compounds described in No. 06, etc.;
Tertiary amine order described in No.-84440; JP-A-49-4
The thiocarbamoyl compounds described in No. 2349 may be used alone or in combination of two or more. Bromine ions, iodide ions, thiol-based or disulfide-based compounds are preferred bleach accelerators. These bleach accelerators are effective when bleach-fixing color light-sensitive materials for photography.

Examples of the fixing agent include thiosulfates, thiocyanates, thioureas of thioether compounds, and large amounts of iodides, but thiosulfates are commonly used. As the preservative for the bleach-fix solution and the fix solution, sulfites, bisulfites, or carbonyl bisulfite adducts are preferred.

After bleach-fixing or fixing, washing with water is usually performed. Various known compounds may be added to the water washing process for the purpose of preventing precipitation and saving water. For example, to prevent precipitation, use water softeners such as inorganic phosphoric acid, aminopolycarboxylic acid, and organic phosphoric acid, fungicides and anti-pyre agents to prevent the growth of various bacteria, algae, and mold, magnesium salts, and aluminum. A hardening agent typified by salt, a surfactant for preventing drying load and unevenness, etc. can be added as necessary. Or the photographic book Science and Engineering by West (L.B. West, Phot, Sci.

Eng, ), Volume 6, pp. 344-359 (19
65) etc. may be added.

The addition of chelating agents and anti-piping agents is particularly effective.

In the washing process, the tanks on the second floor and above are generally washed with countercurrent water to conserve water. Furthermore, instead of the water washing process,
A multi-stage countercurrent stabilization treatment process such as that described in No.-8543 may be implemented. In the case of this step, 2 to 9 countercurrent columns are required. Various compounds are added to this stabilizing bath for the purpose of stabilizing images. For example, various buffers (e.g., borates, metaborates, borax, phosphates, carbonates, potassium hydroxide, sodium hydroxide, ammonia water, Typical examples include monocarboxylic acid, dicarboxylic acid, polycarboxylic acid, etc. (used in combination) and formalin. In addition, water softeners (inorganic phosphoric acid, aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericides (penzoisoticizolinone, isothiazolone, 4-thiazoline, etc.) are added as necessary. (benzimidazole, halogenated phenol, etc.) a Various additives such as surfactants, optical brighteners, hardeners, etc. may be used, and two or more compounds for the same or different purposes may be used in combination.

In addition, ammonium chloride,
It is preferable to add various ammonium salts such as ammonium nitrate, ammonium sulfate, ammonium phosphate, ammonium sulfite, and ammonium thiosulfate.

The silver halide color light-sensitive material of the present invention may contain a color developing agent for the purpose of simplifying and speeding up processing. For this purpose, it is preferable to use various precursors of color developing agents.

For example, indoaniline compounds described in U.S. Pat. No. 3,342.597, U.S. Pat.
Schiff base-type compounds described in JP-A No. 13924, aldol compounds described in US Pat. No. 13924, metal salt complexes described in U.S. Pat. No. 56-6235, No. 56-16133, No. 56-59232, No. 5
No. 6-67842, No. 56-83734, No. 56-8
No. 3735, No. 56-83736, No. 56-8973
No. 5, No. 56-81837, No. 56-54430,
Examples include various salt-type precursors described in No. 56-106241, No. 56-107236, No. 57-97531, and No. 57-83565.

The silver halide color photosensitive material of the present invention may contain various 1-phenyl-
3-pyrazolidones may be incorporated. Typical compounds are JP-A Nos. 56-64339, 57-144547, 57-211147, 58-50532, 58-50536, 5g-50533, and 58-
No. 50534, No. 58-50535 and No. 58-1
It is described in No. 15438, etc.

Various treatment liquids in the present invention are used at 10°C to 50°C. A temperature of 33°C to 38°C is standard, but higher temperatures can be used to accelerate the processing and shorten the processing time.
Conversely, it is possible to improve the image quality and the stability of the processing solution by lowering the temperature. In addition, West German Patent No. 2.226.770 or U.S. Patent No. 3,
A treatment using cobalt intensification or hydrogen peroxide intensification as described in No. 674.499 may also be carried out.

A heater, a temperature sensor, a liquid level sensor, a circulation pump, a filter, a floating pig, a squeegee, etc. may be provided in each of the processing baths as necessary.

The photosensitive material according to the present invention can be developed using a conventional minilab system.

Next, examples of the present invention will be shown. However, it is not limited to this.

Example-1 Metal aluminum was roughly rolled, and further, two sheets of annealed metal aluminum were stacked and rolled on the central rolling roller by rolling the upper and lower two adjacent rolling rollers. An aluminum foil having a thickness of about 10 μm was obtained. Surprisingly, this adjoining surface had a type 2 diffuse reflection property. Low-density polyethylene was extrusion coated onto white photographic paper and laminated with metallic aluminum. Next, the other surface of the substrate was subjected to a corona discharge treatment, and then high-density polyethylene was extrusion coated to form a polyethylene resin layer having a thickness of 30 μm. This aluminum support having the second type of diffusely reflective surface was designated as Sample-1. Furthermore, an ionomer resin was applied to the aluminum surface, and after drying and corona discharge treatment, gelatin and a hardening agent 2,4-
An undercoat layer was provided using dichloro-6-hydroxy-1,3,5-)riazine. This will be referred to as Sample-1a.

In addition, the fluorescent whitening agent WF-1 was added to the aluminum surface in an ionomer resin latex dispersion (methanol and water (1:1).
Dissolve and mix in the mixture of 1) and add W into the iotsumer resin layer.
Sample 1-1 was obtained by containing 50 mg/m'' of F-1 and applying a gelatin undercoat layer in the same manner as Sample 1a.

Three types of samples, 1.1-a and 1-1, were irradiated with xenon light using Hitachi's new Color Analyzer Model 307.
Spectral reflectance was measured. Figure 1 was obtained. The effect of improving the tendency of yellowing due to the application of the undercoat layer to whitish to bluish by emitting light of about 420 to 470 nm can be understood.

Example 2 According to Example 1 of Japanese Patent Application No. 60-52788, thickness 10
A polyethylene phthalate film having a thickness of 0 μm was placed in a vacuum evaporation apparatus R, and an aluminum film having a thickness of 1000 μm was formed on the surface of the substrate at a degree of vacuum of 10°. This was coated with low density polyethylene to form a polyethylene resin layer having a thickness of approximately 15μ. This was designated as sample-2.

4.25g of gelatin at 5QmI! Dissolve 0.25 g of Polymer P-1 and WF-2 in water with tree oil to make a mixture of methanol and WF-2 (1:4). Stir thoroughly to mix both solutions and add the curing agent 1,3-bis. 1.5 mj of 2% methanol solution of vinylsulfonyl-2-propanol! added. After subjecting Sample-2 to corona discharge treatment, water was appropriately added to the coating solution to form an undercoat layer such that WF-2 was 80 mg/m'. This was designated as sample-2-1. On the other hand, an undercoat layer was provided using gelatin and the above-mentioned hardening film as Sample-2-a.

A silver chlorobromide emulsion layer (halogen composition AgCA 67% average grain size 0.4 μm) used for photographic paper was provided thereon, and a protective layer was further provided. They were designated as sample 3 and sample 3-a, respectively.

Silver coverage was 2.1 g/m'.

The resulting two photographic papers were exposed to light through a negative film original, developed for 2 minutes using developer D-72 (1:2 dilution), fixed, and washed with water.

In both cases, the highlights were bright and the tones in the dark areas were rich and sharp. Surprisingly, compared to Sample-2a, Sample-2-1 had a whitish tinge added to the highlights and did not tend to be inferior in maximum density or shadow tightness.

Example-3 In Example-2, dissolve C-41g in the silver halide emulsion of Sample-3-a in methanol, dissolve 1g of polyvinyl alcohol and 0.5g of P-ethoxyacedoanilide in a solution, and disperse in gelatin. Sample 4 was obtained by dispersing C-4 at 80 mg/m'. It was processed in the same manner as in Example 2, and the whiteness of the highlights was improved compared to the photograph given to Sample 3-a.

Example 4 Silver halide emulsion (1) used in the examples of the present invention was prepared as follows.

(1 liquid) (2 liquid) Sulfuric acid (IN) 24CC (3 liquid) The following silver halide solvents (1%) 3CC (4 liquid) (5 liquid) (6 liquid) (7 liquid) (1 liquid) at 56% It was heated to ℃, and (liquid 2) and (liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously for 30 minutes. After another 10 minutes, (6 liquids) and 7 liquids were simultaneously added over a period of 20 minutes. After 5 minutes of addition, the temperature was lowered and desalted. Add water and dispersed gelatin, adjust the pH to 6.2, average particle size 0.45 μm, coefficient of variation (standard deviation divided by average particle size: S / 'T)
A monodispersed cubic silver chlorobromide emulsion containing 0.08% and 70% by mole of silver bromide was obtained.

IJium thiosulfate was added to this emulsion to perform optimal chemical sensitization.

Next, silver halide emulsions (2) (3) with different silver chloride contents
) (4) and (5), the above 4 liquids and 6 liquids of KBr 5
NaC1! Similar preparations were made by changing the amounts and addition times of liquids 4 and 5 as shown in Table 1.

Table 1 Average grain size of silver halide emulsions (1) to (5),
The coefficient of variation and halogen composition are shown in Table 2.

Table 2 Samples 1-1 and 1-a obtained in Example-1 are used as supports.

Layers 1 to 7 shown in Table 1 were layered on each support to obtain a color photosensitive material.

1st layer: Add sensitizing dye (a) to silver halide emulsion (5)
Spectral sensitization was carried out by adding 7.0×10 −' mol per 1 mol of gX. Furthermore, yellow coupler (d) and color image stabilizer (
A predetermined amount of e) was added by mixing and dissolving solvent (f) and dispersing the mixture. This was applied as the first layer.

Third layer: A sensitizing dye (b) is added to the silver halide emulsion (3).
Spectral sensitization was carried out by adding 4.0×10 −′ moles per mole of gX. Furthermore, magenta coupler (h) and color image stabilizer (1
) was mixed and dissolved in solvent (j), dispersed, and a predetermined amount was added.

This was applied as the third layer.

5th layer: A sensitizing dye (C) is added to the silver halide emulsion (2)
Spectral sensitization was carried out by adding 1.0X10-' mole per mole of gX. Furthermore, cyan coupler (n) and color image stabilizer (0) were mixed and dissolved in solvent (f), dispersed, and a predetermined amount was added. This was applied to form the fifth layer.

Coating liquids for the second layer, fourth layer, sixth layer, and seventh layer were obtained in the same manner.

On the undercoat layer of the support, the first layer, second layer, third layer, fourth layer,
Sample 5.6 and Comparative Sample A were coated with 5th layer, 6th layer and 7th layer.
I got it.

Furthermore, using the supports of samples 1-1 and 1-a in the same manner, the sixth
Sample 7 was prepared by using 0.11 g/m' of F-1 in the layer and changing only the fifth layer as follows.

Table 3 *C-1, P-1 and solvent (f) were dissolved in ethyl acetate,
A small amount of commonly used sodium nonylbenzenesulfonate was dispersed and added to a 12% gelatin aqueous solution.

The above sample was subjected to gradation exposure for sensitometry through a three-color separation filter of blue, green, and red using a light source at 2854°, or image exposure for printing by enlarging it through a negative film.

After that, a photographic image was obtained through the steps of color development, bleach-fixing, and rinsing.

When observing the photographic image with the naked eye, the saturation, especially the saturation of yellow and magenta, is extremely excellent. In particular, sharpness was surprisingly improved.

Additionally, gradation details in dark areas were well reproduced.

An image excellent in hue saturation and image sharpness similar to that obtained in Example 1 of Japanese Patent Application No. 168802/1980 was obtained. Furthermore, compared to A, both I and Ul had an improvement in whiteness due to the present invention, especially in sample (2), an improvement in whiteness and brightness in the highlight area was observed, resulting in a more natural-looking photograph.

(a) Blue-sensitive sensitizing dye, etc.) Green-sensitive sensitizing dye (+-1'h), bU3
L, 215 (d) Yellow coupler (f) Solvent uH (Company) Magenta coupler! (i) Color image stabilizer (J) Solvent bleach-fix solution formulation A Ammonium thiosulfate (54 wt%) 50 ml Na2SO,t 5 g NH4CFe (I[I) (εDTA))
55gεDTA・2Na
4 g Glacial acetic acid 8.61 g
Add water and the total amount is 10100O! (pH 5
, 4) Rinse liquid prescription A εDTA-2Na-2) 12[10.4g water was added to make the total amount 10100O! (pH 7,0) Development Prescription A 35℃ 45 seconds bleach fixing Prescription A 35℃ 45 seconds rinse
Prescription A 28-35℃ 1 minute 30 seconds Color developer A Water 80
0CC diethylenetriaminepentaacetic acid 1.0g
Sodium sulfite 0.2 gN,
N'; Ethylene hydroxylamine 4.2g Potassium bromide 0.6g Sodium chloride 1.5g Triethanolamine 8.0g Potassium carbonate
30g N-ethyl N-(β-methanesulfonamidoethyl)-3-methyl-4-aminoaniline sulfate Add 4.5g water at 100OCCKOH
pH10,25

[Brief explanation of the drawing]

FIG. 1 shows the spectral reflectance curve. Figure 1 Wavelength (nm) Procedural Amendment Document Showa Year Month Date Commissioner of the Patent Office Kunio Ogawa 3. Person making the amendment Relationship to the case Applicant name (520) Fuji Photo Film Co., Ltd. 4. Agent 5. Amendment Date of order Vol. 7. Contents of amendment (1) The scope of claims is amended as shown in the attached sheet. (2) The following parts of the specification are corrected as follows. Claims (1) A photographic light-sensitive material in which at least one photosensitive layer is provided on a support having a specular reflective or type 2 diffuse reflective surface; A photographic light-sensitive material characterized in that at least one layer contains a fluorescent brightener. (2) The layer provided on the support is an undercoat layer, a photosensitive layer,
The photographic material according to claim (1), which is an intermediate layer and a protective layer. (3) The photographic material according to claim (2), wherein a fluorescent brightener is contained in at least one of the undercoat layer, intermediate layer, or protective layer. (4) In a photographic light-sensitive material in which at least one photosensitive layer is provided on a support having a specular reflective or type 2 diffuse reflective surface, the photosensitive layer or photosensitive layer provided on the support A photographic light-sensitive material characterized in that an adjacent intermediate layer or protective layer contains a fluorescent brightener that reacts with an oxidized form of a developing agent to release fluorescent whitening residues. (5) The photographic material according to claim (4), wherein the fluorescent brightener is a compound represented by the general formula [I]. A-(L)a, -F IICI] (In the formula, Fl is a residue of a compound with fluorescent whitening properties, L is a linking group, and a represents 1 or 2, A is a colorless coupler residue It represents a coupler residue or a hydroquinone residue, and is a residue of a compound that can undergo an exchange reaction with an oxidized form of a developing agent to release Fl.)

Claims (5)

[Claims] (1) In a photographic material in which at least one photosensitive layer is provided on a support having a specular reflective or type 2 diffuse reflective surface, at least one of the layers provided on the support A photographic material characterized by containing a fluorescent brightener. (2) The layer provided on the support is an undercoat layer, a photosensitive layer,
The photographic material according to claim (1), which is an intermediate layer and a protective layer. (3) The photographic material according to claim (2), wherein a fluorescent brightener is contained in at least one of the undercoat layer, intermediate layer, or protective layer. (4) In a photographic light-sensitive material in which at least one photosensitive layer is provided on a support having a specular reflective or type 2 diffuse reflective surface, the photosensitive layer or photosensitive layer provided on the support A photographic light-sensitive material characterized in that an adjacent intermediate layer or protective layer contains a fluorescent brightener that reacts with an oxidized form of a developing agent to release fluorescent whitening residues. (5) The photographic material according to claim (4), wherein the optical brightener is a compound represented by the general formula [I]. A-(L)_a-Fl[I] (In the formula, Fl is a residue of a compound with fluorescent whitening properties, L is a linking group, and a represents 1 or 2, A is a color coupler residue and a colorless coupler. (represents a hydroquinone residue, which is a residue of a compound that can undergo an exchange reaction with an oxidized form of a developing agent to release Fl).