JPS6324252A - Color photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain the titled material having improved brightness and reproducibility of gradation in a dark part by mounting a silver halide emulsion layer on the surface of a photographic substrate body which is mounted with solid powders having the surface of the 2nd kind diffused reflection on a base material. CONSTITUTION:The silver halide emulsion layer is mounted on the surface of the photographic substrate body which is mounted the filling layer composed of the solid powders having the surface of the 2nd kind diffused reflection on the base material. The surface of the 2nd kind diffused reflection has >=5, preferably 0.7-1.0 reflectance. Said surface has >=5%, preferably >=10%, further preferably >=20% spectral reflectance (measured by the 550nm monochromatic light). The solid powder is preferably composed of a metal powders. To make the surface of the filling layer of the solid powders to the 2nd kind diffused reflection, the mean particle size of the solid powders is preferably about 0.01-1,000mu. If the solid particle is composed of aluminum, the mean particle size of the solid particle is preferably 5-70mu.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a color photographic material that provides excellent color images. For more details, see the brightness and saturation of color images,
This invention relates to a color photographic material for printing that has dramatically improved gradation reproduction and sharpness in dark areas and can be rapidly developed.

[Conventional technology]

Conventionally, color photographic materials have been prepared by forming an antihalation layer, a red photosensitive layer, a green photosensitive layer, and a yellow photosensitive layer on a support such as a film, a film or paper containing a white pigment, e.g. baryta paper, or paper with a water-resistant resin layer on both sides. A filter layer, a blue photosensitive layer, a protective layer, etc. are appropriately provided.

In order to obtain excellent color images, improvements in the transparency of each layer, thinning, layer structure, prevention of irradiation and halation, and improvement in the spectral absorption characteristics of color pigments obtained from the materials used, such as color couplers, are required. Improvements have been made to improve its transparency. In particular, in order to improve sharpness, the selection of silver halide emulsions, such as halogen composition, grain size, etc., and layer structure, which facilitate the multilayer effect of development, have been devised. Additionally, techniques have been used to use materials that release compounds that have the effect of inhibiting or accelerating development during color development.

However, it is still insufficient, especially for photography where color images are formed on reflective supports such as color photographic paper.

A silver halide emulsion is contained in microcapsules,
It is known that bright images can be produced by using a photographic material coated on an aluminum support that reflects light well and has a metallic luster (for example, Japanese Patent Publication No. 49-3378
(description in No. 3). However, when a conventional emulsion is superimposed on this aluminum support, it is not sufficient to produce a slightly brighter image. It is also known that not only is the reflection of light unsightly, but even slight scratches on the surface are noticeable and undesirable. Lithographic printing plates having a silver halide emulsion layer provided on an aluminum support are known (for example, British Patent No. 1227603 and Japanese Patent Application Laid-Open No. 1983-9005).
No. 3, etc.). The Aβ support used in lithographic printing plates has been subjected to surface treatments such as graining, and this has no effect at all, and methods have been proposed to improve this defect by preventing halation (for example, Japanese Patent Application Laid-Open No. 12492T, 1983). ). Nor is it a material that forms color images. It is also known to provide a vapor-deposited metal layer of aluminum or chromium to prevent static (for example, British Patent No. 130403,
Special Publication No. 59-41573 and Special Publication No. 59-10420, etc.). However, it is not related to the present invention, and there is no description that suggests any improvement in color images.

[Problem that the invention seeks to solve]

A first object of the present invention is to provide a color photographic material in which color images are improved, particularly in terms of saturation and gradation reproduction of dark areas, to an extent that cannot be achieved by conventional techniques. The second purpose is
The object of the present invention is to provide a color photographic material that is dramatically improved in sharpness of color images, particularly in the high frequency region. A third object is to provide a color photographic material which has the above-mentioned properties, is compatible with conventional color photographic processing methods, and can be processed particularly quickly. Other purposes will be clear from other entries in the Hu Bishu.

[Means for solving problems]

The above aspects of the present invention are such that at least one silver halide emulsion layer is provided on the surface of a photographic support comprising a substrate provided with a packed layer of solid powder having a type 2 diffuse reflective surface. This was achieved using color photographic materials.

The color photographic material of the present invention will be explained below.

(Photographic support) In general, the reflection characteristics of the surface of an object can be broadly classified 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 of the smooth surface of the material. The reflectance of the smooth surface of the material that gives the first type diffuse reflectance is the second type.
Generally lower than the reflectance of a smooth surface of a material that provides diffuse reflectance. In the present invention, type 2 diffuse reflectance refers to a case where the reflectance R is 0.5 or more. Therefore, the second
The seed diffusely reflective surface has a surface area of 0.5 or more, more preferably 0.5 or more.
It has a reflectance of 7 to 1.0. The reflectance R of a smooth surface made of the same material when irradiated with light in the vertical direction can be determined using a goniole left meter. Incidentally, type 1 diffuse reflectance refers to the reflectivity that, when a light-transmitting solid is made into a fine powder, becomes diffused light due to the total reflection of light that is mostly transmitted through the solid and its multiple reflections. .

Specular reflection and diffuse reflection can be distinguished based on the difference in spectral reflectance. Here, the spectral reflectance is measured using monochromatic light of 550 nm incident at an incident angle of 7 degrees from the normal direction of the test sample, and the angle of view is 10 degrees centered on the direction of regular reflection of the incident light.
A trap is set up at 90° to remove the specularly reflected component, and the other components that are diffusely reflected within a viewing angle range of 90° from the normal are integrated using an integrating sphere and calculated as a percentage of the incident light. The second type diffuse reflectance in the present invention has the above spectral reflectance (measured with monochromatic light of 550 nm) of 5% or more. Therefore, the type 2 diffuse reflective surface of the present invention refers to one that exhibits a spectral reflectance (measured with monochromatic light of 550 nm) of 5% or more, preferably 10%, and more preferably 20% or more. The spectral reflectance can be determined using, for example, Hitachi Color Analyzer Model 307. In the present invention, 550n+ is used as a representative of the green region with high visual sensitivity.
n monochromatic light was used. In addition, in order to accurately measure the spectral reflectance of the second type diffuse reflective material, the measurement is performed without adding dye or pigment to the resin.

As a result, from the reflectance R of the material used to form the surface with respect to light irradiation in the vertical direction, and the value of the spectral reflectance when a trap of a goniole left meter such as a Hitachi color analyzer is provided, the method of the present invention is calculated. Two types of diffuse reflection can be distinguished: specular reflection and first type diffuse reflection.

A packed layer of solid powder providing a type 2 diffusely reflective surface is
Composed of solid powder and resin.

The solid powder is preferably a metal powder. As a metal,
F. Hare, 7 Benford et al. J.
Opt, Soc.

Atner, Vol. 32, pp. 174-184 (1942), such as silver, aluminum, gold,
Copper, chromium nickel, platinum, alloys thereof such as aluminum/magnesium alloy, aluminum/L-aluminum/antimony, sinchu, etc. are used. In addition to metal powders, inorganic powders can also be suitably used. Examples of the inorganic substance powder include pieces of natural mica and pieces of fish scales.

In the present invention, in order to make the surface of the packed layer of solid powder have type 2 diffuse reflection, the solid powder preferably has an average particle size of about 0.01 to 1000 microns. In particular, in the case of aluminum, 1 to 100 μ, preferably 5 to 7
Preferably, it is 0μ. In addition, in the case of silver, 0.1
It is preferable that it is 100μ. 0 for gold. O
It is preferable that it is 1-100 micrometers.

In addition, resins include water-soluble polymers (e.g., gelatin, etc.), aqueous latexes (e.g., styrene-butadiene,
acrylonitrile butadiene type, acrylic type, styrene acrylic type, vinylidene chloride type, acetic acid vinyl chloride type, ethylene-vinyl acetate type, etc.), organic solvent type resin (e.g. acrylic type, polyester type, cellulose type, polystyrene type, (vinyl chloride type, polyvinyl acetate type, etc.).

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

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, 11
Compounds described in Vol., No. 19 (1972) and the like can be suitably used as the photopolymerizable monomer or oligomer.

The irregularities on the outer surface of the solid powder in the packed bed of solid powder can be determined by embedding and fixing the sample in resin, cutting an ultrathin section, and observing the cross section using an electron microscope. It can be directly measured with submicron accuracy using a cross-sectional shape measuring device that uses electron beam irradiation. The number of cylinders with unevenness can be measured as the frequency of surface roughness, and preferably the average frequency is 0.1 to 2.
000 pieces/mtn, more preferably 1 to 1000 pieces/mm
It is.

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. Preferably paper or RC-paper,
It is also possible to use the polyethylene layer of RC-paper in combination with low-density polyethylene and laminate aluminum foil with roughness in advance (as a substrate).

The support according to the present invention can be provided with a silver halide emulsion layer via an undercoat layer.The undercoat layer is made of a thermoplastic resin such as polyethylene or polypropylene, or an ionomer resin containing an epoxy adhesive. can get. On top of this, a gelatin or gelatin silver halide emulsion layer can be provided with or without corona discharge treatment.This undercoat layer improves the adhesion of the silver halide emulsion layer and prevents harmful effects from the support on the silver halide emulsion layer. This prevents adverse photographic effects such as spot formation, fogging, and deterioration of storage stability. Although the undercoat layer is coated uniformly, it is preferable that it be thin. For example, the film thickness is preferably 5 μm or less, and preferably 2 μm or less.

In some cases, the present invention may include a first type of diffusely reflecting fine particles in an upper layer such as an undercoat layer in a small amount, for example, 1 g/m 2 or less, and a slight dispersion of latex or a high boiling point organic solvent in the upper layer to diffusely reflect the first heel. Particles can also be included.

Further, by mixing fine powder of titanium oxide or barium sulfate in the substrate and providing minute holes in the metal thin film layer according to the present invention on the surface thereof, the first type of diffuse reflection is mixed with the second type of diffuse reflection. It is also possible to mix them.

As a result, sharpness is less likely to deteriorate and the viewing angle of observation can be expanded.

(Silver Halide Emulsion Layer) In the present invention, at least one silver halide emulsion layer is provided on the type 2 diffuse reflective surface of the support.

The silver halide emulsion layer will be explained below.

(a) Silver halide emulsion layer RL: mainly 580 to 70
A layer containing silver halide grains and cyan coupler with spectral sensitivity in the 0 mμ wavelength region. The cyan couplers used in RL include oil-protected naphthol-based and phenol-based couplers, and are disclosed in U.S. Patent No. 2.474,
293, preferably U.S. Pat. Nos. 4,052,212 and 4,146.39.
No. 6, No. 4.228,233 and No. 4,296
．． A representative example is the oxygen atom dissociating type two-equivalent naphthol coupler described in No. 200. Specific examples of phenolic couplers include U.S. Patent No. 2.369.9.
No. 29, No. 2.801.171, No. 2,772.
No. 162, No. 2.895.826, etc.

Humidity and temperature robust cyan couplers are preferably used in the present invention and are typically described in U.S. Pat. No. 3,772. Phenolic cyan coupler having an alkyl group higher than ethyl group at the meta-position of the phenol nucleus described in '002, U.S. Patent Nos. 2,772,162, 3.758.308, and 4.126 ,396
No. 4,334.011, No. 4,327,17
3, 2,5-diacylcimino-substituted phenolic couplers described in West German Patent Publication No. 3.329.729 and European Patent No. 121.365, and U.S. Pat. '333.999,
4,451,559 and 4.427,76
Examples include phenolic couplers having a phenylureido group at the 2-position and an acylamino group at the 5-position, as described in No. 7.

Particularly preferred are couplers represented by the following general formula <1) or (II).

General formula (I) 1H General formula (n) H (b) Silver halide emulsion layer GL: Mainly 500 to 58
Eyebrow containing silver halide grains and magenta coupler with spectral sensitivity in the 0 mμ wavelength region.

The magenta couplers used in GL are oil-protected indacylon or cyanoacetyl couplers.
Preferred are pyrazoloazole couplers such as 5-pyrazolone and pyrazolotriazoles.

The 5-pyrazolone coupler is preferably a coupler in which the 3-position is substituted with an arylamino group or an acylamino group from the viewpoint of the hue and color density of the coloring dye. , No. 2.343.
No. 703, No. 2,600,788, No. 2,908
, No. 573, No. 3,062,653, No. 3,15
No. 2,896 and No. 3.936.015, etc.

Particularly preferred as the leaving group for the two-equivalent 5-pyrazolone coupler are the nitrogen atom leaving group described in U.S. Pat. No. 4,310,619 or the arylthio group described in U.S. Pat. No. 4,351,897. Also European Patent No. 73
, No. 636, the 5-pyrazolone coupler having a ballast group can provide high color density.

As a pyrazoloazole coupler, U.S. Patent No. 3,
Pyrazolobenzimidazoles described in US Pat. No. 061,432, preferably pyrazolo[5,1-cl [:1,2°4] triazoles described in U.S. Pat.
0 (June 1984) and JP-A No. 60-33552, and pyrazolo pyrazoles described in Research Disclosure 24230 (June 1984) and JP-A No. 60-43659. It will be done.

The imidazo[
, 1,2-b) Pyrazole order is preferred, as described in U.S. Pat.
．． Pyrazolo [1,5-b:] described in No. 540.654
[:l, 2.41) Riazole is particularly preferred.

Particularly preferred are couplers represented by general formula (III) or (IV).

General formula (II[) General formula (I'V) (c) Silver halide emulsion layer BL: Mainly 400 to 50
A typical example of the yellow coupler used in the layer BL containing silver decogenide grains having spectral sensitivity in the 0 mμ wavelength region and a yellow coupler is an oil-protected type acylacetamide coupler. Specific examples thereof include U.S. Patent Nos. 2.407.210 and 2.8.
No. 75.057 and No. 3.265,506, etc. The use of two-equivalent yellow couplers is preferred for the present invention, such as those disclosed in U.S. Pat. Oxygen atom separation type yellow coupler described in
739, U.S. Patent No. 4.401.752, U.S. Pat.
326,024, RD18053 (April 1979), British Patent No. 1.425,020, West German Application No. 2.219.917, West German Application No. 2,261,361, British Patent No. 2,329.587 A representative example thereof is a nitrogen atom separation type yellow coupler described in Japanese Patent No. 2,433,812. α-pivaloylacetanilide couplers provide color dyes with excellent fastness, particularly light fastness, while α-benzoylacetanilide couplers provide high color density.

Particularly preferred are couplers represented by general formula (V).

General formula (V) CH.

(In the formula, R1, R4 and R5 are each an aliphatic group,
represents an aromatic group, a heterocyclic group, an aromatic amino group or a heterocyclic amino group, R2 represents an aliphatic group, R3 and R6
each represents a hydrogen atom, a halogen atom, an aliphatic group, an aliphatic oxy group, or an acylamino group, R7 and R3 represent a substituted or unsubstituted phenyl group, and R8 represents a hydrogen atom, an aliphatic or aromatic acyl group, group, aliphatic or aromatic sulfonyl group, RIO represents a hydrogen atom or a substituent, Q represents a substituted or unsubstituted N-phenylcarbamoyl group, Za and zb are methine, substituted methine, or = represents N-, Y+, Y2 and Y4 represent a halogen atom or a group capable of leaving during the coupling reaction between the oxidant and the developing agent (hereinafter referred to as a leaving group), and Y3 represents a hydrogen atom or a leaving group. where Y represents a leaving group, and in general formula (I) and general formula (II), R2 and R3
And R6 and R6 may each form a 5.6- or 7-membered ring.

Furthermore, R+, R2, R3 or Y+: R4, Rs%R6
or Y2; R7, Re SR9 or Y3: R
IO1ZaS'Zb or Ys; Q or Y may form a multimer of type 2 or more.

The aliphatic group mentioned here represents a linear, branched or cyclic alkyl, alkenyl or alkynyl.

) The dye-forming couplers and the above-mentioned special couplers may form dimers or higher polymers. A typical example of a polymerized dye-forming coupler is U.S. Pat. No. 3,451.82.
No. 0 and No. 4.080.211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102.173 and US Pat. No. 4,367.2.
It is described in No. 82.

These couplers are dispersed and contained in the emulsion layer in coexistence with at least one type of high boiling point organic solvent.

Preferably, a high boiling point organic solvent represented by the following general formula (A) or E) is used.

General formula (A) W2-0-P=0 General formula (B) n, -Coo -L General formula (C) General formula (D) General formula (E) WI OL (where W, SW, and W3 each represents a substituted or unsubstituted alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, W4 is Wl, ○
represents W1 or S-W, n is an integer from 1 to 5, and when n is 2 or more, W may be the same or different from each other; - In the general formula (E), Wl and W2 may form a condensed ring) In order to correct unnecessary absorption in the short wavelength region of dyes produced from magenta and cyan couplers, it is preferable to use a colored coupler in combination with a color negative sensitive material for photography. U.S. Patent No. 4.163.670 and Japanese Patent Publication No. 5
7-39413, etc. or U.S. Pat. No. 4,004,929, U.S. Pat.
, 138,258 and British Patent No. 1146.368
A typical example is the magenta-colored cyan coupler described in No.

Typical amounts of color couplers used range from 0.001 to 1 mole per mole of photosensitivity/% 10 silver genre, preferably from 0.01 to 0.5 mole for yellow couplers and from 0.01 to 0.5 mole for magenta couplers. 0,003 to 0
．． 3 moles, and 0.002 to 0 for cyan couplers.
．． It is 3 moles. The standard coating amount of color coupler on color paper is 4 to 14 x 10-' and 2 to 14 x 10-' for yellow, magenta, and cyan coupler, respectively.
8 x 10-' and 2 to 9 x 10-' mol
The area is 7m2.

In order to spectral sensitize the silver halide emulsion of the present invention in a predetermined wavelength range, the following dyes can be selected and used. Cyanine dye, merocyanine dye, complex cyanine dye, complex merocyanine dye, holopolar
Included are 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. These pigments include
Any of the nuclei commonly used for cyanine dyes can be used as the basic heterocyclic nucleus. 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, that is, an indolenine nucleus,
Benzindolenine nucleus, indole nucleus, benzoxazole nucleus, naphthoxazole nucleus, benzothiazole nucleus,
A naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, etc. are applicable. These nuclei may have substituents on the hydrocarbon.

Merocyanine dyes or composite merocyanine dyes include a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thioxazolidine-2,
5- to 6-membered heteroartic ring nuclei such as 4-dione nucleus, thiazolidine-2,4-';on nucleus, rhodanine nucleus, and thiobarbic acid nucleus 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. Along with the sensitizing dye, the emulsion may contain a dye that itself does not have a spectral sensitizing effect or a substance that does not substantially absorb visible light and exhibits supersensitization. For example, aminostilbenzene compounds which are nitrogen-containing heteroartic ring nuclei groups and are substituted (for example, U.S. Pat. No. 2.933.3'90, U.S. Pat. No. 3.635.
721), aromatic organic acid formaldehyde condensates (such as those described in US Pat. No. 3,743,510), cadmium salts, azaindene compounds, and the like. U.S. Patent No. 3,615,613, 3
, No. 615,641, No. 3,617,295, No. 3,
635.721 is particularly useful.

In particular, the following general formulas (VI), (■), (■), (IX),
It is preferable to use a sensitizing dye or a supersensitizer selected from the compounds represented by (X), (XI), and (XII).

General formula (VI) In the formula, 2. represents an oxygen atom, a sulfur atom or a selenium atom, and Zl. represents a sulfur atom or a selenium atom.

R11 and R, □ represent an optionally substituted alkyl group or alkenyl group having 6 or less carbon atoms, and RI
Either 1 or R1□ represents a sulfo-substituted alkyl group, and most preferably at least one represents 3
-Sulfopropyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfobutyl group or sulfoethyl group, examples of substituents include alkoxy groups having 4 or less carbon atoms,
Examples include a halogen atom, a hydroxy group, a carbamoyl group, an optionally substituted phenyl group having 8 or less carbon atoms, a carboxy group, a sulfo group, or an alkoxycarbonyl group having 5 or less carbon atoms. Specific examples of R1+ and R1□ include methyl group, ethyl group, propyl group, allyl group, pentyl group, hexyl group, methoxyethyl group, ethoxyethyl group: phenethyl group, 2-p-triethyl group, 2 -p-sulfophenethyl group, 2,2.2-
Trifluoro x-f group, 2,2.3.3-tetrafluoropropyl group, carbamoylethyl group, hydroxyethyl group, 2-(2-hydroxyethyl)ethyl group, carboxymethyl group, carboxyethyl group, ethoxycarbonyl group Methyl group, 2-sulfoethyl group, 2-” lower 3-
Examples include sulfoflovir L 3-sulfopropyl L 2-hydroxy-3-sulpoprobi/14.3-sulfobutyl group or 4-sulfobutyl group.

When Zll represents an oxygen atom, ■11 and ■13 represent a hydrogen atom, and ■1□ is a phenyl group or a carbon number of 3
The following alkyl groups, alkoxy groups, phenyl groups substituted with a chlorine atom (particularly preferably, 12 is a phenyl group), as well as 1, and 1 □ or C1 □ and V
This means that l 3 can be linked to form a condensed benzene ring. Most preferably, Vl1 and Vl3 represent a hydrogen atom, and ■1□ represents a phenyl group.

When Zll represents a sulfur atom or a selenium atom, V
l 1 represents an alkyl group having up to 4 carbon atoms, an alkoxy group, or a hydrogen atom; V and 2 represent an alkyl group having up to 5 carbon atoms, an alkoxy group having up to 4 carbon atoms, a chlorine atom, a hydrogen atom, and Vl3 represents a hydrogen atom, and Vl1 and Vl2
Alternatively, it represents that Vl2 and Vl3 can be linked to form a condensed benzene ring. More preferably ■1. and ■13 represents a hydrogen atom, and ■1□ represents an alkoxy group having 4 or less carbon atoms, a phenyl group, or a chlorine atom, ■1. represents an alkoxy group or an alkyl group having up to 4 carbon atoms, and ■1□ represents a hydroxy group, an alkyl group or a hydroxy group having up to 4 carbon atoms, or ■
This is the case where 1□ and Vl3 are connected to represent a condensed benzene ring.

When Z1□ represents a selenium atom, ■1. are Vll and V
IS represents the same meaning as ■1□, and Vlfl represents the same meaning as Vl3.

When 212 represents a sulfur atom and Zll represents a selenium atom, Vl4 represents a hydrogen atom or an alkoxy group having 4 or less carbon atoms, Vlll represents a hydrogen atom, and Vt
S is an alkoxy group having 4 or less carbon atoms, an optionally substituted phenyl group (preferably a phenyl group, including tolyl group, anisyl group, etc.), an alkyl group having 4 or less carbon atoms, a chlorine atom, or a hydroxy group. , Vle
represents a hydrogen atom, and Vl4 and VIS, or V
This indicates that I5 and Vl6 can be linked to form a condensed benzene ring.

More preferably, V and Vl[+ represent a hydrogen atom, V I 5 represents an alkoxy group having 4 or less carbon atoms, a chlorine atom or a phenyl group, or Vl 5 and Vlll are connected to form a condensed benzene ring. It is.

When Zll and 212 both represent sulfur atoms, V
l4 represents a hydrogen atom, Vl5 represents an optionally substituted phenyl group (for example, a phenyl group, a tolyl group, etc.); represents a hydrogen atom, VIS and v+g
This means that they can be linked together to form a fused benzene ring. When Zll represents an oxygen atom and 212 represents a sulfur atom, Vl4 and Vl6 represent hydrogen atoms, and Vl
5 represents a chlorine atom, an optionally substituted phenyl group, or an alkoxy group having 4 or less carbon atoms, and also represents that Vl5 and Vl6 can be linked to form a condensed benzene ring, and more preferably Vl4 and Vl When 6 represents a hydrogen atom and Vl5 represents a phenyl group, or Vl
This is the case where 5 and Vl6 are connected to represent a fused benzene ring.

X7. represents an acid anion residue.

ml represents 0 or 1, and is 1 when it is an inner salt.

General formula (■) In the formula, Z2+ represents an oxygen atom, a sulfur atom, a selenium atom, or >N R2g, and Z2° represents an oxygen atom or >N R2□.

R2+ and R2□ have the same meaning as R1 or Rl 2 in the general formula ■, and R2+ and R24 and R2□ and R2S
It means that a 5- or 6-membered carbon ring can also be formed by linking with.

R2, at least one of Z2+ or z2□ is /N
When R2g is represented, it represents a hydrogen atom, and in other cases it represents an ethyl group, a propyl group or a butyl group (more preferably an ethyl group). R24 and R2S represent hydrogen atoms.

R24 and R27 have the same meaning as R21 or R2□, but R21 and R2H do not simultaneously represent a substituent having a sulfo group, and R22 and R27 do not simultaneously represent a substituent having a sulfo group. represents something.

V21 represents a hydrogen atom when 22+ represents an oxygen atom; when Z21 represents a sulfur atom or a selenium atom, it represents a hydrogen atom, an alkyl group having 5 or less carbon atoms, or an alkoxy group thereof; and Z21 represents >N R2H. represents a hydrogen atom or a chlorine atom.

In V22, 221 represents an oxygen atom and Z2□ is >N-R2
゜ represents a hydrogen atom, an alkyl group having 5 or less carbon atoms, an alkoxy group, a chlorine atom, or an optionally substituted phenyl group (for example, tolyl group, anisyl group, phenyl group, etc.), and also represents V2+ or V13. More preferably, ■2□ represents an alkoxy group or a phenyl group, or V21 and ■2□ or ■2□ and V22 can be connected to form a condensed benzene ring. a ring), a W bond in which both 22+ and Z2□ represent an oxygen atom, an optionally substituted phenyl group (for example, a tolyl group, anisyl group, a phenyl group, etc., with a phenyl group being more preferred) or V21 or V23 to form a condensed benzene ring, and when 221 represents a sulfur atom or a selenium atom, a hydrogen atom, an alkyl group having 5 or less carbon atoms, an alkoxycarbonyl group having 4 or less carbon atoms, Represents an alkoxy group, an acylamine 7 group, a chlorine atom, or an optionally substituted phenyl group (more preferably 4 carbon atoms)
If Z21 represents a sulfur atom,
23 to form a condensed benzene ring.

When 22+ represents >NR2H, V22 represents a chlorine atom, a trifluoromethyl group, a cyano group, an alkylsulfonyl group having 4 or less carbon atoms, or an alkoxycarbonyl group having 5 or less carbon atoms (when Z2. , , more preferably V21 represents a chlorine atom and V22 represents a chlorine atom, trifluoromethyl group or cyan group).

V24 represents a hydrogen atom when Z2□ represents an oxygen atom, and represents a hydrogen atom or a chlorine atom when Z2□ represents >NR2□.

When Z2° represents an oxygen atom, V2S is an alkoxy group having 4 or less carbon atoms, a chlorine atom, a substituted phenyl group (e.g., anisyl group, phenyl group, etc.), or is linked to V24 or V21i. It means that a fused benzene ring can also be formed, and more preferably 2
When 2+ represents >N R26, it is a case where it is linked with an alkoxy group having 4 or less carbon atoms, a phenyl group, or V24 or V26 to form a condensed benzene ring, and 22+ represents an oxygen atom, a sulfur atom, or a selenium atom. More preferred V2S is a case in which V2S is linked to a phenyl group or V24 to V26 to form a condensed benzene ring. Z2□
When represents >N R27, V2S is a chlorine atom,
It represents a trifluoromethyl group, a cyano group, an alkylsulfonyl group having up to 4 carbon atoms, or a carboxyalkyl group having up to 5 carbon atoms, and particularly preferably, V24 represents a chlorine atom, and V25 represents a chlorine atom, a trifluoromethyl group, or a cyanogen atom. This is a case where it represents a group.

V26 represents a hydrogen atom.

X:1 represents an acid anion residue.

m21 represents 0 or 1, and is 0 in the case of an inner salt.

[General formula■]

In the formula, 231 is thiazoline, thiazonobenzothiazole, naphthothiazole, selenazoline, selenazole, penzoselenazonobairafthoselenazole, benzimidazole, naphthimidazole, oxazole, penzoxazonopenaphthoxazonobepyridine nucleating atom represents a group, and these heterocyclic nuclei may be substituted. When forming a benzimidazole nucleus or a naphthimidazole nucleus, examples of the substituent for nitrogen at the 1-position other than R31 include those listed as R2H or R27 in general formula (2). In addition, the substituents on the condensed benzene ring of benzimidazole include a chlorine atom, a cyan group, and a carbon number of 5.
The following alkoxycarbonyl groups, alkylsulfonyl groups having 4 or less carbon atoms, or trifluoromethyl groups may be mentioned, and the 5th position is particularly preferably substituted with a chlorine atom, and the 6th position is substituted with a cyano group, a chlorine atom, or a trifluoromethyl group. This is the case. As a substituent in the case of a heterocyclic nucleus other than benzimidazole selenazoline and thiazoline nucleus, an optionally substituted alkyl group having a total number of carbon atoms of 8 or less (examples of substituents include a hydroxy group, a chlorine atom, a fluorine atom, , alkoxy group, carboxy group, alkoxycarbonyl group, phenyl group, or substituted phenyl group), hydroxy group, alkoxycarbonyl group having 5 or less carbon atoms, halogen atom, carboxy group, furyl group, chenyl group, pyridyl group , phenyl group or substituted phenyl group (examples include tolyl group, phenyl group, chlorophenyl group, etc.).

Examples of the substituent in the case of the selenazoline or thiazoline nucleus include an alkyl group having 6 or less carbon atoms, a hydroxyalkyl group having 5 or less carbon atoms, or an alkoxycarbonylalkyl group having 5 or less carbon atoms.

R31 represents the same meaning as R8 or Rl2 in general formula (2).

R:12 has the same meaning as RI+ or R1□ in general formula I, and also represents a hydrogen atom, a furfuryl group, or an optionally substituted monocyclic aryl group (e.g., phenyl group, tolyl group, phenyl group, carboxy Phenyl group, hydroxyphenyl group, chlorophenyl group, sulfophenyl group,
Pyridyl group, 5-methyl-2-pyridyl group, 5-chloro-2-pyridyl2. zyl group, chenyl group, furyl group, etc.), and at least one of Rol and R3 is a substituent having a sulfo group or a carboxy group, and the other is a group containing no sulfo group. represents.

R33 represents a hydrogen atom, an alkyl group having 5 or less carbon atoms, a phenethyl group, a phenyl group, or a 2-carboxyphenyl group, more preferably a hydrogen atom, a methyl group, or an ethyl group.

Q31 is an oxygen atom, a sulfur atom, a selenium atom, or >
When N R34 is represented and Z and 1 represent a thiazoline, selenazoline or oxazole nucleating atom group, preferably Q3+ is a sulfur atom, selenium atom or >N
Rs<.

R34 is a hydrogen atom, a pyridyl group, a phenyl group, a substituted phenyl group (e.g. tolyl group, phenyl group, etc.), or may contain an oxygen atom, sulfur atom or nitrogen atom in the carbon chain, or a hydroxy group, a halogen atom, Represents an aliphatic hydrocarbon group with a total carbon number of 8 or less that may contain substituents such as an alkylaminocarbonyl group, an alkoxycarbonyl group, a phenyl group, and more preferably a hydrogen atom, a phenyl group, a pyridyl group, or a carbon chain. Represents an alkyl group that may contain an oxygen atom or a hydroxy group.

k represents 0 or 1, and n represents 0 or 1.

When n represents 1 and 231 represents a pyridyl-forming atomic group, Q31 represents an oxygen atom.

Next, specific examples of compounds represented by the general formula (2), (2) or (2) will be shown.

I-1 VI-3 VI-4 δL1. K δυko I-6 VI-7 l-8 SUsK　　　　　　5IJs- l-9 l-10 l-11 δU3K 5Us- l-12 VI-14 VI-15 Vl-16 error S03′″ ll-2 C2H.

ll-3 C2)+5 ([
:H2-3 bU3-■■-4 ll-5 :) U2K 5Ljs
-IE-6 n-7 C,l(5 ll-8 2Hs Vn-9 C,H5 bush vn-t.

VII-14 VII-15 ll-16 U3- ll-17 ll-18 C,H.

ll-19 To buko ll-20 V II-21 VI[-22 ll-23 m-i SU, to VI[I-3 VIII-4 V[[[-5 VIII-6 lll-9 VIII-10 VII[-11 2H5 VIII-12 SO, Na VI-14 VI [l-17 VIII-18 VII[-20 V II [-21 VIII-22 03K V III-23 VIII-24 ■ C5H,.

VII[-25 V[-26 VI-30 bukonim-32 ■ VI[[-33 C)+2sO3K VI[[-34 VIII-35 VI-36 General formula ■ In the formula, Zll is benzoxazole, naphthoxa Zonopebenzthiazonopenaphthothiazole, dihydronaphthothiazonopebenzoselenazono to naphthoselenazole, dihydronaphthoselenazole-forming atomic group. Z1□ represents an atomic group forming penzothiazonobenaphthothiazonobedihydronaphthothiazole, benzoselenazole, and naphthoselenazonobedihydronaphthoselenazole.

The nitrogen-containing heterocyclic nucleus represented by Zll and Z1□ may have one or more substituents. Examples of preferred substituents include lower alkyl groups (more preferably carbon atoms
the following alkyl groups), lower alkoxy groups (more preferably alkoxy groups with 6 or less carbon atoms), chlorine atoms, lower alkoxycarbonyl groups (more preferably alkoxycarbonyl groups with 5 or less carbon atoms), optionally substituted phenyl groups (e.g., phenyl L) a lyl group, anisyl group, chlorophenyl group, etc.) or a hydroxy group.

Specific examples of the nitrogen-containing heterocyclic nucleus represented by Zll and Z1□ include, for example, 5-hydroxybenzoxazole, 5-methoxyoxazole, 5-ethoxybenzo'oxazole, 5-phenylbenzoxazole, 5.
6-dimethylbenzoxazole, 5-methyl-6-methoxybenzothiazole, 6-nitoxy5-hydrobenzoxazole, naphtho(1,2-dEoxazole, naphtho(2,3-d)oxazole, naphtho[2゜1
-d]Oxazole, 5-methylbenzothiazole, 5
-Methoxybenzothiazole, 5-ethylbenzothiazole, 5-p-tolylbenzothiazole, 6-methylbenzothiazole, 6-ethylbenzothiazole, 6-butylbenzothiazole, 6-methoxybenzothiazole, 6-butoxybenzothiazole, 5 , 6-dimethylbenzothiazole, 5,6-simethoxybenzothiazole, 5-hydroxy-6-methylbenzothiazole, 5-
Ethoxycarbonylbenzothiazole, 5-chloropenzothiazole, 5-chloro-6-methylpenzothiazonopenaphthoC1,2-d]thiazole, naphthoC2,1
-d) Thiazole, 5-methylnaphthoC2,1-d] Thiazonope8,9-dihydronaphtho I: 1.2-d) Thiazole, 8-methoxynaphtho[1,2-d) Thiazonopebenzothiazole, Benzo Selenazole, 5-methylbenzoselenazole, 6-methylbenzoselenazole, 5-methoxybenzoselenazole, 6-methoxybenzoselenazole, 5,6-dimethylbenzoselenazole, 5-ethoxy-6-methylpenzo Serena Zonope 5-
Hydroxy-6-methylbenzoselenazole, naphtho [
1,2-d) selenazole, naphtho(2,1-d) selenacy/L/.

etc.

R11 and RI2 may be the same or different and represent an optionally substituted alkyl group or alkenyl group having 10 or less carbon atoms, and at least one group of RI+ or R1□ contains a sulfo group. indicates that

Examples of substituents for alkyl and alkenyl groups include the above-mentioned sulfo group, alkoxy groups having 6 or less carbon atoms, halogen atoms, hydroxy groups, and optionally substituted aryl groups having 8 or less carbon atoms (for example, phenyl groups, Furyl group, chenyl L) + JruM, p-buphenyl group, xylyl group, anisyl group, sulfophenyl group, hydroxyphenyl group, carboxyphenyl group, chlorophenyl group, etc.), substituted groups having 8 or less carbon atoms a phenoxy group (substituents include, for example, a fluorine atom, a chlorine atom, a sulfo group, a hydroxy group, a carboxy group,
alkoxycarbonyl group, alkyl group, alkoxy group, etc.), acyl group having 8 or less carbon atoms (e.g. phenylsulfonyl group, tosyl group, methylsulfonyl group,
Examples include hendiyl group, acetyl group, propionyl group, etc.), alkoxycarbonyl group having 6 or less carbon atoms, and carboxy group.

R+3 and RIB represent hydrogen atoms. Also in the corner.

and RIS may be linked to form a 5- or 6-membered ring.

R14 is a hydrogen atom, or when R13 and R1ft represent a hydrogen atom, an alkyl group having 4 or less carbon atoms, 1 carbon number
Represents a phenylalkyl group of 0 or less.

More preferably, R14 represents a hydrogen atom, and R13 and R
15 to form a 5- or 6-membered ring, or R13 and RIS represent a hydrogen atom and R14 represents a benzyl group.

RI6 represents that it can be combined with a hydrogen atom or R1 to form a 5- or 6-membered carbon ring.

In the nitrogen-containing heterocyclic nucleus-forming atom group represented by e and l, more preferable heterocyclic nuclei include naphthoxazoles and at least one electron-donating group with a negative Hammett's σ2 value. Benzothiazoles, dihydronaphthothiazoles, naphthothiazole m I 1 represents 0 or 1, and is 0 in the case of an inner salt.

General formula In the formula, 22+ represents a sulfur atom or a selenium atom.

R21 and R2□ have the same meaning as R1□ or R1□ in the general formula (2), and represent that at least one of them is a substituent containing a sulfo group or a carboxy group.

R23 represents a hydrogen atom or a lower alkyl group having 4 or less carbon atoms.

V21 represents a hydrogen atom, an alkyl group having 6 or less carbon atoms, an alkoxy group, a fluorine atom, a chlorine atom, or a hydroxy group.

■2□ and V2S represent hydrogen atoms.

V23 represents a hydrogen atom, a lower alkyl group (preferably an alkyl group having 6 or less carbon atoms), a lower alkoxy group (preferably an alkyl group having 6 or less carbon atoms), or a hydroxy group.

V24 is a hydrogen atom, a lower alkyl group (preferably an alkyl group having 6 or less carbon atoms), a lower alkoxy group (preferably an alkoxy group having 6 or less carbon atoms), a chlorine atom, a lower alkoxycarbonyl group, or an optionally substituted phenyl group. Group (
For example, it represents a phenyl group, tolyl group, anisyl group, etc.) or a hydroxy group.

Also, VH and V23, V2'J and V24, and V24 and V
B also represents that it can be linked to form a condensed benzene ring, and these condensed benzene rings may be substituted.

Examples of the substituent include a chlorine atom, a lower alkyl group (preferably having 4 or less carbon atoms), and a lower alkoxy group (preferably having 4 or less carbon atoms).

In the nitrogen-containing heterocyclic nucleus containing 221, the most preferable petero ring is naphthoC1,2-dEthiazole,
naphtho(2,1-d)thiazole, naphthoC1,2-d
) selenazole, naphtho[2°1-d]selenazole, or benzoselenazole containing at least one electron-donating group having a negative Hammett's σ value.

X9 represents an acid anion residue.

m2. represents 0 or 1, and is 0 in the case of an inner salt.

General Formula XI In the formula, Z3I has the same meaning as 21□ in General Formula I, and also represents naphthoxazole. The nitrogen-containing heterocyclic nucleus represented by Zffl may have one or more substituents, and examples of substituents include Z in general formula I or the substituent of the nitrogen-containing heterocyclic nucleus represented by Z12. Examples include the substituents listed above.

Z32 represents a sulfur atom, a selenium atom or >NR3s.

R36 may be a hydrogen atom, a pyridyl group, a phenyl group, a substituted phenyl group (e.g. tolyl group, anisyl group, hydroxyphenyl group, etc.), or may contain an oxygen atom, sulfur atom or nitrogen atom in the carbon chain. <, may have a substituent such as a hydroxy group, a halogen atom, an alkylaminocarbonyl group, an alkoxycarbonyl group, or a phenyl group. Represents an aliphatic hydrocarbon group having a total of 8 or less carbon atoms, more preferably a hydrogen atom, a phenyl group, a pyridyl group, or an alkyl group which may contain an oxygen atom in the carbon chain and may contain a hydroxy group. represents a group.

R31 represents the same meaning as R1+ or R12 in General 2).

R32 has the same meaning as R11 or RI2 in general formula group, chlorophenyl group, sulfophenyl group, pyridyl group, 5-methyl-2-pyridyl group, 5-chloro-2-
pyridyl group, furyl group, chenyl group, etc.).

R33 and R3S represent hydrogen atoms, and R33 and R3S represent hydrogen atoms.
This indicates that 5- and 6-membered rings can also be formed by linking with 3S.

Rff4 has the same meaning as R14 in general formula (2).

Furthermore, at least one of R31 and R32 is a group not containing a sulfo group, and the other is a group containing a sulfo group or a carboxy group.

X-1 12) 20CJS (CH2)
3SO, --I shi4H9 C2) 1゜I-1 shi112t, 11tJIkoH Xl-2 XI-3 shi2iS XI-5 XI-6 XI-7 H XI-8 shiH3 XI-9 Xl-11 XI -12 Xl-14 Xl-15 Xl-16 (C)12) 3S03K +(CL)
zOcL General formula X■ In the formula, Y41 and Y42 may be the same or different.
=CH- or =N-.

R41, R4□, R42 and R44 may be the same or different and each represents a hydrogen atom, a hydroxy group, a lower alkoxy group (preferably 10 or less carbon atoms), an aryloxy group (for example, a phenoxy group, a tolyloxy group, a sulfophenoxy group) , β-naphthoxy group, α-naphthoxy group, 2
．． 4-dimethylphenoxy group, etc.), halogen atom, (e.g. chlorine atom, bromine atom, etc.), heterocyclic nucleus (e.g. morpholinyl group, piperidine group, etc.), alkylthio group (e.g. methylthio group, ethylthio group), Heterocyclylthio group (e.g. benzothiazylthio group), arylthio group (e.g. phenylthio group, tolylthio group), amine group, alkylamino group or substituted alkylamino group (e.g. methylamino group, ethylamino group,
Propylamine group, dimethylamino group, diethylamine 7
group, dodecylamino group, cyclohexylamine 7 group, β-
hydroxyethylamino group, di-β-hydroxyethylamino group, β-sulfoethylamino group), arylamino group or substituted arylamino group (e.g. anilino group,
O-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, ○-anisylamino group, m-anisylamino group, p-anisylamino group, 0-methylanilino group, O-methylanilino group, pt-amylanili7 group, 〇- Carboxyanilino group, m-carboxyanilino group, p-carboxyanilino group, hydroxyanilino group, naphthylamino group, sulfonaphthylamino group), heterocyclylamino group (e.g. 2-benzothiazole amino group, 2-pyridylamino group) ), an aryl group (for example, a phenyl group), and a mercapto group.

A41 represents a group containing an arylene group, and the following criteria can be cited.

Here, M represents a hydrogen atom or a cation that supports water solubility.

Furthermore, in the compound represented by general 2), R41
% At least one of R42, R43, R44 and A41 is a group containing a sulfo group.

Furthermore, among the compounds represented by the general formula (2), the most preferred compound is a stilbene derivative.

RLSGL and BL used in the present invention are sequentially arranged on a support as follows: BLSGL, BL, RL, GL; RLSG
L, BL, etc. are provided, and the lower layer, middle layer, and upper layer of each layer are the protective layer PL, the middle layer ML, and the lower layer is the antihalation layer HL.
Further, a yellow filter layer YL can be used.

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 color photographic light-sensitive material used in the present invention, a fine powder of a so-called organic or inorganic white pigment giving the first type of diffuse reflection is added to the base layer of the support and at least one layer above it in a small amount, for example, 1 g/m2. Preferably less than 0.5 g/m
2 or less can be used. However, if used in large quantities, the characteristics of the immersed color image, especially the brightness, may be reduced.

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 caused by pH
It is preferable to use a method that controls 1ρAg or the like and implants only a predetermined amount of silver ions or halogen ions.

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. 8) Any one is fine. These silver halides can be sensitized using activated gelatin, chemical sensitizers such as allylthiocarbamide, cystine, and thiosulfate, reduction sensitizers such as polyamines and dichloromethane, noble metal sensitizers, and rhodium and iridium complex salts. Chemical sensitization may be performed using a sensitizer such as a sensitizer.

Furthermore, fog suppressants such as mercaptotriazoles, mercaptotetrazoles, and benzotriazoles can be used in combination in the silver halide emulsion layer.

For rapid development processing, a silver chlorobromide emulsion or a silver chloride emulsion is preferred, and a fog suppressor or stabilizer that strongly adsorbs to silver halide, such as a mercapto compound, a nitrobenzotriazole compound, or a benzo-IJ azole compound, is used. . Further, commonly used development accelerators, antihalation agents, antiirradiation agents, fluorescent whitening agents, and the like can also be used in combination.

The present invention can be used for all color photographic reflective materials, but especially for color photographic paper, color reversal photographic paper, direct positive color photographic paper, and color copies using the light fogging method. It can also be used for photosensitive materials.

(Color Development Processing) The color developer used in the development process of the light-sensitive material of the present invention is preferably an alkaline aqueous solution containing an aromatic primary amine color developing agent as a main component. Although amine phenol compounds are also useful as color developing agents, 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-methyl-4-amino-7-N-ethyl-N-β-methanesulfonamidoethylaniline, 3-methyl-4-amino-N-methyl-N
-β-methoxyethylaniline and their sulfates,
Examples include hydrochloride and p-toluenesulfonate. These diamines are generally more stable in their salt form than in their free state, and are therefore preferably used.

The color developer may contain pH aids such as alkali metal carbonates, borates or phosphates, development inhibitors or antifoggants such as bromides, iodides, benzimidazoles, benzothiazoles or mercapto compounds. Generally, it contains agents such as agents. Also, if necessary, preservatives such as hydroxylamine or sulfites, organic solvents such as triethanolamine, diethylene glycol,
Development accelerators such as benzyl alcohol, polyethylene glycol, quaternary ammonium salts, amines, dye-forming couplers, competitive couplers, nucleating agents such as IJum boron hydride, 1-phenyl-3-pyrazolidone, etc. Auxiliary developers, viscosity imparting agents, various chelating agents such as aminopolycarboxylic acids, aminopolyphosphonic acids, alkylphosphonic acids, and phosphonocarboxylic acids;
Antioxidants such as those described in West German Patent Application (○LS) 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 dihydroxybenzene such as hydroquinone, 1-phenyl-
3-pyrazolidones such as 3-pyrazolidone or N-
Known black and white developers such as aminophenols such as methyl-p-aminephenol 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. Examples of bleaching agents include iron (■),
Compounds of polyvalent metals such as cobalt (m), chromium (■), and copper (II), oxidized acids, quinones, nitrone compounds, and the like are used. Typical bleaching agents include ferricyanide; dichromate; organic complex salts of iron (I) or cobalt (■), such as ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propyl Complex salts of aminopolycarboxylic acids such as tool tetraacetic acid or 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(I) salt and persulfate are preferred from the viewpoint of rapid processing and environmental pollution. Additionally, the ethylenediaminetetraacetic acid iron (II [Hf salt) is particularly useful in both stand-alone bleach solutions and -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
No. 4-52534 and U.S. Patent No. 3.893.858
Thiol-based compounds such as those shown in JP-A-49
-59644, 50-140129, 53-2
No. 8426, No. 53-141623, No. 53-104
Heterocyclic compounds described in JP-A Nos. 232 and 54-35727, etc.: JP-A-52-20832 and JP-A-55-25
064 and 55-26506; tertiary amines described in JP-A-48-84440; thiocarbamoyl compounds described in JP-A-49-42349; It may be used or two or more types may be used in combination. Bromine ions, iodide ions, thiol-based or disulfide-based compounds are preferred bleach accelerators. These bleach accelerators are particularly 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 thiosulfuric acid sulfate is 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, amine polycarboxylic acid, and organic phosphoric acid, fungicides and anti-pyre agents that 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 West, Photographic Science and Engineering (L, E, West, Phot.

It is also possible to add compounds described in, for example, Sci', M. Sci', Vol. 6, pp. 344-359 (1965).

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

In the washing process, two or more tanks are generally used for countercurrent washing to save 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, ami/polyphosphonic acid, phospho/carboxylic acid, etc.), disinfectants (benzisothiazolinone, isothiazolone, 4-thiazoline benzimidazole, etc.) as necessary. , halogenated phenols, etc.), surfactants, fluorescent brighteners, hardeners, and the like 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 US Pat. No. 3,342,597, US Pat. No. 3,342,599, Research Disclosure No. 14850 and US Pat. No. 15159
In addition to Schiff base type compounds described in JP-A No. 13924, aldol compounds described in US Pat. No. 13924, metal salt complexes described in US 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, 58-50533, 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 the various processing baths as necessary.

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

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

(1 liquid) (2 liquid) Sulfuric acid (IN) 24 cc (3 liquid) The following silver halide solvent (1%) 3 cc H3 ■ (4 liquid) (5 liquid) (6 liquid) Add 600 cc ( 1 liquid) to 5
It was heated to 6°C, and (liquid 2) and (liquid 3) were added. Thereafter, (liquid 4) and (liquid 5) were added simultaneously over a period of 30 minutes. After another 10 minutes, (Liquid 6) and (Liquid 7) were added simultaneously 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: a/d) 0.08, silver bromide 70
A monodisperse cubic silver chlorobromide emulsion of mol % was obtained.

Sodium 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,
Similar preparations were made by changing the amount of NaCl and the addition times of liquids 4 and 5 as shown in Table 1.

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

Table 2 A support (1) according to the present invention and a comparative support (A) used in a conventional method were obtained as follows.

Support (r): Metallic aluminum powder was mixed in polyethylene and laminated on top of a white base paper for photography to obtain a white base paper. The amount of aluminum powder used is approximately 5g/m2
Met. After performing corona discharge treatment on this, gelatin and its hardening agent were added to 1=oxy-3,5-dichloro-5.
-) An undercoat layer was provided using sodium riazine.

Comparative support (A): On the surface of white base paper for photography, white fine powder of titanium oxide was mixed in advance with polyethylene to a concentration of about 4 g/m2 after lamination, and on the back side of white base paper, polyethylene was used, and both sides were laminated at the same time. I got the RC paper. On the white polyethylene surface, support (I
) A gelatin undercoat layer was obtained.

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

1st layer: A sensitizing dye (a) is added to the silver halide emulsion (5)
gX1 mole F) 7. Spectral sensitization was carried out by adding 10-' mol of OX. Furthermore, yellow coupler (d) and color image stabilizer (e) were mixed and dissolved in solvent (f), dispersed, and added in predetermined amounts. This was applied as the first layer.

Third layer: A sensitizing dye (b) is added to the silver halide emulsion (3).
gX per mole 4. Spectral sensitization was performed by adding 10-'% OX. Furthermore, magenta coupler (h) and color stabilizer (1) were mixed and dissolved in solvent (j), dispersed, and added in a predetermined amount. This was applied to form a 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 1.2 and comparative sample a after applying the 5th layer, 6th layer and 7th layer
I got it.

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.

(a) Blue-sensitive sensitizing dye (b) Green-sensitive sensitizing dye (C) Red-sensitive sensitizing dye (d) Yellow coupler (f) Solvent (g) Color mixing inhibitor (i) Color image stabilizer (D Solvent development Prescription A Bleach fix at 35℃ for 45 seconds Prescription A Rinse at 35℃ for 45 seconds
Prescription A 28-35℃ 1 minute 30 seconds Color developer A Water 80
0CC diethylenetriaminepentaacetic acid 1.0g
Sodium sulfite 0.2gN, N
-Diethylene 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-amine aniline sulfate 4.5g4.4
'-Diaminostilbene-based fluorescent whitening agent (Seiseikagaku@(Shitex4) 2
．． Add 0g water and make 1000c
cKOH pH 10.25 Bleach-fix formulation A Ammonium thiosulfate (54 wt%) 150 mβ Na2S [] 315 g NH4CFe (III) (EDTA))
55 gEDTA-2Na 4
g Glacial acetic acid 8.61g Add water and total amount is 1000mβ (pH 5.4) Rinse liquid prescription A EDTA・2Na・2H200.4g Add water and total amount is 1000m! (pH7
, 0) According to the naked eye observation of the photographic image, 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.

Next, the results are illustrated below as photographic physical properties.

Experimental Example 1 Using Sample 1 and Comparative Sample-a obtained in Example 1,
Three-color separation exposure was performed using a light beam of 12,854°K through a band-pass filter (spectral transmittance shown in FIG. 5).

Yellow, magenta, and cyan color images were obtained through the steps of color development, bleach-fixing, and rinsing in accordance with Example 1. The spectral absorption characteristics were measured using Hitachi Color Analyzer Model 307 and are shown in Figure 1 (BL, yellow color image), Figure 2 (GL, magenta color image), and Figure 3 (RL, cyan color image).
I got it. The solid line indicates the sample obtained from Sample 1 according to the present invention, and the broken line indicates the sample obtained from Comparative Sample-a. The maximum concentration point is 1
．． It is set to 0. It can be seen that the spectral absorption distribution of the color image according to the present invention is sharp and the chroma is improved.

Experimental example 2 RL and CL of the color photographic material according to the present invention.

The CTF of each layer of BL was measured. CTF is essentially the ratio of the concentration amplitude at frequency 0 and the concentration amplitude at each frequency.

Using sample 1 according to the present invention and comparative sample-a, R,
Example 1: A rectangular wave chart with different frequencies is closely exposed through a G583 color separation filter and subjected to prescribed development processing.
I followed the instructions. The resulting image was microtraced using a microdensitometer (aperture 2μ x 100μ width) to obtain Figure 4. The solid line indicates that of sample 1, and the sample -
The one according to a is shown by a broken line. It is shown that the image sharpness of Sample-1 according to the present invention is extremely high. In particular, the sharpness of silver halide emulsions close to the support is abnormally high. This can be said to be a surprising effect.

[Brief explanation of drawings]

Figures 1 to 3 show the spectral absorption curves, and Figure 4 shows the CTF
FIG. 5 shows the spectral transmittance curve of the bandpass filter. Figure 1: Wavelength (mp) Figure 2: Wavelength (mp-) Figure 3: Wavelength (mp-) Figure 4: Frequency (to)

Claims (12)

[Claims] (1) Color photographic photosensitive material comprising at least one silver halide emulsion layer provided on the surface of a photographic support comprising, on a substrate, a packed layer of solid powder having a type 2 diffuse reflective surface. material. (2) The color photographic material according to claim 1, wherein the solid powder filling layer is composed of solid powder and resin. (3) The color photographic material according to claim 1 or 2, wherein the solid powder is a metal powder. (4) The color photographic material according to claim 3, wherein the metal powder is a powder of aluminum, silver, gold, nickel, magnesium, or an alloy thereof. (5) The color photographic material according to claim 3 or 4, wherein the metal powder has an average particle diameter of 0.01 to 100 μm. (6) The color photographic material according to claim 3, wherein the resin is a water-resistant resin. (7) Claims 1 to 6 in which a thermoplastic resin layer or an adhesive layer is provided between the solid powder filling layer and the base layer.
The color photographic material described in any one of paragraphs. (8) The color photographic material according to any one of claims 1 to 7, wherein the substrate is paper. (9) The color photographic material according to claim 8, wherein a thermoplastic resin layer or a water-resistant resin layer is provided on the surface of the substrate opposite to the surface on which the filled layer of solid fine powder is provided. (10) A color photographic light-sensitive material according to claim 1, comprising two or more silver halide emulsion layers having different spectral sensitivities. (11) Emulsion layer (BL) containing halogen particles having spectral sensitivity in the wavelength region of 400 to 500 mμ and finely dispersed particles of yellow color coupler, 500 to 580 mμ
An emulsion layer (GL) containing silver halide grains having spectral sensitivity in the wavelength region of mμ and finely dispersed particles of magenta color coupler; and silver halide grains having spectral sensitivity in the wavelength region of 580 to 740 mμ. an emulsion layer (RL) containing finely dispersed particles of cyan color coupler;
) in any order. (12) The color photographic light-sensitive material according to any one of claims 1 to 11, wherein a resin layer is provided on the support between the support and the silver halide emulsion layer.