JPH071386B2 - Silver halide color-photographic material - Google Patents

Description

The present invention relates to a silver halide color photographic material, and more particularly to a silver halide color light-sensitive material excellent in color saturation.

(Prior Art) Silver halide color photographic materials are generally blue, green and red.
It has a silver halide emulsion layer sensitive to each of the primary colors, and each develops yellow, magenta, and cyan to form a color image using a so-called subtractive color method. This color is usually produced by an aromatic primary amine type color developing agent,
It is carried out by reacting with a coupler in an exposed silver halide color photographic light-sensitive material to form a dye. In the material for directly observing the formed image, the performance required for each coupler is that it has good spectral absorption characteristics for color development, good color development efficiency, and does not cause problems such as precipitation in the production of photosensitive materials. Furthermore, the obtained image is less likely to be discolored or discolored due to light, heat, humidity, or the like. Of particular importance is the spectral absorption characteristic of color development, which is not always the theoretically best due to constraints such as other characteristics on the compound used. Particularly, the coloring hue of the magenta coupler is important in the color reproduction theory, and various improvements have been made.

For example, in order to improve the coloring hue of magenta couplers, in the 5-pyrazolone system, anilino type magenta couplers (JP-A-49-74027 and JP-A-49-111631) which are superior in spectral absorption characteristics to ureido type and acylamino type are disclosed. Etc.) were developed. Further, a pyrazoloazole type magenta coupler (US Pat. No. 3,725,067 type, etc.) with less unnecessary side absorption has been developed. Compared with the color image obtained from the 5-pyrazolone type magenta coupler, this type of coupler has less unnecessary absorption in the blue light region and the red light region, and is advantageous in color reproduction. .

(Problems to be Solved by the Invention) However, this pyrazoloazole type magenta coupler is applied to resin coated paper in which the front and back of the paper are laminated with polyethylene containing titanium white, which is used as a general photographic reflective support. With the silver halide color photographic light-sensitive material formed by coating the silver halide color photographic emulsion used, the expected improvement in color saturation was not necessarily observed, and improvement in color reproduction was not yet satisfactory. I can't say that.

Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material having an improved color saturation by using a pyrazoloazole type magenta coupler.

(Means for Solving Problems) As a result of intensive studies conducted by the present inventors to develop a silver halide color photographic light-sensitive material satisfying such demands, as a result, a pyrazoloazole type coupler and a silver halide were selected. The light-sensitive material including the light-sensitive material was treated with a developing solution containing an aromatic primary amine as a main agent, and it was found that the saturation of the color-forming dye generated depends on the reflective support of the light-sensitive material. That is, it has been found that, when a light beam is incident perpendicularly to the plane of the reflective support, it depends on the directional distribution of the light reflected or scattered on the surface of the support. More specifically, when a light beam is incident perpendicularly on the plane of the reflection support, the angle (variation angle) formed by the optical axes of the reflected light and the incident light is 5 degrees, and the distance L from the light incident point of the support is L. The reflected light intensity I _{5 at} the position of is 45 degrees, and the chromaticness of the coloring pigment depends on the ratio of the reflected light intensity at the position of the distance L from the light incident point of the support, I _45. I found it.

The present invention has been accomplished based on this finding.

That is, the present invention provides that a hydrophilic colloid containing at least one pyrazoloazole-based coupler represented by the following general formula (I) and at least one compound represented by the general formula (II) satisfies the following condition (I). A silver halide color photographic light-sensitive material characterized by being present on a filling opaque support.

General formula (Ic) General formula (Id) (In the formula, R ¹¹ and R ¹² represent a hydrogen atom or a substituent,
X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Further, R ¹¹ , R ¹² or X may form a dimer or higher multimer.

General formula (II) In the formula, R ₅₁ and R ₅₂ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

However, the total carbon number of R ₅₁ and R ₅₂ is 4 or more and 11 or less.

Condition (I) When a light beam is incident on the plane of the opaque support in a direction perpendicular to the plane, reflected light at a position having a distance L from the light incident point of the support in the direction of a 5 ° angle of deviation with respect to the incident optical axis. Strength, I ₅ and Deflection 45
The ratio of the reflected light intensity, I ₄₅ , at a position that is the distance L from the light incident point of the support in the direction of degree is 0.02 ≦ I ₄₅ / I ₅ ≦ 0.35.

In formulas (Ic) and (Id), R ¹¹ and R ¹² may be the same or different from each other, and each is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, an alkoxy group, or aryl. Oxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, silyloxy group, sulfonyloxy group, acylamino group, anilino group, ureido group, imide group, sulfamoylamino group, carbamoylamino group, alkylthio group, arylthio group, Heterocyclic thio group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group, carbamoyl group, acyl group, sulfamoyl group,
It represents a sulfonyl group, a sulfinyl group, an alkoxycarbonyl group or an aryloxycarbonyl group, and particularly preferred are an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an acylamino group and an anilino group. X represents a hydrogen atom, a halogen atom, a carboxy group, or a group which is coupled to carbon at the coupling position via an oxygen atom, a nitrogen atom or a sulfur atom and which is capable of coupling off. R
¹¹ , R ¹² or X may be a divalent group to form a bis form.

Further, it may be in the form of a polymer coupler in which the coupler residue represented by the general formulas (Ic) and (Ie) is present in the main chain or side chain of the polymer, and particularly derived from a vinyl monomer having a moiety represented by the general formula. Polymers are preferred, where R ¹¹ , R ¹² or X represents a vinyl group or a linking group.

The linking group represented by R ¹¹ , R ¹² or X in the case where the vinyl monomer contains those represented by the general formulas (Ic) and (Id) is an alkylene group (a substituted or unsubstituted alkylene group, for example, a methylene group, an ethylene group, 1,10-decylene _{group, -CH 2 CH 2 OCH 2 CH} 2 -, etc.), with phenylene group (a substituted or unsubstituted phenylene group, for example, 1,4-phenylene group, 1,3-phenylene group, -NHCO-, -CONH-, -O-, -OCO- and aralkylene groups (for example, Includes groups that are formed by combining those selected from.

The following are preferred linking groups.

_{-NHCO -, - CH 2 CH 2} -, -CONH-CH ₂ CH ₂ NHCO-, -CH ₂ CH ₂ O-CH ₂ CH ₂ -NHCO-, The vinyl group may have a substituent other than those represented by the general formulas (Ic) and (Id), and preferable substituents are a hydrogen atom, a chlorine atom, or a lower alkyl group having 1 to 4 carbon atoms (for example, Represents a methyl group or an ethyl group).

Monomers including those represented by general formulas (Ic) and (Id) may form copolymers with non-color forming ethylene-like monomers that do not couple with the oxidation products of aromatic primary amine developers.

As is well known in the art of polymer color couplers, the non-chromogenic, ethylenically unsaturated monomers for copolymerization with solid water-insoluble monomeric couplers are the physical and / or chemical properties of the copolymers formed such as Solubility, compatibility with photographic colloid composition binders such as gelatin, its flexibility,
It can be chosen such that the thermal stability etc. is positively affected.

The polymer coupler used in the present invention may be either water-soluble or water-insoluble, and among them, polymer coupler latex is particularly preferable.

Among the pyrazoloazole-based magenta couplers represented by the general formulas (Ic) and (Id), more preferable ones are represented by the following general formulas (If) and (Ig).

In formulas (If) and (Ig), R ₃₁ represents an alkyl group, and R ₃₂ represents an alkyl group, an alkoxy group, or an alkylthio group.

Of R ₁₁ and R ₁₂ , particularly preferred are alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylamino groups, and anilio groups.

More preferred pyrazoloazole-based magenta couplers are those represented by the general formulas (If) and (Ig) in which R ₁₁ has 3 to 16 carbon atoms.
Is an alkyl group, an alkoxy group having 1 to 16 carbon atoms, or an alkylthio group.

Specific examples of typical magenta couplers and vinyl monomers thereof according to the present invention are shown below, but the present invention is not limited thereto.

Examples of compounds of the couplers represented by the general formulas up to (Ic) and (Id), synthetic methods, and the like are described in the following documents.

The compound of general formula (Ic) is described in JP-A-60-33552, and the compound of general formula (Id) is described in US Pat. No. 3,061,432.

In addition, JP-A-58-42045, JP-A-59-177,553,
59-174,836, JP-A-59-177,554, JP-A-59-177,557
Nos. 59-177556, 59-177,555 and the like have high color-developing ballast groups applicable to any of the compounds of the above general formulas (Ic) and (Id).

The magenta couplers represented by formulas (Ic) and (Id) are preferably used in the green-sensitive layer.

A plurality of magenta couplers represented by the general formulas (Ic) and (Id) may be used in combination, or may be used in combination with other magenta couplers. Formula (Ic) and the amount of the coupler represented by (Id) is 1.0 g / m ² or less 0.01 g / m ² or more is desirable, further 0.7 g / m ² or less 0.05 g / m ² or more.

The amount of the silver halide emulsion used in the coupler-containing layer represented by the general formulas (Ic) and (Id) depends on the coupler.
The molar ratio is 10 to 0.1, more preferably 6 to 0.5.
Is.

The weight ratio of the couplers represented by the general formulas (Ic) and (Id) to the high boiling point oil is preferably 8 or less, more preferably 2 or less and 0.2 or more.

The high-boiling solvent used for the couplers represented by the general formulas (Ic) and (Id) is preferably a phosphate type or a phthalic acid ester type having a dielectric constant of 6.0 or less.

Furthermore, it is desirable to use the compound represented by the general formula (II) as an antifoggant in an amount of 10 mol% or less of the coupler. That is, it is desirable to dissolve and disperse in a high boiling point solvent together with the coupler before use.

General formula (II) In the formula, R ₅₁ and R ₅₂ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.

However, the total carbon number of R ₅₁ and R ₅₂ is 4 or more and 11 or less.

Examples of desirable compounds contained in the general formula (II) are shown below.

Next, an opaque support satisfying the condition (I) will be described.

When light is incident on the plane of the opaque support, the incident light is reflected not only in specular reflection but in all directions due to the effect of fine irregularities on the scattering surface existing near the surface of the support. Considering the case where light is incident on the plane of the support from the vertical direction, the intensity of light reflected in the vertical direction is usually the highest, but due to the influence of fine irregularities on the scattering surface existing near the surface of the support, It is also reflected in directions other than the vertical direction, that is, in the oblique direction.

Therefore, as a measure of the reflected light intensity in the vertical direction, I ₅ ,
That is, the reflected light intensity is obtained at a position that is a distance L from the light incident point of the support in the direction of an angle of deviation of 5 degrees with respect to the incident optical axis, and as a measure of the reflected light intensity in an oblique direction,
I ₄₅ , that is, the reflected light intensity at a position that is the distance L from the light incident point of the support in the direction of the angle of deviation of 45 ° with respect to the incident optical axis is obtained.

Further, the ratio I ₄₅ / I ₅ of I ₄₅ and I ₅ is calculated and used as a standard for the ratio of the reflected light intensity in the oblique direction to the reflected light intensity in the vertical direction. This value does not depend on L. The larger this value, the more the proportion of reflected light in the oblique direction increases, and the opaque support becomes isotropically scattered. The smaller this value, the smaller the proportion of reflected light in the oblique direction becomes. Is specular.

The chroma of the coloring dye is remarkably improved when the value of I ₄₅ / I ₅ is 0.35 or less. The smaller the value of I ₄₅ / I _5, the higher the saturation of the coloring pigment.
The value of I ₄₅ / I ₅ is preferably 0.35 or less. However I
_{When the 45} / I ₅ value is too small, the image tends to be dark when the light-sensitive material is observed from an oblique direction, so the I ₄₅ / I ₅ value is
It is more preferably 0.02 or more and 0.35 or less.

The value of I ₄₅ / I ₅ can be easily measured using a goniophotometer (for example, JSG-21 type machine manufactured by Jonan Seisakusho Co., Ltd.).

Examples of the opaque support suitably used in the present invention include:
Polyester, polyethylene terephthalate, triacetylacetate base containing white pigments (such as titanium oxide, aene oxide, barium sulfate, etc.) dispersed therein, or a white pigment applied to one or both sides of the film to make it substantially opaque plastic. There is a support.

The white pigment used by being dispersed is used in an amount of 1% by weight or more and 50% by weight or less, preferably 5% by weight or more and 30% by weight or less, based on the polymer.

Further, it is also possible to use a rigid support such as glass or earthenware which is made substantially opaque by the above-mentioned method.

Furthermore, a resin-coated paper in which the front and back of the paper are laminated with polyethylene is coated with a metal thin film such as aluminum, or one or both sides of polyester, polyethylene terephthalate, or triacetylacetate base is coated with a metal thin film such as aluminum. It is also possible to use a substantially opaque material.

The light-sensitive material produced by using these supports can be used not only for ordinary photographic prints but also for exhibition by irradiating light from the back surface.

The thickness of the support is not particularly limited, but is preferably 10 microns or more and 10 millimeters or less, and more preferably 50 microns or more and 1500 microns or less. The transmittance of the support is 80% when the transmitted light is measured using an integrating sphere including the diffuse light.
The following is preferable, and 0.001% to 60% is particularly preferable.

Any silver halide of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used in the photographic emulsion layer of the photographic light-sensitive material used in the present invention. A preferred silver halide is silver iodobromide, silver iodochloride or silver iodochlorobromide containing about 30 mol% or less of silver iodide. The ratio of silver chloride is preferably 0 mol% to 100 mol%.

The silver halide grains in the photographic emulsion may be so-called Regular grains having regular crystal bodies such as cubes, octahedra and tetradecahedrons, and those having irregular crystal shapes such as spheres, It may have a crystal defect such as a twin plane or a composite form thereof. Also, a mixture of particles having various crystal forms may be used.

The grain size of silver halide may be fine grains of about 0.1 micron or less or large size grains having a projected area diameter of up to about 10 microns, and it may be a monodisperse emulsion having a narrow distribution or a polydisperse emulsion having a wide distribution. Good.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, Research Disclosure,
Volume 176, No. 17643 (December 1978), pp. 22-23, "I. Emulsion Preparation and Types" and ibid.
Vol. 187, No. 18716 (November, 1979), p.648 can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Graphide, published by Paul Montel (P.Glafkides, Chim.
ie et Physique Photographique Paul Montel, 1967),
Duffin, "Photoemulsion Chemistry", published by Forcal Press, Inc. (GFDuffin, Photographic Emulsion Chemistry (Foca
Press, 1966), "Manufacturing and coating of photographic emulsions" by Zelikman et al., published by Forcal Press (VLZelikman et al, Mak
ing and Coating Photographic Emulsion, Focal Press,
1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and a method of reacting a soluble silver salt and a soluble halogen salt may be a one-sided mixing method, a simultaneous mixing method or a combination thereof. Good. A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. As one form of the simultaneous mixing method, a method of keeping pAg in a liquid phase where silver halide is formed constant, that is, a so-called controlled double jet method can be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Further, known silver halide solvents (for example, ammonia, rodan potassium or U.S. Pat. No. 3,271,157, JP-A-51-1236).
0, JP-A-53-82408, JP-A-53-144319, JP-A-54
Physical aging can be carried out in the presence of thioethers and thione compounds described in JP-A No. -100717 or JP-A No. 54-155828. By this method also, a silver halide emulsion having a regular crystal form and a nearly uniform grain size distribution can be obtained.

The silver halide emulsion composed of the above-mentioned regular grains can be obtained by controlling pAg and pH during grain formation. For details, see, for example, Photographic Science and Engineering.
eering) Vol. 6, pp. 159-165 (1962); Journal of Photo.
graphic Science, 12: 242-251 (1964), U.S. Pat. No. 3,655,394 and British Patent 1,413,748.

A typical monodisperse emulsion that can be used in the present invention is an emulsion having an average grain diameter of silver halide grains larger than about 0.05 micron, at least 95% by weight of which is within ± 40% of the average grain diameter. Is. Further, an emulsion having an average grain diameter of 0.15 to 2 μm and having at least 95% by weight or at least 95% (number of grains) of silver halide grains within the average grain diameter ± 20% can be used. A method of making such emulsions is described in U.S. Pat.
No. 3,655,394 and US Pat. No. 1,413,748. Further, JP-A-48-8600, JP-A-51-39027,
51-83097, 53-137133, 54-48521, 54-99
Monodisperse emulsions such as those described in Nos. 419, 58-37635 and 58-49938 can also be preferably used.

Further, tabular grains having an aspect ratio of 5 or more can be used in the present invention. Tabular grains are described by Gatov, Gutoff, Photographic Science and Engineering,
Volume 14, Pages 248-257 (1970); U.S. Pat. No. 4,434,226.
No. 4,414,310, No. 4,433,048, No. 4,439,520, and British Patent No. 2,112,157, and the like. When tabular grains are used,
It has advantages such as increased covering power and increased color sensitization efficiency due to the sensitizing dye, and the above-cited U.S. Pat.
It is described in detail in No. 4,226.

In the grain forming process, grains having a crystal shape controlled by using a sensitizing dye or a certain kind of additive can be used.

The crystal structure may be uniform, may have different halogen compositions inside and outside, or may have a layered structure. These emulsion grains are described in British Patent No. 1,027,146,
U.S. Pat.Nos. 3,505,068, 4,444,877 and Japanese Patent Application No. 58
-248469 etc. are disclosed. Further, silver halides having different compositions may be joined by epitaxial joining, or may be joined with compounds other than silver halides such as silver rhodanide and lead oxide. These emulsion grains are described in U.S. Patent Nos. 4,094,684, 4,142,900 and
4,459,353, British Patent 2,038,792, U.S. Patent 4,34
9,622, 4,395,478, 4,433,501, 4,463,087
No. 3,656,962, No. 3,852,067, JP-A-59-162540
No., etc.

Further, the surface of the crystal is chemically aged to form photosensitized nuclei (Ag ₂ S, Agn, Au
It is also possible to use one having a so-called inner latent type grain structure in which silver halide is further grown around after the formation of ().

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt may coexist.

These various emulsions may be either a surface latent image type which forms a latent image mainly on the surface or an internal latent image type which is formed inside the grain.

Further, a direct reversal emulsion may be used. The direct reversal emulsion may be any of a solarization type, an internal latent type, an optical fogging type, a type using a nucleating agent, or a combination thereof.

In order to remove the soluble silver salt from the emulsion before and after physical ripening, the Nudel washing, the flocculation precipitation method or the ultrafiltration method is used.

The emulsion used in the present invention is usually one which has been physically ripened, chemically ripened and spectrally sensitized. The additives used in such a process are the aforementioned Research Disclosure No. 17643 (December 1978) and No. 18716 (1979).
(November), and the relevant parts are summarized in the table below.

Known photographic additives that can be used in the present invention are also described in the above-mentioned two Research Disclosures, and the locations described in the table below are shown.

Various color couplers can be used in the present invention, and specific examples thereof include Research Disclosure mentioned above.
No.17643, VII-C to G. As the dye-forming coupler, a coupler that gives the three primary colors of the subtractive color method (that is, yellow magenta and cyan) by color development is important, and the diffusion-resistant hydrophobic
As specific examples of 4-equivalent or 2-equivalent couplers, in addition to the couplers described in the patents mentioned in Research Disclosure No. 17643, VII-C and D, the following can be preferably used in the present invention.

A typical example of the yellow coupler that can be used in the present invention is a hydrophobic acylacetamide coupler having a ballast group. A specific example is U.S. Pat.
No. 7,210, No. 2,875,057 and No. 3,265,506. In the present invention, it is preferable to use a two-equivalent yellow coupler, and US Pat.Nos. 3,408,194 and 3,4
No. 47,928, No. 3,933,501 and No. 4,022,620 oxygen atom desorption type yellow couplers described in JP-B-58-10739, U.S. Pat.Nos. 4,401,752 and 4,3.
26,024, RD18053 (April 1979), British Patent No. 1,425,0
No. 20, West German Application Publication No. 2,219,917, No. 2,261,361,
Typical examples thereof include nitrogen atom-releasing yellow couplers described in JP-A Nos. 2,329,587 and 2,433,812. In particular, α-pivaloylacetanilide type couplers are desirable because they are excellent in fastness of color forming dyes, particularly in light fastness and color hue.

Examples of magenta couplers that can be used in the present invention include hydrophobic, indazolone-based or cyanoacetyl-based, preferably 5-pyrazolone-based couplers having a ballast group. The 5-pyrazolone-based 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 color forming dye,
Typical examples thereof are U.S. Patent Nos. 2,311,082 and 2,343,703.
No. 2, No. 2,600,788, No. 2,908,573, No. 3,062,65
3, No. 3,152,896 and No. 3,936,015. As the leaving group of the 2-equivalent 5-pyrazolone-based coupler, the nitrogen atom leaving group described in US Pat. No. 4,310,619 or the arylthio group described in US Pat. No. 4,351,897 is particularly preferable. Also European Patent 73,636
The 5-pyrazolone-based couplers having a ballast group described in JP-A No. 1994-A1 provide high color density.

Cyan couplers that can be used in the present invention include hydrophobic and diffusion-resistant naphthol-based and phenol-based couplers, and the naphthol-based couplers described in U.S. Pat.No. 2,474,293, preferably U.S. Pat.Nos. 4,052,212 and 4 , 1
Representative examples thereof include oxygen atom elimination type two-equivalent naphthol couplers described in Nos. 46,396, 4,228,233 and 4,296,200. Further, specific examples of the phenol-based coupler are described in U.S. Patent Nos. 2,369,929 and 2,801,171.
No. 2,772,162, No. 2,895,826 and the like.

Cyan couplers that are fast against humidity and temperature are preferably used in the present invention, and typical examples thereof include a phenol system having an alkyl group of ethyl group or higher at the meta position of the phenol nucleus described in US Pat. No. 3,772,002. Cyan coupler, U.S. Pat.Nos. 2,772,162, 3,758,308,
No. 4,126,396, No. 4,334,011, No. 4,327,173
, German Patent Publication No. 3,329,729 and European Patent No. 121,3
2,5-diacylamino-substituted phenol-based couplers described in U.S. Patent No. 65, and U.S. Pat.Nos. 3,446,622 and 4,3.
33,999, 4,451,559 and 4,427,767 and the like, and has a phenylureido group at the 2-position and 5
Examples thereof include a phenol-based coupler having an acylamino group at the -position.

The dye-forming coupler may form a dimer or higher polymer. Typical examples of polymerized dye-forming couplers are:
It is described in US Pat. Nos. 3,451,820 and 4,080,211. Specific examples of polymerized magenta couplers are described in British Patent No. 2,102,173 and U.S. Patent No. 4,367,282.

The coupler used in the present invention can be introduced into the light-sensitive material by various known dispersion methods, and examples thereof include a solid dispersion method, an alkali dispersion method, preferably a latex dispersion method, and more preferably an oil-in-water dispersion method. be able to. In the oil-in-water dispersion method, a high-boiling point organic solvent having a boiling point of 175 ° C. or higher and a low-boiling point so-called auxiliary solvent are dissolved in a single liquid or a mixed liquid of both, and then water or gelatin is added in the presence of a surfactant. Finely dispersed in an aqueous medium such as an aqueous solution. Examples of high boiling organic solvents are described in U.S. Pat.No. 2,322,027
No. etc. The dispersion may be accompanied by phase inversion, and if necessary, the auxiliary solvent may be removed or reduced by distillation, washing with noodles or ultrafiltration, and then used for coating.

The process of the latex dispersion method, effects, and specific examples of the latex for impregnation are described in US Pat. No. 4,199,363 and West German Patent Application (OLS) 2,541,230.

The light-sensitive material produced by using the present invention is, as a color antifoggant or color mixing inhibitor, a hydroquinone derivative, an aminophenol derivative, an amine, a gallic acid derivative, a catechol derivative, an ascorbic acid derivative, a colorless coupler, a sulfonamidephenol. You may contain a derivative etc.

Various anti-fading agents can be used in the light-sensitive material of the present invention. Hydroquinones as organic anti-fading agents,
6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols,
Hindered phenols centered on bisphenols, gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines and ether or ester derivatives obtained by silylating and alkylating the phenolic hydroxyl groups of these compounds As a representative example. Further, a metal complex represented by (bissalicylaldoximato) nickel complex and (bis-N, N-dialkyldithiocarbamato) nickel complex can also be used.

The invention is applicable to multilayer multicolor photographic materials having at least two different spectral sensitivities on the support. A multilayer natural color photographic material usually has at least one red-sensitive emulsion layer, one green-sensitive emulsion layer and one blue-sensitive emulsion layer on a support.

The light-sensitive material according to the present invention, in addition to the silver halide emulsion layer,
Protective layer, intermediate layer, filter layer, anti-halation layer,
It is preferable to appropriately provide an auxiliary layer such as a back layer.

For coating the photographic emulsion layer and other hydrophilic colloid layers, for example, a day coating method, a roller coating method, a curtain coating method,
Various known coating methods such as extrusion coating method can be used. US Patent Nos. 2681294, 2nd as required
Multiple layers may be simultaneously coated by the coating method described in 761791, No. 3526528, No. 3508947, or the like.

The color photographic light-sensitive material according to the present invention includes the aforementioned Research Disclosure, No. 17643, pages 28-29 and the same,
Development can be carried out by a usual method described in the left column to the right column of page 651 of No. 18716. The color photographic light-sensitive material of the present invention is usually subjected to washing treatment or stabilizing treatment after development, bleach-fixing or fixing treatment.

That is, color negative processing (composed of color development, bleaching, fixing, stabilizing bath, etc.) and color reversal processing (composed of black and white development, reversal, color developing, bleaching, fixing, stabilizing bath, etc.) it can. In particular, in color reversal processing, it is desirable to use a developing agent composed of a hydroquinone derivative and a phenidone derivative in the black and white developing bath, and further to use a silver halide solvent such as rhodan salt or sulfite salt. In the reversing step, a fogging agent such as tin salt may be used, or it may be reversed by irradiation with light. As the bleaching bath / fixing bath, a one- bath bleach-fixing bath may be used, and a stabilizing bath may not be used. Further, it is preferable to provide a washing bath (including a rinsing bath in which the amount of water is reduced compared to a normal washing bath) between each treatment step.

In the water washing step, it is general to carry out countercurrent water washing of two or more tanks to save water. A typical example of the stabilizing treatment is a multistage countercurrent stabilizing treatment as described in JP-A-57-8543 instead of the water washing step. In the case of this step, a countercurrent bath of 2 to 9 tanks is required. Various compounds are added to the stabilizing bath for the purpose of stabilizing the image. For example, various buffer agents for adjusting the membrane pH (for example, pH 3 to 8) can be cited as typical examples. In addition, if necessary, a water softener (aminopolycarboxylic acid, organic phosphoric acid, aminopolyphosphonic acid, phosphonocarboxylic acid, etc.), bactericide (benzisothiazolinones, isothiazolones, 4-thiazolinebenzimidazoles, Various additives such as halogenated phenols), surfactants, fluorescent brighteners and hardeners may be used, and two or more kinds of the same or different target compounds may be used in combination.

Further, it is preferable to add various ammonium salts as a membrane pH adjuster after the treatment.

Examples The present invention is described below with reference to examples, but the present invention is not limited to these.

Example 1 Paper support laminated on both sides with polyethylene (hereinafter referred to as S-
1)) to prepare a color photographic light-sensitive material in which the following first to twelfth layers were multilayer-coated. On the side coated with the first layer of polyethylene, titanium white and a white pigment are contained. The I ₄₅ / I ₅ value of this support was 0.45.

(Photosensitive layer composition) The components and the coating amounts shown in g / m ² are shown below. However,
When two or more materials are used in combination, the solvent means an equal weight ratio, and the other means an equimolar ratio. For silver halide, the coating amount in terms of silver is shown.

1st layer (gelatin layer) Gelatin ...... 1.30 2nd layer (antihalation layer) Black colloidal silver ...... 0.10 Gelatin ...... 0.70 3rd layer (low sensitivity red sensitive layer) Red sensitizing dye (* 1 and * 2) ) Spectrally sensitized silver iodobromide (silver iodide 5.0 mol%, average grain size 0.4μ) …… 0.15 gelatin …… 1.00 cyan coupler (* 3) …… 0.14 cyan coupler (* 4) …… 0.07 Anti-fading agent (* 5, * 6 and * 7) ...... 0.10 Coupler solvent (* 8 and * 9) ...... 0.06 4th layer (high sensitivity red sensitive layer) Red sensitizing dye (* 1 and * 2) Spectral sensitized silver iodobromide (silver iodide 6.0 mol%, average grain size 0.7μ) …… 0.15 Gelatin …… 1.00 Cyan coupler (* 3) …… 0.20 Cyan coupler (* 4) …… 0.10 Fading prevention Agent (* 5, * 6 and * 7) …… 0.15 Coupler solvent (* 8 and * 9) …… 0.10 Fifth layer (intermediate layer) Magenta Coro De-silver: 0.02 Gelatin: 1.00 Color mixing inhibitor (* 10): 0.08 Color mixing agent solvent (* 11 and * 12): 0.16 Polymer latex (* 13): 0.10 6th layer (low sensitivity green) Sensitive layer) Silver iodobromide (2.5 mol% silver iodide, grain size 0.4μ) spectrally sensitized with a green sensitizing dye (* 14) ...... 0.10 Gelatin ...... 0.80 Magenta coupler (M-5) ...... 0.10 Anti-fading agent (* 16) ...... 0.10 Anti-staining agent (* 17) ...... 0.01 Anti-staining agent (II-3) ...... 0.001 Coupler solvent (* 11 and * 19) ...... 0.15 7th layer (high sensitivity Green Sensitive Layer) Silver iodobromide spectrally sensitized with a green sensitizing dye (* 14) (3.5 mol% silver iodide, grain size 0.9μ) …… 0.10 gelatin …… 0.80 magenta coupler (M-5) …… … 0.10 Anti-fading agent (* 16) …… 0.10 Anti-staining agent (* 17) …… 0.01 Anti-staining agent (II-3) …… 0.001 Coupler solvent (* 11 and * 19) …… 0.15 8th layer (yellow filter layer) Yellow colloidal silver …… 0.20 Gelatin …… 1.00 Color mixing inhibitor (* 10) …… 0.06 Color mixing inhibitor solvent (* 11 and * 12) …… 0.15 Polymer latex (*) 13) ...... 0.10 9th layer (low-sensitivity blue-sensitive layer) Silver iodobromide spectrally sensitized with a blue sensitizing dye (* 20) (2.5 mol% silver iodide, grain size 0.5μ) ...... 0.15 Gelatin ...... 0.50 Yellow coupler (* 21) ...... 0.20 Anti-staining agent (* 18) ...... 0.001 Coupler solvent (* 9) ...... 0.05 10th layer (high sensitivity blue sensitive layer) With blue sensitizing dye (* 20) Spectral sensitized silver iodobromide (silver iodide 2.5 mol%, grain size 1.2μ) ...... 0.25 Gelatin ...... 1.00 Yellow coupler (* 21) ...... 0.40 Anti-staining agent (* 18) ...... 0.002 Coupler solvent (* 9) ...... 0.10 11th layer (UV absorbing layer) Gelatin ...... 1.50 UV absorber (* 22, * 6 and *) ) 1.00 Color mixture inhibitor (* 23) ...... 0.06 Color mixture solvent (* 9) ...... 0.15 Irradiation prevention dye (* 24) ...... 0.02 Irradiation prevention dye (* 25) ...... 0.02 12th layer (protection) Layer) Fine grained silver chlorobromide (97 mol% silver chloride, average size 0.2μ)
...... 0.07 Gelatin ...... 1.50 Gelatin hardening agent (* 26) ...... 0.17 * 1 5,5'-dichloro-3,3'-di (3-sulfobutyl) -9-ethylthiacarbocyanine Na salt * 2 Triethylammonium -3- [2- {2- [3
-(3-Sulfopropyl) naphtho (1,2-d) thiazoline-2-indenemethyl] -1-butenyl} -3-naphtho (1,2-d) thiazolino] propanesulfonate * 3 2- [α- ( 2,4-di-t-amylphenoxy)
Hexanamide] -4,6-dichloro-5-ethylphenol * 4 2- [2-chlorobenzoylamide] -4-chloro-5- [α- (2-chloro-4-t-amylphenoxy) octanamide] phenol * 5 2- (2-hydroxy-3-sec-5-t-butylphenyl) benzotriazole * 6 2- (2-hydroxy-5-t-butylphenyl) benzotriazole * 7 2- (2-hydroxy-3,5 -Di-t-butylphenyl) -6-chlorobenztriazole * 8 Di (2-ethylhexyl) phthalate * 9 Trinonyl phosphate * 10 2,5-Di-t-octylhydroquinone * 11 Tricresyl phosphate * 12 Dibutyl Phthalates * 13 Polyethyl acrylate * 14 5,5'-Diphenyl-9-ethyl-3,3'-disulfopropyloxacarbaoxy Anine Na salt * 15 7-chloro-6-methyl-2- [1- {2-octyloxy-5- (2-octyloxy-5-t-octylbenzene-sulfonamide} 2-propyl] -1H-
Pyrazolo [1,5-b] [1,2,4] triazole * 16 3,3,3 ', 3'-tetramethyl-5,6,5', 6'-tetrapropoxy-1,1'-bis Spiroindane * 17 3- (2-Ethylhexyloxycarbonyloxy) -1- (3-hexadecyloxyphenyl) -2-
Pyrazoline * 18 2-Methyl-5-t-octylhydroquinone * 19 Trioctyl phosphate * 20 Triethylammonium-3- [2- (3-benzylrhodanine-5-ylidene) -3-benzoxazolinyl] propanesulfonate * 21 α-pivaloyl-α-[(2,4-dioxo-1-
Benzyl-5-ethoxyhydantoin-3-yl) -2
-Chloro-5- (α-2,4-di-t-amylphenoxy) butanamide] acetanilide * 22 5-chloro-2- (2-hydroxy-3-t-butyl-5-t-octyl) phenylbenztriazole * 23 2,5-di-sec-octyl hydroquinone * 26 1,2-Bis (vinylsulfonylacetamido) ethane Sample 101 was prepared as described above. The magenta couplers of the 6th and 7th layers of Sample 101 were replaced with M-26, 32, 3
The samples replaced with Nos. 4 and 41 were designated as Samples 102 to 105.

Next, the support of Samples 101 to 105 was replaced with a support (described as S-2, I ₄₅ / I ₅ value is 0.15) obtained by heat-treating a polyester base containing titanium oxide and a foaming agent, and Sample 111 was replaced. It was set to ~ 115.

Each of these samples was exposed to red, green, and blue individually (red + green)
Combined exposure of light, (red + blue) light, and (green + blue) light, and development processing by the following processing steps, red,
Green, blue, yellow, magenta, cyan (hereafter R, G,
B, Y, M, and C are abbreviated).

[Treatment process]

First development (black and white development) 38 ℃ 1'15 "water wash 38 ℃ 1'30" reverse exposure 100Lux or more 1 "or more color development 38 ℃ 2'15" water wash 38 ℃ 45 "bleach-fix 38 ℃ 2'00" water wash 38 ℃ 2'15 ″ [Processing solution composition] First developer Nitrilo-N, N, N-trimethylenephosphonic acid pentasodium salt 0.6g Diethylenetriaminepentaacetic acid pentasodium 0.4g Potassium sulfite 30.0g Potassium thiocyanate 1.2g Potassium carbonate 35.0g Hydroquinone monosulfonate / potassium salt 25.0g Diethylene glycol 15.0ml 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 2.0g Potassium bromide 0.5g Potassium iodide 5.0mg Add water 1 (pH9.70 ) Color developer Benzyl alcohol 15.0 ml Diethylene glycol 12.0 ml 3,6-Dithia-1,8-octanediol 0.2 g Nitrilo-N, N, N-trimethylene phosphone Acid / pentasodium salt 0.5g Diethylenetriaminepentaacetic acid / pentasodium salt 2.0g Sodium sulfite 2.0g Potassium carbonate 25.0g Hydroxylamine sulfate 3.0g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4- Aminoaniline sulphate 5.0g Potassium bromide 0.5g Potassium iodide 1.0mg Add water 1 (pH 10.40) Bleach-fix solution 2-mercapto-1,3,4-triazole 1.0g Ethylenediaminetetraacetic acid / disodium / 2 Hydrate 5.0g Ethylenediaminetetraacetic acid / Fe (III) / ammonium-hydrate 80.0g Sodium sulfite 15.0g Sodium thiosulfate (700g / l solution) 160.0ml Glacial acetic acid 5.0ml Water 1 (pH6.50) Obtained in this way The B, G, R, Y, M, and C samples were each color-measured with a Hitachi M-307 type color analyzer, and the CIE1964 uniform color space was plotted. It was to evaluate the goodness of the line there is no color saturation.

The color saturation can be expressed by the size of the reproduction area in the CIE1964 uniform color space, but at this time, in order to comprehensively evaluate the changes in all colors, it is necessary to consider the importance of each color. . This method is described in detail in Journal of Photographic Engineering Science, Vol. 14, p. 87 (1966), and each color is weighted accordingly and the A value shown below is defined. The larger the A value, the wider the overall color reproduction range.

A = 32C _R ^* + 28C _G ^* + 24C _B ^* + 16C _Y ^* + 10C _M ^* + 12C _C ^* (I = R, G, B, C, M, Y) The values of A thus obtained are shown in Table 1.

From Table 1, it can be seen that the sample using S-2 of the present invention has significantly improved color saturation as compared with the sample using S-1 of the prior art. Further, the sample after the development treatment was stored for a long period of time, but no magenta stain was generated in the white background portion.

Example 2 A color photosensitive material was prepared by coating the following photosensitive layers consisting of the first to seventh layers on the support (S-1).

(Structure of Photosensitive Layer) The numbers corresponding to the respective components represent the coating amount expressed in units of g / m ² , and the silver halide coating amount represents the coating amount in terms of silver.
However, in the case of two or more materials used in combination, the solvent means an equal weight ratio, and the other means an equimolar ratio.

1st layer (blue sensitive layer) Silver chlorobromide emulsion (80 mol% silver bromide) ...... Silver 0.40 Yellow coupler (* 21) ...... 0.60 Same as above Solvent (* 9) ...... 1.00 Gelatin ...... 1.20 Second layer (Intermediate layer) Gelatin ...... 1.50 Third layer (green sensitive layer) Silver chlorobromide emulsifier (70 mol% of brominating agent) ...... Silver 0.35 Magenta coupler (M-5) ...... 0.35 Same as solvent (* 11 and * 19) …… 0.44 Anti-fading agent (* 16) …… 0.10 Anti-staining agent (II-3) …… 0.0035 Gelatin …… 1.00 4th layer (UV absorbing intermediate layer) UV absorber (* 22 / * 6) / * 7) …… 0.15 Same solvent (* 9) …… 0.06 Fifth layer (red sensitive layer) Silver chlorobromide emulsion (50 mol% silver bromide) …… Silver 0.3 Cyan coupler (* 3 and * 4) …… 0.5 Coupler solvent (* 9) …… 0.24 Gelatin …… 0.6 6th layer (UV absorbing intermediate layer) UV absorber (＊ 22 / * 6 / * 7) …… 0.20 Same as above solvent (* 9) …… 0.08 Gelatin: 0.15 7th layer (protective layer) Gelatin: 1.5 This sample was designated as sample 201. Sample 202 is a sample in which the magenta coupler of the third layer of sample 201 is replaced with M-26 and 32.
It was set to ~ 203.

Next, samples 211 to 213 were prepared by replacing the supports of samples 201 to 203 with S-2.

Each of these samples was exposed to red, green, and blue individually (red + green)
Light, (red + blue) light, (green + blue) light combined exposure is performed, development processing is performed by the following processing steps, C,
Samples were produced so as to develop colors of M, Y, B, G and R.

Processing process Temperature Time Developer 33 ° C 3.5 minutes Bleach-fixer 33 ° C 1.5 minutes Washing with water 28-35 ° C 3.0 minutes Developer nitrilotriacetic acid ・ 3Na 2.0g Benzyl alcohol 15ml Diethylene glycol 10ml Na ₂ SO ₃ 2.0g MBr 0.5g Hydroxylamine sulfate 3.0g 4-Amino-3-methyl-N-ethyl-N- [β- (methanesulfonamide) ethyl] -p-phenylenediamine / sulfate 5.0g Na ₂ CO ₂ (monohydrate) 30g Water was added Bleach-fixing solution ammonium thiosulfate (70wt%) 150ml Na ₂ SO ₃ 15g NH ₄ [Fe (EDTA)] 55g EDTA2 ・ 2Na 4g Add water to make 1 liter (pH6.9) The value of A obtained by treating the sample thus obtained in the same manner as in Example 1 is shown in Table 2.

From Table 2, it can be seen that the sample using S-2 of the present invention has a significantly improved color saturation as compared with the sample using S-1 of the prior art. Further, the sample after the development treatment was stored for a long period of time, but no magenta stain was generated in the white background portion.

Comparative Example In the sample 111 of Example 1, S- which is the support of the invention is used.
2 (Titanium oxide-containing polyester base, surface-foamed and adjusted to a suitable surface roughness. I ₄₅ / I ₅
= 0.15) to S-3 (polyester base containing titanium oxide, without special surface treatment. I ₄₅ / I ₅ = 0.01
The sample changed to 5) is used as Sample 131. In addition, sample 111
In Sample 132, the support was changed from S-2 to S-4 (resin-coated paper in which the front and back sides of paper were laminated with polyethylene and coated with an aluminum thin film. I ₄₅ / I ₅ = 0.001). These were processed in the same manner as in Example 1 and their images were evaluated.

When an illuminating light source was placed in front of the image and the image was viewed from the front, the samples 131 and 132 showed remarkable improvement in color saturation equal to or higher than 111. However, when the viewpoint is shifted and observed obliquely, a dark image appears due to insufficient light amount, which is not preferable.

Therefore, the sample 111 using S-2 with I ₄₅ / I ₅ = 0.15 is most preferable from the viewpoint that the saturation of the image is high and the dependence of the observation angle is small.

Example 3 A sample was prepared by using II-5 and T-1 (to be described later) for comparison, respectively, instead of II-3 which was the compound of the present invention in the sixth and seventh layers in the sample 112 of Example 1. They are 141 and 142. Further, a sample obtained by removing II-3 from the sixth and seventh layers of the sample 112 is referred to as a sample 143.

The entire surface of each of these samples was exposed, and the same treatment as in Example 1 was performed to measure the magenta density M ₀ . 2 this sample at room temperature
After aging for a week in the dark, the magenta density M ₁ was measured again, and the increase amount ΔM = M ₁ −M ₀ of the magenta density over time was obtained. This is shown in Table 3.

It can be seen that the sample using the compound of the present invention has a smaller increase in magenta concentration over time after the treatment and is preferable as compared with the comparative sample.

Continuation of front page (56) Reference JP 61-158333 (JP, A) JP 62-275261 (JP, A) JP 62-169159 (JP, A) JP 62-169160 (JP , A) JP 62-172358 (JP, A) JP 62-172359 (JP, A) JP 61-269153 (JP, A) JP 61-158324 (JP, A)

Claims (1)

[Claims] 1. A pyrazoloazole-based coupler represented by the following general formula (I) and at least one general formula (II).
A silver halide color photographic light-sensitive material characterized in that a hydrophilic colloid containing at least one compound represented by the formula (1) is present on an opaque support satisfying the following condition (I). General formula (Ic) General formula (Id) (In the formula, R ¹¹ and R ¹² represent a hydrogen atom or a substituent,
X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developing agent. Further, R ¹¹ , R ¹² or X may form a dimer or higher multimer. General formula (II) In the formula, R ₅₁ and R ₅₂ represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. However, the total carbon number of R ₅₁ and R ₅₂ is 4 or more and 1 or less. Condition (I) When a light beam is made incident on the plane of the opaque support in a direction perpendicular to the plane, the reflected light intensity at a position at a distance L from the light incident point of the support in the direction of a 5 ° angle of deviation with respect to the incident optical axis. , I ₅ and the reflected light density at a position L which is the distance L from the light incident point of the support in the direction of the angle of deviation of 45 degrees, I ₄₅ is 0.02 ≦ I ₄₅ / I ₅ ≦ 0.35.