JPH11338108A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a silver halide photographic sensitive material for enjoyment having improved color reproducibility, maintaining the effect even after preservation and not deteriorating white surface properties by incorporating a colored coupler into one layer, specifying the whiteness of a reflective substrate and the content of a white pigment and incorporating specified compds. SOLUTION: The silver halide photographic sensitive material has a layer contg. a colored coupler on the reflective substrate and the whiteness b* value of the substrate in the L*a*b* indication system is >-6. The sensitive material has a layer having >=12 wt.% content of a white pigment and contains a compd. represented by formula I and cyan couplers represented by formulae II-V. In the formulae I-V, each of R0 -R5 and R12 is a substituent, each of R11 , R13 , R16 , and R17 is H or a substituent, each of R14 and R15 is an electron withdrawing group having a Hammett's substituent constant σp of >=0.20.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic light-sensitive material, and more particularly, to an ornamental silver halide photographic light-sensitive material having a large improvement in color reproducibility. Also, the present invention relates to an ornamental silver halide photographic material having excellent color reproducibility even after storage over time.

[0002]

2. Description of the Related Art Various types of color prints are known. Typical examples include imagewise exposure of a silver halide photographic light-sensitive material (hereinafter, also simply referred to as a light-sensitive material),
And color prints created by processing. Various characteristics are required for such a color print, but color reproducibility is an important performance, and various improved methods have been proposed. Of these, the coupler, the basic technical material of the color development process, greatly affects the color reproducibility of photos,
Various methods have been proposed for improving the spectral absorption characteristics.

For example, a compound represented by the general formula 1 described in JP-A-6-67388 has been proposed as a coupler having good spectral absorption of a yellow dye. Further, as a coupler having good spectral absorption of a magenta dye, a pyrazolotriazole coupler is known, and a compound represented by the general formula M-1 described in JP-A-4-114154 has been proposed.

The dyes formed from these couplers are:
Color reproduction is improved due to low absorption of the secondary absorption portion at wavelengths other than the main absorption wavelength. In particular, in a direct-viewing photosensitive material having a reflective support, since it is observed at a reflection density, turbidity in a low-density portion such as secondary absorption is emphasized, and the influence is large. However, couplers that form dyes with good spectral absorption properties require a unique structure in order to exhibit the properties, and thus the problem is that the compounds are expensive and often have low color development. . Further, in these methods, the performance is determined by the characteristics of the coupler, and the effect of improving color reproduction is limited, and is insufficient.

On the other hand, various mask techniques for adding a colored coupler to a photographic material are known. However, these are intended to improve the performance of the photosensitive material for photography, and are not intended to improve the performance of the photosensitive material for direct viewing having a reflective support.

In particular, as a result of studying the improvement of the color reproducibility of a direct-viewing photosensitive material, it has been found that the color reproducibility of a color print can be improved by preparing a color print using a photosensitive material containing a colored coupler. I found it.

However, such a method alone has not been able to sufficiently improve color reproducibility. Furthermore,
It was necessary to have excellent color reproduction even under various storage conditions. Another problem is that simply adding a colored coupler to a light-sensitive material having a reflective support easily deteriorates the whiteness of the ornamental light-sensitive material.

As one of means for improving the whiteness of an ornamental light-sensitive material, a technique for adjusting the whiteness of a reflective support is known, and the b * value of a whiteness L * a * b * display system is-. 6
The following materials have good white background, and a support in this range is preferably used for photographic paper.

However, such a white support is
It was found that such an effect was not found when applied to a photosensitive material having the above colored coupler.

Thus, it contains a colored coupler,
In order to solve these new problems in a photosensitive material having a reflective support, it has been necessary to find an improved technique specific to a photosensitive material having a reflective support.

[0011]

Accordingly, a first object of the present invention is to provide an ornamental silver halide photographic light-sensitive material having a large degree of improvement in color reproducibility. Another object of the present invention is to provide an ornamental silver halide photographic material having excellent color reproducibility even after storage over time. Still another object of the present invention is to provide an ornamental silver halide photographic material having improved color reproducibility without deterioration of white background.

[0012]

The above object of the present invention has been attained by the following constitutions.

(1) In a silver halide photographic material having a layer containing a coupler on a reflective support, at least one layer contains a colored coupler and the whiteness of the reflective support is L * a *. A silver halide photographic material having a b * value of greater than -6 in a b * display system.

(2) In a silver halide photographic light-sensitive material having a layer containing a coupler on a reflective support, at least one layer contains a colored coupler, and the silver halide photographic light-sensitive material contains a white pigment. 12% by weight content
A silver halide photographic material having the above layers.

(3) In a silver halide photographic material having a coupler-containing layer on a reflective support, at least one layer contains a colored coupler, and the silver halide photographic material has the general formula [I] ] A silver halide photographic material comprising a compound represented by the following formula:

(4) A silver halide photographic light-sensitive material having a coupler-containing layer on a reflective support, wherein at least one layer contains a colored coupler and the silver halide photographic light-sensitive material has the general formula [II] ] A silver halide photographic light-sensitive material containing a compound represented by the formula [2].

(5) A ≦ 0.04 (1),
The silver halide photographic material according to (2), (3) or (4).

Here, A represents an increase in green, blue or red light transmission density of a silver halide photographic light-sensitive material which is increased by containing a colored coupler.

Hereinafter, the present invention will be described in detail.

The colored coupler used in the present invention is a coupler which has a hue even in an unreacted state (substantially has a spectral absorption in a visible portion) and which has a different hue after color development from an unreacted hue, or A coupler which has a hue even in an unreacted state and becomes colorless after coloring. The colored coupler may form a dye image such as yellow, magenta, cyan, and black by a coupling reaction with a color developing agent, or may become colorless.

Examples of preferred colored couplers in the present invention include magenta colored cyan coupler, yellow colored magenta coupler, yellow colored cyan coupler, magenta colored yellow coupler, cyan colored magenta coupler, cyan colored yellow coupler, magenta colored colorless coupler, cyan Colored colorless couplers and the like (in the case of a magenta colored cyan coupler, a coupler which is colored magenta when unreacted and develops cyan after coupling).

Of these, couplers colored with magenta or cyan are preferred, and couplers colored with magenta are more preferred. Particularly preferred are magenta colored cyan couplers.

Hereinafter, typical colored couplers will be described.

In the present invention, the magenta colored cyan coupler refers to a coupler having an absorption maximum in the visible absorption region of the coupler between 500 and 600 nm, and coupling with an oxidized aromatic primary amine developing agent to form a visible absorption region. Refers to a cyan coupler which forms a cyan dye having an absorption maximum between 630 and 750 nm.

As the magenta colored cyan coupler, a compound represented by the following general formula (1) is preferable.

[0026]

Embedded image

In the formula, COUP represents a cyan coupler residue, J represents a divalent linking group, n represents 0 or 1, and R ¹ represents an aryl group.

The cyan coupler residue represented by COUP includes a phenol type coupler residue and a naphthol type coupler residue, and is preferably a naphthol type coupler residue.

As the divalent linking group represented by J, those represented by the following general formula (2) are preferable.

[0030]

Embedded image

[0031] In the formula, Y is -O -, - S -, - represents OCO- or -OCOO-, R ² represents an alkylene group or an arylene group of 1 to 4 carbon atoms, R ³ is 1 to carbon atoms 4 represents an alkylene group. The alkylene group of R ² and R ³ may be substituted by an alkyl group, a carboxyl group, a hydroxyl group, a sulfo group, or the like.

Z is -C (R ⁵ ) (R ⁶ )-, -O-, -S
-, - SO -, - SO 2 -, - SO 2 NH -, - CONH -, - COO -, -
NHCO -, - NHSO ₂ - or an -OCO-, R ⁵ and R ^6,
Each represents an alkyl group or an aryl group.

R ⁴ is an alkyl group, aryl group, heterocyclic group, hydroxyl group, cyano group, nitro group, sulfonyl group, alkoxy group, aryloxy group, carboxyl group, sulfo group, halogen atom, carbonamide group, sulfonamide. A carbamoyl group, an alkoxycarbonyl group or a sulfamoyl group.

P represents 0 or a positive integer, and q represents 0 or 1.
And r represents an integer of 1 to 4. When p is 2 or more, R
² and Z may be the same or different. When r is 2 or more, R ⁴ may be the same or different.

The aryl group represented by R ¹ is preferably a phenyl group or a naphthyl group when n = 0. This phenyl group and naphthyl group may have a substituent, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a mercapto group, Examples of the substituent include an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an acylamino group, a sulfonamide group, a carbamoyl group, and a sulfamoyl group.

When n = 1, the aryl group represented by R ¹ is preferably a naphthol group represented by the following general formula (3).

[0037]

Embedded image

In the formula, R ⁷ represents a linear or branched alkyl group having 1 to 4 carbon atoms (methyl, ethyl, propyl, i-propyl, butyl, s-butyl, t-butyl, etc.), and M represents a photograph. Inactive cations such as cations of alkali metals such as hydrogen atom, sodium atom and potassium atom, ammonium, methylammonium, ethylammonium, diethylammonium, triethylammonium, ethanolammonium, diethanolammonium, pyridinium, piperidinium, anilinium , Toluidinium, p-nitroanilinium, anisidium and the like.

Specific examples of the magenta colored cyan coupler represented by the general formula (1) are shown below, but it should not be construed that the invention is limited thereto.

[0040]

Embedded image

[0041]

Embedded image

[0042]

Embedded image

[0043]

Embedded image

[0044]

Embedded image

These compounds are described in JP-A-50-1233.
No. 41, No. 55-65957, No. 56-94347
No., JP-B-42-11304, 44-46461
Nos. 48-17899, 53-34733, U.S. Pat. No. 3,034,892, British Patent 1,084,4
The compound can be synthesized with reference to the method described in No. 80 or the like.

In the present invention, a yellow colored magenta coupler refers to a coupler having an absorption maximum in the visible absorption region of the coupler between 400 and 500 nm, and coupling with an oxidized aromatic primary amine developing agent to form a visible absorption region. Is a magenta coupler that forms a magenta dye having an absorption maximum between 510 and 580 nm.

As the yellow colored magenta coupler, those represented by the following general formula (4) are preferred.

Formula (4) C _P -N = NR ^{11 In the} formula, C _P represents a magenta coupler residue having an azo group bonded to the active site, and R ¹¹ represents a substituted or unsubstituted aryl group. Represents

[0049] As a magenta coupler residue represented by C _P is, coupler residues derived from the 5-pyrazolone magenta couplers and pyrazolotriazole magenta couplers are preferably represented by, particularly preferably the following general formula (5) Residue.

[0050]

Embedded image

In the formula, R ¹² represents a substituted or unsubstituted aryl group, R ¹³ represents an acylamino group, an anilino group, a ureido group or a carbamoyl group, which may have a substituent.

The aryl group represented by R ¹² is preferably a phenyl group. Examples of the substituent of the aryl group include a halogen atom, an alkyl group (e.g., methyl and ethyl), an alkoxy group (e.g., methoxy and ethoxy), an aryloxy group (e.g., phenyloxy and naphthyloxy), and an acylamino group (benzamide, α- (2 , 4-di-t-amylphenoxy) butylamide, etc.), sulfonylamino group (benzenesulfonamide, hexadecanesulfonamide, etc.), sulfamoyl group (methylsulfamoyl, phenylsulfamoyl, etc.), carbamoyl group (butylcarbamoyl, phenyl) Carbamoyl), a sulfonyl group (eg, methylsulfonyl, dodecylsulfonyl, benzenesulfonyl), an acyloxy group, an ester group, a carboxyl group, a sulfo group, a cyano group, a nitro group, and the like.

Specific examples of R ¹² include phenyl, 2,
4,6-trichlorophenyl, pentachlorophenyl,
Pentafluorophenyl, 2,4,6-trimethylphenyl, 2-chloro-4,6-dimethylphenyl, 2,6
-Dichloro-4-methylphenyl, 2,4-dichloro-
6-methylphenyl, 2,4-dichloro-6-methoxyphenyl, 2,6-dichloro-4-methoxyphenyl,
Each group such as 2,6-dichloro-4- [α- (2,4-di-t-amylphenoxy) acetamido] phenyl is exemplified.

The acylamino group represented by R ¹³ includes
Pivaloylamino, tetradecaneamide, α- (3-pentadecylphenoxy) butyramide, 3- [α-
(2,4-di-t-amylphenoxy) acetamide]
Groups such as benzamide, benzamide, 3-acetamidobenzamide, 3- (3-dodecylsuccinimide) benzamide, and 3- (4-dodecyloxybenzenesulfonamido) benzamide.

The anilino group represented by R ¹³ includes anilino, 2-chloroanilino, 2,4-dichloroanilino, 2,4-dichloro-5-methoxyanilino, 4-cyanoanilino, 2-chloro-5- [Α- (2,4-di-
t-amylphenoxy) butyramide] anilino, 2-
Chloro-5- (3-octadecenylsuccinimide) anilino, 2-chloro-5-tetradecanamidoanilino, 2-chloro-5- [α- (3-t-butyl-4-hydroxyphenoxy) tetradecanamide Anilino,
And groups such as 2-chloro-5-hexadecanesulfonamidoanilino.

The ureido group represented by R ¹³ includes methyl ureide, phenyl ureide, 3- [α- (2,4-
Di-t-amylphenoxy) butyramido] phenylureide and the like.

The carbamoyl group represented by R ¹³ includes
Tetradecylcarbamoyl, phenylcarbamoyl, 3
-[Α- (2,4-di-t-amylphenoxy) acetamido] phenylcarbamoyl and the like.

The aryl group represented by R ¹¹ is preferably a phenyl group or a naphthyl group. Examples of the substituent of the aryl group include a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, a hydroxyl group, an acyloxy group, a carboxyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, Examples thereof include an arylsulfonyl group, an acyl group, a sulfonamide group, a carbamoyl group, and a sulfamoyl group, and particularly preferred are an alkyl group, a hydroxyl group, an alkoxy group, and an acylamino group.

These yellow colored magenta couplers are described in JP-A-49-123625 and JP-A-49-1314.
No. 48, No. 52-42121, No. 52-102723
No. 54-52532, No. 58-172647,
U.S. Pat. Nos. 2,763,552 and 2,801,171
No. 3,519,429 and the like.

In the present invention, a yellow colored cyan coupler refers to a coupler having an absorption maximum in the visible absorption region of the coupler between 400 and 500 nm, and coupling with an oxidized aromatic primary amine developing agent in the visible absorption region. Is a cyan coupler forming a cyan dye having an absorption maximum between 630 and 750 nm.
No. 44, pages 8 to 26.

The yellow colored cyan coupler is represented by the following general formulas (6) to (8), and is a water-soluble cyan coupler by coupling reaction with an oxidized aromatic primary amine developing agent.
A cyan coupler capable of releasing a compound residue containing a -hydroxy-2-pyridin-5-ylazo group, a pyrazolidone-4-ylazo group, a 2-acylaminophenylazo group or a 2-sulfonamidophenylazo group is preferred.

[0062]

Embedded image

In the general formulas (6) to (8), Cp is a cyan coupler residue (Time is bonded to the coupling position), Time is a timing group, k is an integer of 0 or 1, and X represents N, O or S and represents a divalent linking group which binds to (Time) _k and binds to A, and A represents an arylene group or a divalent heterocyclic group.

In the general formula (6), R ²¹ and R ²² independently represent a hydrogen atom, a carboxyl group, a sulfo group, a cyano group,
Alkyl group, cycloalkyl group, aryl group, heterocyclic group, carbamoyl group, sulfamoyl group, carbonamido group, sulfonamido group or alkylsulfonyl group, R
²³ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, respectively. Where Time,
At least one of X, A, R ²¹ , R ²² or R ²³ contains a water-soluble group (hydroxyl, carboxyl, sulfo, amino, ammonium, amyl, phosphono, phosphino, hydroxysulfonyloxy, etc.).

In the general formula (7), R ²⁴ represents an acyl group or a sulfonyl group, R ²⁵ represents a substitutable group, and j represents an integer of 0 to 4. When j is an integer of 2 or more, R ²⁵ may be the same or different. Provided that at least one of Time, X, A, R ^{24 and} R ²⁵ is a water-soluble group (hydroxyl,
Carboxyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammonium, etc.).

In the general formula (8), R ²⁶ represents a hydrogen atom, a carboxyl group, a sulfo group, a cyano group, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heterocyclic group, R ²⁷ represents a carbamoyl group, a sulfamoyl group, a carbonamido group, a sulfonamido group or an alkylsulfonyl group, and R ²⁷ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group. Where Time, X, A, R
^At least one of ²⁶ contains a water-soluble group (hydroxyl, carbamoyl, sulfo, phosphono, phosphino, hydroxysulfonyloxy, amino, ammonium, etc.). Z ₀ represents O or NH.

These yellow colored cyan couplers are disclosed in JP-B-61-52827, US Pat.
Nos. 170 and 4,004,929, JP-A-61-72.
No. 244, No. 61-273543, JP-A-4-444
And the method described in JP-A No. 4-151655 or the like.

These colored couplers can be added to any layer according to the purpose.

The colored coupler is preferably used by mixing with a normal coupler which is colorless in an undeveloped state. At this time, the amount of the colored coupler added is such that the increase in the spectral reflection density due to the addition of the colored coupler causes the secondary absorption wavelength (-100 nm or +100 nm from the main absorption wavelength) when the colorless coupler develops the maximum color in an unreacted state. Is preferably not more than の of the spectral reflection density.

In the present invention, in the color image portion having only the hue in the layer to which the colored coupler is added, the reflection density at the wavelength at which the spectral reflection density of the dye is maximized is:
0.2, 0.3, 0.4, 0.5, 1.0, 1.5,
When the spectral reflection density is measured at a portion where 2.0 is obtained, it is preferable that there is no wavelength at which the spectral reflection density becomes equal between the portions.

The A value in the present invention represents an increase in the green, blue or red light transmission density of the light-sensitive material which is increased by containing the colored coupler. The light-sensitive material of the present invention and the colored coupler are removed. After processing the same sample as above except for the above, the optical transmission density of the uncolored portion (unexposed portion) was measured using an X-rite 310 densitometer (manufactured by X-rite).
And the difference in optical transmission density when measured with green light, blue light, and red light. If the color of the unreacted colored coupler is magenta, green light
Blue light is used for yellow, and red light is used for cyan. When two or more types of colored couplers are used, the A value at any corresponding light may be within the present invention, but the A value at two or more types of measurement light is within the present invention. The effect of the present invention is larger and more preferable.

The A value is preferably A ≦ 0.04, more preferably 0 <A ≦ 0.03, and still more preferably 0.001 ≦ A.
A ≦ 0.02, more preferably 0.002 ≦ A ≦ 0.0
15, particularly preferably 0.003 ≦ A ≦ 0.01
0.

The photosensitive material of the present invention is one of the preferred forms for use in color proofing. In order to form an image, it is preferable to use a light source unit scanning exposure type automatic developing machine. Equipment for particularly preferred image formation,
A specific example of the system is Konsens manufactured by Konica Corporation.
usL, Konsensus570, Konsensu
sII and the like can be mentioned.

The reflecting support according to the first aspect of the present invention is:
The whiteness of the support is represented by L * a * b *, and the b * value is larger than -6. The whiteness of L * a * b * display is J
The spectral absorption was measured under the illumination and light reception geometric conditions c of ISZ 8722-1982, and the calculated X.T. Y. From the Z value, the L * a * b * value can be determined by the method described in JIS Z 8730-1980. As a device that can be used for this measurement, a 607 type color analyzer, a C-2000 type color analyzer (all manufactured by Hitachi, Ltd.) and the like can be used. The b * value is preferably greater than -5, more preferably 0.4
Larger, most preferably 1.0 or more.

The b * value is adjusted according to the type, shape, particle size distribution, colorant addition amount, pulp whiteness, fluorescent brightener addition amount, and the like of the white pigment contained in the support.

The reflecting support according to the second invention of the present invention is:
The content of the white pigment is 12% by weight or more. This white pigment is preferably added to the resin layer on the image forming side of the double-sided resin-coated paper. At this time, the resin layer on the image forming side
It is particularly preferred to have two or more layers.

As the white pigment, those usually used can be used, and titanium oxide is particularly preferred.

The compound represented by formula (I) according to the third invention of the present invention will be described.

[0079]

Embedded image

Wherein R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and R
₅ represents a substituent.

The substituents represented by R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ may be any substituents, but are preferably hydrogen atoms and C 1-20. Alkyl group (methyl, ethyl, t-butyl, t-octyl, dodecyl, etc.)
Alkoxy group (ethoxy, butoxy, octyloxy, etc.), phenyl group (2,5-diamylphenyl etc.), phenoxy group (2,5-diamylphenoxy etc.) alkyloxycarbonyl group (dodecyloxycarbonyl etc.) phenyloxycarbonyl Groups (such as 2,5-diamylphenoxycarbonyl) and cycloalkyl groups (such as cyclopentyl and cyclohexyl). These groups may be further substituted with another substituent.

Preferred compounds of the general formula [I] are R ₀ to
R ₅ is a compound which is an optionally substituted alkyl group or a hydrogen atom, of which more preferred compounds has a molecular weight of compounds 150 to 400, more preferably a compound having a molecular weight of 200 to 300. Most preferably,
Compounds in which R ₀ , R ₂ , and R ₄ are hydrogen atoms, and R ₁ , R ₃ , and R ₅ are unsubstituted alkyl groups. Of these, compounds having a molecular weight of 150 to 400 are particularly preferable.

Preferred specific examples of the compound represented by the formula [I] are shown below, but it should not be construed that the invention is limited thereto.

[0084]

Embedded image

The compound represented by the general formula [I] is
It is preferably contained in the same layer as the layer containing the colored coupler.

Next, the compounds (cyan couplers) represented by the general formulas [II] to [V] will be described.

[0087]

Embedded image

In the formula, R ₁₁ represents a hydrogen atom or a substituent;
R ₁₂ represents a substituent. m represents the number of substituents R _12. When m is 0, R ₁₁ represents an electron-withdrawing group having a Hammett's substituent constant σ _P of 0.20 or more. When m is 1 or 2 or more, R ₁₁ represents R _11.
And at least one of R ₁₂ is a Hammett's substituent constant σ _P
Represents an electron-withdrawing group of 0.20 or more.

Z ₁ represents a nonmetallic atom group necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be condensed with a benzene ring or the like.

R ₁₃ represents a hydrogen atom or a substituent, Z ₂ represents a group of non-metallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring by condensing with the pyrazole ring together with —NH—, 6
The membered ring may have a substituent and may be condensed with a benzene ring or the like in addition to the pyrazole ring.

R ₁₄ and R ₁₅ each represent an electron-withdrawing group having a Hammett's substituent constant σ _P of 0.20 or more. However, the sum of the σ _P values of R ₁₄ and R ₁₅ is 0.65 or more. Z ₃
Represents a group of nonmetal atoms necessary to form a nitrogen-containing 5-membered heterocyclic ring, and the 5-membered ring may have a substituent.

R ₁₆ and R ₁₇ each represent a hydrogen atom or a substituent; Z ₄ represents a group of non-metallic atoms necessary to form a nitrogen-containing 6-membered heterocyclic ring; May be provided.

X ₁ , X ₂ , X ₃ and X ₄ each represent a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized form of a color developing agent.

First, the cyan coupler represented by the general formula [II] will be described in detail.

Examples of the substituent having a substituent constant σ _P defined by Hammett according to the present invention of +0.20 or more include sulfonyl, sulfinyl, sulfonyloxy, sulfamoyl, phosphoryl, carbamoyl, and the like.
Examples include groups such as acyl, acyloxy, oxycarbonyl, carboxyl, cyano, nitro, halogen-substituted alkoxy, halogen-substituted aryloxy, pyrrolyl, and tetrazolyl, and halogen atoms.

Examples of the sulfonyl group include alkylsulfonyl, arylsulfonyl, halogen-substituted alkylsulfonyl, halogen-substituted arylsulfonyl and the like; sulfinyl groups such as alkylsulfinyl and arylsulfinyl; sulfonyloxy groups such as alkylsulfonyloxy and Groups such as arylsulfonyloxy; sulfamoyl groups include N, N-dialkylsulfamoyl, N, N-diarylsulfamoyl, N
-Alkyl-N-arylsulfamoyl and the like; phosphoryl groups as alkoxyphosphoryl, aryloxyphosphoryl, alkylphosphoryl, arylphosphoryl and other groups; carbamoyl groups as N, N-dialkylcarbamoyl, N, N-diarylcarbamoyl, N-alkyl-N-arylcarbamoyl, etc .; acyl groups, alkylcarbonyl, arylcarbonyl, etc .; acyloxy groups, alkylcarbonyloxy, etc .; oxycarbonyl groups,
Groups such as alkoxycarbonyl and aryloxycarbonyl; halogen-substituted alkoxy groups such as α-halogen-substituted alkoxy; halogen-substituted aryloxy groups such as tetrafluoroaryloxy and pentafluoroaryloxy; pyrrolyl groups Is 1-pyrrolyl and the like; Examples of the tetrazolyl group include 1-tetrazolyl and the like.

In addition to the above substituents, trifluoromethyl,
Heptafluoro-i-propyl, nonylfluoro-t-
Each group such as butyl, tetrafluoroaryl, and pentafluoroaryl is also preferably used.

Among the substituents represented by R ₁₁ or R ₁₂ , examples of the substituent other than the electron-withdrawing group include various ones and are not particularly limited. Representative examples thereof include alkyl, aryl, anilino, Acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl, cycloalkenyl, alkynyl, heterocycle, alkoxy, aryloxy, heterocycleoxy, siloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino , Aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, hydroxyl and mercapto, spiro compound residue, bridged hydrocarbon compound residue and the like.

The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched. As the aryl group, a phenyl group is preferable.

As the acylamino group, an alkylcarbonylamino group or an arylcarbonylamino group; as the sulfonamide group, an alkylsulfonylamino group or an arylsulfonylamino group; Groups.

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, particularly 5
To 7 are preferable, and the alkenyl group may be linear or branched. A cycloalkenyl group having 3 to 12 carbon atoms;
Particularly, those having 5 to 7 are preferable.

As the ureido group, an alkylureido group,
An arylureido group or the like; a sulfamoylamino group as an alkylsulfamoylamino group, an arylsulfamoylamino group, or the like; a 5- to 7-membered heterocyclic group is preferable, specifically a 2-furyl group, 2-thienyl group,
2-pyrimidinyl group, 2-benzothiazolyl group and the like; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1- A phenyltetrazol-5-oxy group or the like; the heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3 , 5-
Triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group;
3-heptadecyl succinimide group, phthalimide group, glutarimide group and the like; spiro compound residues such as spiro [3.3] heptane-1-yl; and bridged hydrocarbon compound residues as bicyclo [2.2. 1] heptan-1-yl, tricyclo [3.3.1.1 ^3.7] decan-1-yl, 7,7-dimethyl - bicyclo [2.2.1] heptane-1-yl, and the like.

These groups may further contain a substituent such as a long-chain hydrocarbon group or a diffusion-resistant group such as a polymer residue.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X ₁ include, for example, a halogen atom (hydrochloric acid, bromine, fluorine, etc.), alkoxy, aryloxy,
Heterocyclic oxy, acyloxy, sulfonyloxy, alkoxycarbonyloxy, aryloxycarbonyl,
Alkyloxalyloxy, alkoxyoxalyloxy, alkylthio, arylthio, heterocyclic thio, alkoxythiocarbonylthio, acylamino, sulfonamide, nitrogen-containing heterocyclic ring linked by N atom, alkoxycarbonylamino, aryloxycarbonylamino, carboxyl, etc. Each group is exemplified, and among them, preferred are a hydrogen atom and a nitrogen-containing heterocyclic group bonded by an alkoxy, aryloxy, alkylthio, arylthio, or N atom.

The nitrogen-containing 5-membered heterocyclic ring formed by Z ₁ includes rings such as pyrazole, imidazole, benzimidazole, triazole and tetrazole.

More specifically, the compound represented by the general formula [II] is represented by the following general formulas [II] -1 to [II] -7.

[0107]

Embedded image

In the above general formula, R _{11 in} [II] -1
And at least one of R _21, [II] at least one of the in -2 R ₁₁ and R _22, [II] in the -3 R _11, R
_At least one of R _23, R ₂₄ and at least one of R ₁₁ , R ₂₅ and R ₂₆ in [II] -4, [II] -5
At least one of R ₁₁ and R ₂₇ in, [II] R ₁₁ in -6, [II] at least one sigma _P of the R ₁₁ and R ₂₈ in -7 0.20 Is an electron-withdrawing group.

X ₁ has the same meaning as X ₁ in formula [II], and p represents an integer of 0 to 4.

Further, among R ₁₁ and R _{21 to} R ₂₈ , the value of σ _P is equal to 0.
What is not an electron-withdrawing group of 20 or more represents a hydrogen atom or a substituent, and among R ₂₈ , those which are not an electron-withdrawing group are not particularly limited as substituents. Specifically, in the general formula [II], , R _{11 and} R ₁₂ are the same as the substituents represented by R ₁₁ or R ₁₂ when they are other than the electron-withdrawing group.

The cyan coupler having an electron-withdrawing group according to the present invention is disclosed in JP-A-64-554 and JP-A-64-555.
, And can be easily synthesized according to the methods described in JP-A Nos. 64-557 and JP-A-1-105251.

Next, the compound represented by formula (III) will be described.

The cyan coupler of the general formula [III] has a structure in which a 6-membered heterocyclic ring is formed by condensation with a pyrazole ring, and the substituent represented by R ₁₃ is not particularly limited. Examples include alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl groups.In addition, halogen atoms and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl,
Acyl, carbamoyl, sulfamoyl, cyano, alkoxy, sulfonyloxy, aryloxy, heterocyclic oxy, siloxy, acyloxy, carbamoyloxy,
Amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxyl, hydroxyl, mercapto, nitro, sulfo and other groups, And spiro compound residues, bridged hydrocarbon compound residues, and the like.

The alkyl group represented by R ₁₃ preferably has 1 to 32 carbon atoms, may be linear or branched, and the aryl group is preferably a phenyl group.

The acylamino group represented by R ₁₃ includes
Alkylcarbonylamino group, an arylcarbonylamino group or the like; The sulfonamide group, an alkylsulfonylamino group, an aryl sulfonyl amino group; an alkylthio group, the alkyl moiety in the arylthio group, the aryl component is an alkyl group represented by R _3, Aryl groups.

The alkenyl group represented by R ₁₃ has 2 to 32 carbon atoms, and the cycloalkyl group has 3 carbon atoms.
~ 12, particularly preferably 5 ~ 7, and the alkenyl group may be linear or branched. The cycloalkenyl group preferably has 3 to 12 carbon atoms, particularly preferably 5 to 7 carbon atoms.

The sulfonyl group represented by R ₁₃ is an alkylsulfonyl group, an arylsulfonyl group, etc .; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group, etc .; Oxyphosphonyl group, arylphosphonyl group, etc .; acyl group as alkylcarbonyl group, arylcarbonyl group, etc .; carbamoyl group as alkylcarbamoyl group, arylcarbamoyl group, etc .; sulfamoyl group as alkylsulfamoyl group, arylsulfa Moyl group and the like; acyloxy group as alkylcarbonyloxy group and arylcarbonyloxy group and the like; carbamoyloxy group as alkylcarbamoyloxy group and arylcarbamoyloxy group and the like; As the id group, an alkylureido group, an arylureido group, etc .; as the sulfamoylamino group, an alkylsulfamoylamino group, an arylsulfamoylamino group, etc .; as the heterocyclic group, a 5- to 7-membered group is preferable. Typically, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, a 2-benzothiazolyl group,
-Pyrrolyl group, 1-tetrazolyl group, etc .; As the heterocyclic oxy group, those having a 5- to 7-membered heterocyclic ring are preferable, for example, 3,4,5,6-tetrahydropyranyl-2-oxy group, 1-phenyl As a heterocyclic thio group, a 5- to 7-membered heterocyclic thio group is preferable. For example, a 2-pyridylthio group, a 2-benzothiazolylthio group, a 2,4-diphenoxy-1,3,3 5-triazole-6-thio group and the like; siloxy group as trimethylsiloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group, 3-heptadecylsuccinimide group, phthalimide group and glutarimide A spiro compound residue such as spiro [3.3]
Heptane-1-yl and the like; as bridged hydrocarbon compound residue bicyclo [2.2.1] heptane-1-yl, tricyclo [3.3.1.1 ^3.7] decan-1-yl, 7,7
-Dimethyl-bicyclo [2.2.1] heptan-1-yl and the like.

The above-mentioned groups may further have a substituent such as a long-chain hydrocarbon group or a non-diffusible group such as a polymer residue.

Examples of the group capable of leaving by reaction with an oxidized form of the color developing agent represented by X ₂ include the same groups as those of X _{1 in the} general formula [II].

The nitrogen-containing 6-membered heterocyclic ring formed by Z ₂ is preferably a 6π electron system or an 8π electron system, and contains from 1 to 4 nitrogen atoms including at least one —NH—, The at least one carbonyl group contained in the 6-membered ring represents a group such as> C = O or> C = S. Further, the at least one sulfonyl group the 6-membered ring contains -SO ₂ - represents a group.

Preferred specific examples of the cyan coupler of the present invention include compounds represented by the following general formulas [III] -1 to [III] -6.

[0122]

Embedded image

Wherein R ₁₃ , R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R
₃₅ , R ₃₆ , R ₃₇ and R ₃₈ represent R ₁₁ in the general formula [II]
In the above formula, X ₂ has the same meaning as X ₁ in the general formula [II], in the general formula [III] -5, n represents an integer of 0 to 4, when n is 2 to 4, a plurality of R ₃₆ may be the same or different.

R ₃₄ , R ₃₅ , R ₃₇ and R ₃₈ in formulas [III] -4 and [III] -6 are the same as those in formula [II].
Same as ₁₁ , except that R ₃₄ and R ₃₇ are not hydroxyl groups.

Next, the compound represented by formula (IV) will be described.

R ₁₄ and R ₁₅ are Hammett's substituent constant σ _P
Represents an electron withdrawing group of 0.20 or more, and examples of these electron withdrawing groups include the same groups as the electron withdrawing groups of R ₁₁ and R ₁₂ in the general formula [II]. However, the sum of the σ _P values of R ₁₄ and R ₁₅ is 0.65 or more.

Examples of the nitrogen-containing 5-membered heterocyclic ring formed by Z ₃ include a pyrazole, imidazole or tetrazole ring. These 5-membered nitrogen-containing heterocycles may have a substituent.

More specifically, the compound represented by the general formula [IV] is represented by the following general formulas [IV] -1 to [IV] -8.

[0129]

Embedded image

In the formula, R ₁₄ , R ₁₅ and X ₃ are represented by the general formula [I
V]. R ₄₁ represents a hydrogen atom or a substituent, and R ₄₂ represents an electron-withdrawing group having a Hammett's substituent constant σ _P of 0.20 or more.

The substituent represented by R ₄₁ is represented by the general formula [II
The same groups as those of R _{13 in} I] can be mentioned, and examples of the electron withdrawing group represented by R ₄₂ include the same groups as the electron withdrawing groups of R ₁₁ and R ₁₂ in the general formula [II]. it can.

As for the cyan coupler represented by the general formula [IV], the cyan coupler represented by the general formula [IV] -1, [IV] -2 or [IV]-
The cyan coupler represented by 3 is preferable, and particularly, [IV]-
The cyan coupler represented by 2 is preferred.

Next, the cyan coupler represented by the formula [V] will be described.

R ₁₆ and R ₁₇ each represent a hydrogen atom or a substituent, and examples of these substituents include the same groups as R _{13 in} formula [III].

Z ₄ represents a nonmetallic atom group necessary for forming a nitrogen-containing 6-membered heterocyclic ring. However, the heterocyclic ring has at least one dissociating group. Examples of four divalent linking groups for forming a nitrogen-containing 6-membered heterocyclic ring include -NH-,
-N (R)-, -N =, -CH (R)-, -CH =,-
C (R) =, - CO -, - S -, - SO -, - SO 2 -
(R represents a substituent, and specific examples include R ₁₃
And the substituents mentioned above). Examples of the dissociating group include those having an acidic proton such as -NH-, -CH (R)-, and preferably have a pKa of 3 to 12 in water.
It has a value of

Among the couplers represented by the general formula [V], preferred specific examples include the following general formulas [V] -1 to [V]-
6 is mentioned.

[0137]

Embedded image

In the formula, R ₁₆ , R ₁₇ and X ₄ have the same meanings as in the general formula [V]. R ₅₁ and R ₅₂ each represent a hydrogen atom or a substituent, and R ₅₃ represents an electro-attractive group having a Hammett's substituent constant σ _P value of 0.20 or more.

Specific examples of the substituent of R ₅₁ and R ₅₂ are the same as those of R _{13 in the} general formula [III], and specific examples of the electron-withdrawing group represented by R ₅₃ are R ₁₁ in the general formula [II]. And the electron-withdrawing group for R ₁₂ .

Examples of the group capable of leaving by reaction with the oxidized form of the color developing agent represented by X ₄ include the same groups as those of X _{1 in} formula [II].

Hereinafter, cyan couplers represented by the general formulas [II] to [V] (hereinafter referred to as cyan couplers of the present invention)
The following are specific examples, but the present invention is not limited thereto.

[0142]

Embedded image

[0143]

Embedded image

[0144]

Embedded image

The cyan coupler of the present invention is generally used in an amount of 1 × 10 ^-3 to 1 mol, preferably 1 × 10 ^-3 mol, per mol of silver halide.
It can be used in the range of × 10 ^-2 to 8 × 10 ^-1 mol. Further, the coupler of the present invention can be used in combination with another type of cyan coupler.

The cyan coupler of the present invention is preferably contained in the same layer as the layer containing the colored coupler.

The composition of the silver halide photographic emulsion used in the present invention may be any halogen composition such as silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide and silver chloroiodide. However, silver chlorobromide containing 95 mol% or more of silver chloride and substantially containing no silver iodide is preferable. Quick processing,
From the standpoint of processing stability, a silver halide emulsion containing preferably 97 mol% or more, more preferably 98 to 99.9 mol%, of silver chloride is preferred.

In order to obtain a silver halide emulsion, a silver halide emulsion having a portion containing silver bromide at a high concentration is particularly preferably used. In this case, the portion containing silver bromide at a high concentration may be epitaxy-bonded to silver halide emulsion grains, may be a so-called core-shell emulsion, or may be only partially formed without forming a complete layer. May simply have regions with different compositions. The composition may change continuously or may change discontinuously. It is particularly preferable that the portion where silver bromide exists at a high concentration is the top of crystal grains on the surface of silver halide grains.

It is advantageous that the silver halide emulsion contains heavy metal ions. Heavy metal ions that can be used for such purposes include iron, iridium, platinum,
Group 8-10 metals such as palladium, nickel, rhodium, osmium, ruthenium, cobalt and cadmium,
Group 12 transition metals such as zinc and mercury, lead, rhenium,
Examples include molybdenum, tungsten, gallium, and chromium ions. Among them, metal ions of iron, iridium, platinum, ruthenium, gallium, and osmium are preferable. These metal ions can be added to the silver halide emulsion in the form of a salt or a complex salt.

When the heavy metal ion forms a complex, the ligand or ion may be cyanide ion, thiocyanate ion, isothiocyanate ion, cyanate ion, chloride ion, bromide ion, iodide ion, or the like. Examples include nitrate ion, carbonyl, ammonia and the like. Among them, cyanide ion, thiocyanate ion, isothiocyanate ion, chloride ion, bromide ion and the like are preferable.

In order to make the silver halide emulsion contain heavy metal ions, the heavy metal compound is added to the silver halide emulsion during the formation of silver halide grains, during the formation of silver halide grains, and during the physical ripening after the formation of silver halide grains. It may be added at any place in the process. In order to obtain a silver halide emulsion satisfying the above conditions, the heavy metal compound can be dissolved together with the halide salt and added continuously over the whole or a part of the grain forming step.

When the heavy metal ion is added to the silver halide emulsion, the amount is 1 × 10 ^-9 per mol of silver halide.
To 1 × 10 ⁻² mol, preferably 1 × 10 ^{−8 to} 5 × 1
0 ^-5 mol are preferred.

The shape of the silver halide grains can be arbitrary. A preferred example is a cube having a (100) plane as a crystal surface. Also, U.S. Pat.
Nos. 3,756, 4,225,666;
No. 26589, JP-B-55-42737, and The Journal of Photographic Science (J.
Photogr. Sci. ), 39, (1973), etc., by an octahedron, a tetrahedron,
Particles having a dodecahedral shape or the like can be produced and used. Further, particles having a twin plane may be used.

As the silver halide grains, grains having a single shape are preferably used, but it is particularly preferable to add two or more kinds of monodispersed silver halide emulsions to the same layer.

The particle size of the silver halide grains is not particularly limited, but is preferably 0.1 to 1.2 μm, more preferably 0.2 to 1.2 μm, in consideration of other photographic properties such as rapid processing and sensitivity. The range is 1.0 μm. This particle size can be measured using the projected area or diameter approximation of the particle. If the particles are substantially uniform in shape, the particle size distribution can be expressed quite accurately as diameter or projected area.

The particle size distribution of the silver halide grains used in the present invention is preferably a monodispersed silver halide grain having a coefficient of variation of 0.22 or less, more preferably 0.15 or less, and particularly preferably 0. .15 or less is added to the same layer.

Here, the coefficient of variation is a coefficient representing the width of the particle size distribution, and is defined by the following equation. Coefficient of variation = S /
R (S is the standard deviation of the particle size distribution, R is the average particle size) The particle size here is the diameter of a spherical silver halide particle, or the diameter of a cubic or non-spherical particle. In this case, the diameter represents the diameter when the projected image is converted into a circular image having the same area.

As a device and a method for preparing a silver halide emulsion, various methods known in the art can be used.

The silver halide emulsion may be obtained by any of an acidic method, a neutral method, and an ammonia method. The particles may be grown at one time or may be grown after seed particles have been made. The method of producing the seed particles and the method of growing them may be the same or different.

The form of reacting the soluble silver salt with the soluble halide salt may be any of a forward mixing method, a reverse mixing method, a simultaneous mixing method, a combination thereof, and the like. Is preferred. Further, as one form of the simultaneous mixing method, p-type described in JP-A-54-48521 or the like is used.
The Ag controlled double jet method can also be used.

Also, JP-A-57-92523 and JP-A-57-92523.
No. 92524, etc., a device for supplying an aqueous solution of a water-soluble silver salt and a water-soluble halide salt from an addition device arranged in a reaction mother liquor, and a water-soluble silver salt described in, for example, German Offenlegungsschrift 2,921,164. And a device for continuously adding an aqueous solution of a water-soluble halide salt while changing its concentration, Japanese Patent Publication No. 56-5
No. 01776, etc., a reaction mother liquor may be taken out of the reactor and concentrated by an ultrafiltration method to form grains while keeping the distance between silver halide grains constant.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound having a mercapto group, a nitrogen-containing heterocyclic compound or a compound such as a sensitizing dye may be added at the time of forming silver halide grains or after the completion of grain formation.

The silver halide emulsion can be used in combination with a sensitization method using a gold compound and a sensitization method using a chalcogen sensitizer.

Examples of the chalcogen sensitizer include a sulfur sensitizer,
A selenium sensitizer, a tellurium sensitizer, or the like can be used, but a sulfur sensitizer is preferable. Examples of the sulfur sensitizer include thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, cystine, p-toluenethiosulfonate, rhodanine, and inorganic sulfur.

The addition amount of the sulfur sensitizer is preferably changed depending on the kind of the silver halide emulsion to be applied, the expected effect size, and the like, but is preferably from 5 × 10 ^{−10 to} 5 × 10 ^-10 per mol of the silver halide. In the range of ^10-5 mol, preferably 5
It is used in an amount of ^10-8 to ^310-5 mol.

As a gold sensitizer, various gold complexes such as chloroauric acid, gold sulfide and the like can be added. Examples of the ligand compound used include dimethyl rhodanine, thiocyanic acid, mercaptotetrazole, and mercaptotriazole. The amount of the gold compound used is not uniform depending on the type of silver halide emulsion, the type of compound to be used, the ripening conditions, etc., but is usually from 1 × 10 ^-4 to 1 × 10 ^-8 per mol of silver halide. Preferably it is molar. More preferably, it is 1 × 10 ⁻⁵ to 1 × 10 ⁻⁸ mol.

The chemical sensitization of a silver halide emulsion includes:
A reduction sensitization method may be used.

The silver halide emulsion may contain a known antifoggant such as a fogging agent for the purpose of preventing fogging during the preparation of the light-sensitive material, reducing performance fluctuation during storage, or fogging during development. Agents can be used. Examples of preferred compounds that can be used for such purposes include compounds represented by the general formula (II) described in JP-A-2-14636, page 7, lower column.
More preferred specific compounds include (IIa-1) to (IIa-8) and (IIb-1) to (IIb-1) described on page 8 of the publication.
b-7) or 1- (3-methoxyphenyl)-
Compounds such as 5-mercaptotetrazole and 1- (4-ethoxyphenyl) -5-mercaptotetrazole can be mentioned.

These compounds are added according to the purpose in the steps of preparing silver halide emulsion grains, chemical sensitizing step, finishing the chemical sensitizing step, and preparing a coating solution. When chemical sensitization is performed in the presence of these compounds, 1 × 10 ^{−5 to} 5 × 10 ⁻⁴ per mol of silver halide is used.
It is preferably used in a molar amount. When added at the end of chemical sensitization, 1 × 10
^-6 to 1 × 10 ⁻² mol is preferable, and 1 × 10 ^-5 to
5 × 10 ⁻³ mol is more preferred. When added to the silver halide emulsion layer in the coating solution preparation step, the amount is preferably about 1 × 10 ^-6 to 1 × 10 ^-1 mol per mol of silver halide, and 1 × 10 ^-5 to 1 × 10 ¹ mol. ^-2 mol is more preferred. When added to a layer other than the silver halide emulsion layer, the amount in the coating film is 1 × 10 ^-9 to 1 × 1 per m ^2.
0 ^-3 mol are preferred.

In the light-sensitive material of the present invention, dyes having absorption in various wavelength ranges can be used for the purpose of preventing irradiation and halation. For this purpose, any of known compounds can be used. Particularly, as dyes having absorption in the visible region, JP-A-3-251840,
Dyes of AI-1 to 11 described on page 308;
The dye described in No. 3770 is preferably used. As the infrared absorbing dye, compounds represented by general formulas (I), (II) and (III) described in the lower left column of page 2 of JP-A-1-280750 may be used. It has preferable spectral characteristics, has no effect on the photographic characteristics of the silver halide photographic emulsion, and is free from contamination due to residual color. As a specific example of a preferred compound, see Japanese Patent Publication No.
Exemplified Compounds (1) listed in the lower left column of page 5 to the lower left column of page 5
(45).

In order to improve the sharpness, the amount of these dyes to be added is 680 nm of the unprocessed sample of the light-sensitive material.
Is preferable to make the spectral reflection density 0.7 or more, more preferably 0.8 or more.

It is preferable to add a fluorescent whitening agent to the light-sensitive material because whiteness can be improved. Preferred examples of the compound include compounds represented by the general formula described in JP-A-2-232652.

When the light-sensitive material of the present invention is used as a color light-sensitive material, 400 to 900 nm
Has a layer containing a silver halide emulsion spectrally sensitized to a specific region of the wavelength range of The silver halide emulsion contains one or more sensitizing dyes in combination.

As the spectral sensitizing dye used in the present invention, any of the known compounds can be used. Examples of the blue sensitizing dye include BS-1 described in JP-A-3-251840, page 28. To 8 can be preferably used alone or in combination. As the green photosensitive sensitizing dye, GS-1 to GS-5 described on page 28 of the same publication are preferably used.
As the red-sensitive sensitizing dye, RS described in p.
-1 to 8 are preferably used. When performing image exposure with infrared light using a semiconductor laser or the like,
It is necessary to use an infrared-sensitive sensitizing dye. As the infrared-sensitive sensitizing dye, JP-A-4-285950, 6-8.
The dyes of IRS-1 to 11 described on page are preferably used. In addition, these infrared, red, green, blue photosensitive sensitizing dyes,
JP-A-4-285950, pages 8 to 9, supersensitizers SS-1 to SS-9 and JP-A-5-66515, 15
It is preferable to use compounds S-1 to S-17 described on pages 17 to 17 in combination.

The sensitizing dye may be added at any time from the formation of silver halide grains to the end of chemical sensitization. As a method of adding the sensitizing dye, methanol, ethanol, fluorinated alcohol, acetone, may be dissolved in water-miscible organic solvents such as dimethylformamide or water and added as a solution, or added as a solid dispersion. Is also good.

As the coupler used in the light-sensitive material of the present invention, any compound capable of forming a coupling product having a spectral absorption maximum wavelength in a wavelength region longer than 340 nm by coupling reaction with an oxidized form of a color developing agent is used. Can also be used, but a typical example is a wavelength band of 3
Known as a yellow dye-forming coupler having a spectral absorption maximum wavelength at 50 to 500 nm, a magenta dye-forming coupler having a spectral absorption maximum wavelength at a wavelength range of 500 to 600 nm, and a cyan dye-forming coupler having a spectral absorption maximum wavelength at a wavelength range of 600 to 750 nm. Are typical.

Examples of the cyan coupler which can be preferably used in the present invention include couplers represented by formulas (C-I) and (C-II) described in JP-A-4-114154, page 5, lower left column. be able to. Specific compounds are:
In the publication, those described as CC-1 to CC-9 in the lower right column on page 5 to the lower left column on page 6 can be mentioned.

Examples of magenta couplers that can be preferably used include couplers represented by general formulas (MI) and (M-II) described in JP-A-4-114154, upper right column on page 4. . Specific compounds include those described as MC-1 to MC-11 in the lower left column of page 4 to the upper right column of page 5 of the same publication. Among the above magenta couplers, a coupler represented by the general formula (MI) described in the upper right column on page 4 of the same publication is preferable, and among them, R _M of the general formula (MI) is preferably Couplers that are tertiary alkyl groups are particularly preferred because of their excellent light resistance. Publication 5
MC-8 to MC-11 described in the upper column of the page are preferable because they are excellent in reproducing colors from blue to purple and red, and are also excellent in detail description.

As a yellow coupler which can be preferably used, a coupler represented by formula (YI) described in JP-A-4-114154, upper right column on page 3, can be mentioned. Specific compounds include those described as YC-1 to YC-9 in the lower left column on page 3 of the publication. Among them, the general formula [Y-1]
Wherein R _Y1 is an alkoxy group;
The coupler represented by the general formula [I] described in No. 67388 is preferable because it can reproduce yellow having a preferable color tone. Of these, particularly preferred examples of the compounds are described in JP-A-4-114154.
Publication, YC-8, YC-9 described in the lower left column of page 4,
And JP-A-6-67388, pages 13-14.
o. Compounds represented by (1) to (47) can be mentioned. Further most preferred compounds are described in JP-A-4-818.
No. 47, page 1 and the general formula [Y
-1].

When the oil-in-water type emulsification dispersion method is used to add the coupler or other organic compound used in the light-sensitive material of the present invention, it is usually added to a water-insoluble high-boiling organic solvent having a boiling point of 150 ° C. or higher. If necessary, a low boiling point and / or water-soluble organic solvent is used in combination to dissolve, and emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant. As a dispersing means, a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic disperser, or the like can be used. After or simultaneously with the dispersion, a step of removing the low-boiling organic solvent may be added. Examples of high boiling organic solvents that can be used for dissolving and dispersing the coupler include phthalic acid esters such as dioctyl phthalate, di-i-decyl phthalate, and dibutyl phthalate; phosphoric acids such as tricresyl phosphate and trioctyl phosphate; Esters are preferably used. The high-boiling organic solvent preferably has a dielectric constant of 3.5 to 7.0. Further, two or more kinds of high-boiling organic solvents can be used in combination.

In place of the method using a high-boiling organic solvent or in combination with a high-boiling organic solvent, a water-insoluble and organic solvent-soluble polymer compound may be added, if necessary, to a low-boiling and / or water-soluble organic solvent. In a hydrophilic binder such as an aqueous gelatin solution by using a surfactant and emulsifying and dispersing by various dispersing means. Examples of the water-insoluble and organic solvent-soluble polymer used at this time include poly (Nt-butylacrylamide).

Preferred compounds used as surfactants for dispersing photographic additives and adjusting the surface tension during coating include a hydrophobic group having 8 to 30 carbon atoms and a sulfo group or a salt thereof in one molecule. To do. Specifically, A-1 to A-11 described in JP-A-64-26854.
Is mentioned. Further, a surfactant in which a fluorine atom is substituted for an alkyl group is also preferably used. These dispersions are usually added to a coating solution containing a silver halide emulsion, and it is better that the time until the addition to the coating solution after the dispersion and the time from the addition to the coating solution to the coating are shorter. , Preferably within 10 hours, more preferably within 3 hours and within 20 minutes.

It is preferable that each of the above couplers is used in combination with a fading inhibitor for preventing fading of the formed dye image due to light, heat, humidity and the like. Particularly preferred compounds include phenyl ether compounds represented by formulas I and II described in JP-A-2-66541, p.
A phenolic compound represented by the general formula IIIB described in JP-A-174150; a general formula A described in JP-A-64-90445;
An amine compound represented by the formula:
The metal complexes represented by the general formulas XII, XIII, XIV and XV described above are particularly preferable for magenta dyes. Also, JP
Compounds represented by the general formula I 'described in JP-A-196049 and compounds represented by the general formula II described in JP-A-5-11417 are particularly preferable for yellow and cyan dyes.

Further, for the purpose of shifting the absorption wavelength of the coloring dye, compound (d-11) described in JP-A-4-114154, page 9, lower left column, and compound (A ') described in page 10, lower left column of JP-A-4-114154. Compounds such as -1) can be used. or,
In addition, the fluorescent dye releasing compounds described in U.S. Pat. No. 4,774,187 can also be used.

In the light-sensitive material, a compound which reacts with the oxidized developing agent is added to a layer between the light-sensitive layers to prevent color turbidity, or added to a silver halide emulsion layer to prevent fog or the like. It is preferred to improve. As the compound for this, a hydroquinone derivative is preferable, and more preferably, 2,5.
Dialkylhydroquinone such as -di-t-octylhydroquinone. Particularly preferred compounds are disclosed in
The compound is a compound represented by the general formula II described in JP-A-1333056, and includes compounds II-1 to II-14 described on pages 13 to 14 and compound 1 described on page 17.

It is preferable to add an ultraviolet absorber to the light-sensitive material to prevent static fog or to improve the light fastness of the dye image. Preferable ultraviolet absorbers include benzotriazoles, and particularly preferable compounds are those represented by general formula-3 described in JP-A-1-250944.
A compound represented by the general formula described in JP-A-64-66646, UV-1L to UV-27L described in JP-A-63-187240, and a general formula I described in JP-A-4-1633. Compound shown in JP-A-5-1651
Compounds represented by the general formulas (I) and (II) described in No. 44 are exemplified.

In the light-sensitive material of the present invention, it is advantageous to use gelatin as a binder. If necessary, another gelatin derivative, a graft polymer of gelatin and another polymer, a protein other than gelatin, a sugar derivative, A hydrophilic colloid such as a cellulose derivative or a synthetic hydrophilic polymer such as a homopolymer or a copolymer can also be used.

As the hardener of these binders, it is preferable to use a vinyl sulfone hardener, a chlorotriazine hardener or a carboxy active hardener alone or in combination. Specifically, JP-A-61-249054, 6
It is preferable to use the compounds described in 1-245153 and the like.

Further, in order to prevent the growth of fungi and bacteria which adversely affect the photographic performance and the image storability, JP-A-3-15.
It is preferable to add a preservative and an antifungal agent described in No. 7646. It is preferable to add a slipping agent or matting agent described in JP-A-6-118543 or JP-A-2-73250 to the protective layer in order to improve the physical properties of the photosensitive material or the surface of the photosensitive material after processing.

As the support used for the light-sensitive material, any material may be used, including paper coated with polyethylene or polyethylene terephthalate, a paper support made of natural pulp or synthetic pulp, a vinyl chloride sheet, and a white pigment. For example, polypropylene, polyethylene terephthalate support, baryta paper, etc. may be used. Among them, a support having a water-resistant resin coating layer on both sides of the base paper is preferable.

As the water-resistant resin, polyethylene, polyethylene terephthalate or a copolymer thereof is preferred.

As the white pigment used for the support, inorganic and / or organic white pigments can be used, and preferably, inorganic white pigments are used. For example, sulfates of alkaline earth metals such as barium sulfate, carbonates of alkaline earth metals such as calcium carbonate, silicas such as fine silica powder, synthetic silicates, calcium silicate, alumina, alumina hydrate, titanium oxide, oxide Zinc, talc, clay and the like can be mentioned. Barium sulfate and titanium oxide are preferred as white pigments.

The degree of dispersion of the white pigment in the water-resistant resin layer of the paper support according to the present invention can be measured by the method described in JP-A-2-28640. When measured by this method, the degree of dispersion of the white pigment is preferably 0.20 or less, more preferably 0.15 or less, as the coefficient of variation described in the above-mentioned publication.

The center surface average roughness (SRa) value of the support is preferably 0.15 μm or less, more preferably 0.12 μm or less, because the effect of improving the glossiness is obtained, which is preferable. Also, in the white pigment-containing water-resistant resin of the reflective support or in the applied hydrophilic colloid layer, to improve the whiteness by adjusting the spectral reflection density balance of the white background after treatment, ultramarine blue, oil-soluble dyes, etc. It is preferable to add a small amount of a bluing agent or a reddish agent.

The light-sensitive material may be subjected to corona discharge, ultraviolet irradiation, flame treatment, etc. on the support surface, if necessary, and then directly or undercoating (adhesion, antistatic property, dimensional stability on the support surface). , One or more subbing layers to improve rub resistance, hardness, antihalation properties, friction properties and / or other properties).

In coating a light-sensitive material using a silver halide emulsion, a thickener may be used to improve coatability. As a coating method, extrusion coating and curtain coating, which can simultaneously apply two or more layers, are particularly useful.

In order to form a photographic image using the photosensitive material of the present invention, the image recorded on the negative may be optically focused on the photosensitive material to be printed and printed. Is once converted into digital information, the image is formed on a CRT (cathode ray tube), and this image may be formed on a photosensitive material to be printed and printed, or a laser based on the digital information may be used. Printing may be performed by scanning while changing the light intensity.

The present invention is preferably applied to a light-sensitive material in which a developing agent is not incorporated in the light-sensitive material, and particularly preferably to a light-sensitive material having a reflective support.

As the aromatic primary amine developing agent used in the present invention, known compounds can be used. The following compounds can be mentioned as examples of these compounds.

CD-1: N, N-diethyl-p-phenylenediamine CD-2: 2-amino-5-diethylaminotoluene CD-3: 2-amino-5- (N-ethyl-N-laurylamino) toluene CD-4: 4- (N-ethyl-N-β-hydroxyethylamino) aniline CD-5: 2-methyl-4- (N-ethyl-N-β-hydroxyethylamino) aniline CD-6: 4- Amino-3-methyl-N-ethyl-N-
(Β-methanesulfonamidoethyl) aniline CD-7: 4-amino-3-β-methanesulfonamidoethyl-N, N-diethylaniline CD-8: N, N-dimethyl-p-phenylenediamine CD-9: 4-amino-3-methyl-N-ethyl-N-
Methoxyethylaniline CD-10: 4-amino-3-methyl-N-ethyl-N
-(Β-ethoxyethyl) aniline CD-11: 4-amino-3-methyl-N-ethyl-N
-(Γ-hydroxypropyl) aniline In the present invention, the color developer can be used in an arbitrary pH range, but from the viewpoint of rapid processing, the pH is preferably 9.5 to 13.0, more preferably pH 9.8. ~ 12.
Used in the range of 0.

The processing temperature for color development is preferably from 35 to 70 ° C. The higher the temperature, the shorter the processing time is possible, which is preferable. However, it is preferable that the temperature is not too high from the viewpoint of the stability of the processing solution.

Conventionally, the color development time is generally 3 minutes 30 minutes.
Although it is performed in about seconds, in the present invention, it is preferably performed within 40 seconds, and more preferably within 25 seconds.

To the color developing solution, known developing component compounds can be added in addition to the above color developing agents.
Usually, an alkali agent having a pH buffering action, a chloride ion, a development inhibitor such as benzotriazoles, a preservative, a chelating agent and the like are used.

After the color development, the light-sensitive material is subjected to a bleaching process and a fixing process. The bleaching process may be performed simultaneously with the fixing process. After the fixing process, a washing process is usually performed.
Further, a stabilization process may be performed as an alternative to the water washing process.

The developing apparatus used for developing the photosensitive material of the present invention may be a roller transport type in which the photosensitive material is conveyed between rollers arranged in a processing tank. An endless belt system may be used in which the processing tank is formed in a slit shape, and a processing liquid is supplied to the processing tank and the photosensitive material is transported. A web system by contact with a carrier impregnated with a treatment liquid, a system using a viscous treatment liquid, and the like can also be used.

When a large amount of photosensitive material is processed, it is usual to carry out a running process using an automatic developing machine. At this time, the smaller the replenishing amount of the replenisher is, the more preferable the processing form is, for example, environmental suitability. Is to add a processing agent in the form of a tablet as a replenishment method.
The method described in No. 6935 is most preferred.

[0207]

EXAMPLES The present invention will be described below with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 A paper support was prepared by laminating high-density polyethylene on both sides of a paper pulp having a basis weight of 180 g / m ² . However, on the side to be coated with the emulsion layer, a molten polyethylene containing a surface-treated anatase-type titanium oxide dispersed in a content of 15% by weight was laminated to produce a reflective support. After subjecting this reflective support to a corona discharge treatment, a gelatin undercoat layer was provided, and each layer having the following constitution was further applied to prepare a multilayer color photosensitive material. The coating solution was prepared as follows.

Coating solution for first layer 23.4 g of yellow coupler (Y-1), 3.34 g of dye image stabilizer (ST-1), 3.34 of (ST-2)
g, (ST-5) 3.34 g, a stain inhibitor (HQ-
1) 60 ml of ethyl acetate was added to 0.34 g, 5.0 g of image stabilizer A, 3.33 g of a high boiling point organic solvent (DBP), and 1.67 g of (DNP), and dissolved.
U-1) 10% aqueous gelatin solution containing 7 ml 220
The resulting mixture was emulsified and dispersed in the mixture using an ultrasonic homogenizer to prepare a yellow coupler dispersion.

This dispersion was mixed with a blue-sensitive silver halide emulsion prepared under the following conditions to prepare a first layer coating solution.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer so that the coating amounts were as shown in Tables 1 and 2.

(H-1) and (H-2) as hardening agents
Was added. Surfactants (SU-
2) and (SU-3) were added to adjust the surface tension.
The total amount of the fungicide (F-1) was 0.04 g / m ² in each layer.
Was added so that

[0213]

[Table 1]

[0214]

[Table 2]

SU-1: sodium tri-i-propylnaphthalenesulfonate SU-2: di (2-ethylhexyl) sodium sulfosuccinate sodium salt SU-3: di (2,2,3,3,4) sulfosuccinate , 4,
5,5-octafluoropentyl) · sodium salt DBP: dibutyl phthalate DNP: dinonyl phthalate DOP: dioctyl phthalate DIDP: di-i-decyl phthalate PVP: polyvinylpyrrolidone H-1: tetrakis (vinylsulfonylmethyl) methane H-2 : 2,4-dichloro-6-hydroxy-s-triazine sodium HQ-1: 2,5-di-t-octylhydroquinone HQ-2: 2,5-di-sec-dodecylhydroquinone HQ-3: 2 5-di-sec-tetradecylhydroquinone HQ-4: 2-sec-dodecyl-5-sec-tetradecylhydroquinone HQ-5: 2,5-di {(1,1-dimethyl-4-hexyloxycarbonyl) butyl ｝ Hydroquinone Image Stabilizer A: pt-octylph Enol

[0216]

Embedded image

[0219]

Embedded image

[0218]

Embedded image

[0219]

Embedded image

(Preparation of Blue-Sensitive Silver Halide Emulsion) 40 ° C.
In a liter of a 2% aqueous gelatin solution kept warm in
Solution) and (solution B) were added simultaneously over 30 minutes while controlling pAg = 7.3 and pH = 3.0, and the following (solution C) and (solution D) were further added at pAg = 8.0, pH = 5.5 and added simultaneously over 180 minutes. At this time, pAg was controlled by the method described in JP-A-59-45437.
H was controlled using sulfuric acid or an aqueous solution of sodium hydroxide.

(Solution A) Sodium chloride 3.42 g Potassium bromide 0.03 g Water was added to 200 ml (Solution B) Silver nitrate 10 g Water was added to 200 ml (Solution C) Sodium chloride 102.7 g K ₂ IrCl ₆ 4 × 10 ^-8 mol / mol Ag K ₄ Fe (CN) ₆ 2 × 10 ^-5 mol / mol Ag Potassium bromide 1.0 g Add water 600 ml (Solution D) Silver nitrate 300 g Add water 600 ml after completion of addition, Kao Atlas After desalting using a 5% aqueous solution of Demol N and 20% aqueous solution of magnesium sulfate, the mixture was mixed with an aqueous gelatin solution to give an average particle size of 0.71 μm.
m, coefficient of variation of particle size distribution 0.07, silver chloride content 99.
A 5 mol% monodispersed cubic emulsion EMP-1 was obtained. Next, the addition time of (Solution A) and (Solution B) and (Solution C) and (Solution D)
Except that the addition time was changed in the same manner as EMP-1.
Average particle size 0.64 μm, coefficient of variation of particle size distribution 0.07,
Monodisperse cubic emulsion EMP having a silver chloride content of 99.5 mol%
-1B was obtained.

The above EMP-1 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-1B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-1 and EMP-1B were mixed at a silver ratio of 1: 1 to obtain a blue-sensitive silver halide emulsion (Em-B).

Sodium thiosulfate 0.8 mg / mol AgX Chloroauric acid 0.5 mg / mol AgX Stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX Stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX sensitizing color BS-1 4 × 10 ^-4 mol / mol AgX sensitizing color BS-2 1 × 10 ^-4 mol / mol AgX (green-sensitive silver halide emulsion Preparation) (Solution A) and (Solution B)
The average particle size was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08, and a monodispersed cubic emulsion EMP-2 having a silver chloride content of 99.5%. Next, an average particle size of 0.50
A monodisperse cubic emulsion EMP-2B having a thickness of 0.08 μm, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-2 was optimally subjected to chemical sensitization at 55 ° C. using the following compounds. Also, EMP-2B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-2 and EMP-2B were mixed at a silver amount of 1: 1 to obtain a green-sensitive silver halide emulsion (Em-G).

Sodium thiosulfate 1.5 mg / mol AgX Chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ^-4 mol / mol AgX Sensitizing color GS-1 4 × 10 ^-4 mol / mol AgX (Preparation of red-sensitive silver halide emulsion) (solution A) and (solution B)
The average particle size was 0.40 μm in the same manner as in EMP-1 except that the addition time of (C) and (C solution) and (D solution) were changed.
m, a coefficient of variation 0.08 and a monodisperse cubic emulsion EMP-3 having a silver chloride content of 99.5%. The average particle size is 0.38
A monodisperse cubic emulsion EMP-3B having a particle size of 0.08, a coefficient of variation of 0.08 and a silver chloride content of 99.5% was obtained.

The above-mentioned EMP-3 was optimally subjected to chemical sensitization at 60 ° C. using the following compounds. Also, EMP-3B
Similarly, after the optimal chemical sensitization, the sensitized E
MP-3 and EMP-3B were mixed at a silver ratio of 1: 1 to obtain a red-sensitive silver halide emulsion (Em-R).

Sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 3 × 10 ⁻⁴ mol / mol AgX stabilizer STAB-2 3 × 10 ⁻⁴ mol / mol AgX stability Agent STAB-3 3 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-2 1 × 10 ⁻⁴ mol / mol AgX STAB-1: 1- ( 3-acetamidophenyl) -5-mercaptotetrazole STAB-2: 1-phenyl-5-mercaptotetrazole STAB-3: 1- (4-ethoxyphenyl) -5-mercaptotetrazole SS-1 was added in an amount of 2.0 × 10 ⁻³ mol per mol of silver halide.

[0228]

Embedded image

[0229]

Embedded image

[0230] The sample thus manufactured was used as sample 101.
And Next, Samples 102 to 108 were prepared in which the addition of the colored coupler to the fifth layer of Sample 101 and the b * value of the support were changed in the combinations shown in Table 3.

Each of the samples was exposed to wedges with red light and white light by a conventional method, and then subjected to a developing process in the following developing process to produce a color print having a cyan wedge image and a black wedge image.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 45 seconds 80 ml Bleaching and fixing 35.0 ± 0.5 ° C. 45 seconds 120 ml Stabilization 30-34 ° C. 60 seconds 150 ml Dry Drying 60 to 80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank liquid and replenisher tank liquid Replenisher Pure water 800 ml 800 ml triethylenediamine 2 g 3 g diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl -N- (β methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.0 g 10.0 g N, N-diethylhydroxylamine 6.8 g 6.0 g triethanolamine 10.0 g 10.0 g diethylenetriamine Sodium pentaacetate 2.0 g 2.0 g Optical brightener (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Water was added to make the whole volume 1 liter, and the tank solution was pH = 10.10, replenisher is pH Adjusted to 10.60.

Bleach-fix solution and replenisher Ferric ammonium diethylenetriaminepentaacetate dihydrate 65 g Diethylenetriaminepentaacetic acid 3 g Ammonium thiosulfate (70% aqueous solution) 100 ml 2-amino-5-mercapto-1,3,4-thiadiazole 2 2.0 g Ammonium sulfite (40% aqueous solution) 27.5 ml Water is added to make up to 1 liter, and the pH is adjusted to 5.0 with potassium carbonate or glacial acetic acid.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Fluorescent whitening agent (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g Bismuth chloride (45% aqueous solution) 0.65 g Magnesium sulfate heptahydrate 0.2 g PVP 1 0.0 g ammonia water (25% aqueous solution of ammonium hydroxide) 2.5 g nitrilotriacetic acid / trisodium salt 1.5 g Water is added to make up to 1 liter, and the pH is adjusted to 7.5 with sulfuric acid or aqueous ammonia.

The color reproducibility and white background of the cyan image portion thus obtained were evaluated.

The color reproducibility was measured by measuring the spectral absorption of a portion having a spectral reflection density of 1.0 at the maximum absorption wavelength of the cyan image portion using a 607 type color analyzer (manufactured by Hitachi, Ltd.), and based on the measured JIS. L * by the method of Z-8730
a * b * was calculated, and the color difference ΔE between the white background portion and the dye image portion was calculated. At the same time, the cyan image portion was visually observed to observe the vividness of the color.

The white background was observed by visual observation.

Table 3 shows the obtained results.

[0240]

[Table 3]

As is clear from Table 3, the sample of the present invention provided an ornamental image having a large degree of improvement in color reproducibility.

Example 2 A sample similar to the sample 101 of Example 1 was prepared, and a sample 20 was prepared.
It was set to 1. Samples 202 to 206 were prepared in the same manner as in Sample 201 except that the amounts of the colored coupler of the fifth layer and the white pigment of the support were changed by the combinations shown in Table 4.

These samples were exposed to light in the same manner as in Example 1, and the produced cyan image and white background were evaluated for color reproducibility and white background in the same manner as in Example 1.

[0244]

[Table 4]

As is clear from Table 4, the sample of the present invention provided an image having good color reproducibility.

Example 3 A sample similar to the sample 101 of Example 1 was prepared, and a sample 30 was prepared.
It was set to 1. Samples 302 to 305 similar to Sample 301 were prepared except that the colored coupler and cyan coupler of the fifth layer of Sample 301 were changed in the combinations shown in Table 5.

These samples were exposed to light in the same manner as in Example 1, and the produced cyan image and white background were evaluated for color reproducibility and white background in the same manner as in Example 1.

[0248]

[Table 5]

As is clear from Table 5, the sample of the present invention provided an image with good color reproducibility.

Example 4 A sample similar to the sample 101 of Example 1 was prepared, and a sample 40 was prepared.
It was set to 1. Sample 40 was the same as Sample 40 except that the colored coupler and the additive in the fifth layer of Sample 401 were changed in the combinations shown in Table 6.
Samples 402, 403, and 404 similar to 1 were produced.

These samples were exposed to light in the same manner as in Example 1, and the resulting cyan image was exposed to sunlight for 30 days using an underglass outdoor exposure table, and had a reflection density of 1.0 part. Measure the color difference fluctuation width before and after fading of
The color reproducibility after the lapse of time was evaluated by visual evaluation.

The results are shown in Table 6.

[0253]

[Table 6]

As is clear from Table 6, in the sample of the present invention, color variation with time was small, and an image having excellent color reproducibility was obtained even after storage with time.

Example 5 The same processing as in Example 1 was performed as described below.

Processing step Processing temperature Time Replenishment amount Color development 38.0 ± 0.3 ° C. 22 seconds 81 ml Bleaching and fixing 35.0 ± 0.5 ° C. 22 seconds 54 ml Stabilization 30-34 ° C. 25 seconds 150 ml Dry Drying 60 to 80 ° C. for 30 seconds The composition of the developing solution is shown below.

Color developer tank solution and replenisher tank solution Replenisher Pure water 800 ml 800 ml diethylene glycol 10 g 10 g potassium bromide 0.01 g-potassium chloride 3.5 g-potassium sulfite 0.25 g 0.5 g N-ethyl-N- ( β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline sulfate 6.5 g 10.5 g N, N-diethylhydroxylamine 3.5 g 6.0 g N, N-bis (2-sulfoethyl) hydroxylamine 3. 5 g 6.0 g Triethanolamine 10.0 g 10.0 g Diethylenetriaminepentaacetic acid sodium salt 2.0 g 2.0 g Fluorescent whitening agent (4,4'-diaminostilbene disulfonic acid derivative) 2.0 g 2.5 g Potassium carbonate 30 g 30 g Add water to make the total volume 1 liter, Liquor to pH = 10.10, replenishing solution is adjusted to pH = 10.60.

Bleach-fixing solution tank solution and replenisher tank solution Replenisher diethylenetriaminepentaacetate ammonium ferric dihydrate 100 g 50 g diethylenetriaminepentaacetic acid 3 g 3 g ammonium thiosulfate (70% aqueous solution) 200 ml 100 ml 2-amino-5-mercapto-1 2,3,4-thiadiazole 2.0 g 1.0 g Ammonium sulfite (40% aqueous solution) 50 ml 25 ml Add water to make the total volume 1 liter, use potassium carbonate or glacial acetic acid to adjust the tank solution to pH = 7.0, Adjust to pH = 6.5.

Stabilizing solution tank solution and replenisher solution o-phenylphenol 1.0 g 5-chloro-2-methyl-4-isothiazolin-3-one 0.02 g 2-methyl-4-isothiazolin-3-one 0.02 g Diethylene glycol 1.0 g Optical brightener (Tinopearl SFP) 2.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 1.8 g PVP 1.0 g Aqueous ammonia (25% aqueous solution of ammonium hydroxide) 2.5 g Ethylenediaminetetraacetic acid 1 0.0 g Ammonium sulfite (40% aqueous solution) 10 ml Add water to make the total volume 1 liter, and adjust the pH to 7.5 with sulfuric acid or aqueous ammonia.

Evaluation was performed in the same manner as in Example 1, and it was confirmed that the effect of the present invention was effectively obtained with the sample of the present invention.

Example 6 In Example 1, KPS NPS was used as an automatic developing machine.
-868J, ECOJET-P was used as a processing chemical, and a running process was performed according to the process name CPK-2-J1. Evaluation was performed in the same manner as in Example 1. As a result, it was confirmed that the effects of the present invention can be obtained with the color print of the present invention.

[0262]

According to the present invention, color reproducibility is improved,
This effect is maintained even after storage over time, and an ornamental silver halide photographic light-sensitive material which does not deteriorate whiteness can be provided.

Claims (5)

[Claims] 1. A silver halide photographic material having a layer containing a coupler on a reflective support, wherein at least one layer contains a colored coupler and the whiteness of the reflective support is L * a * b. * In the display system, b * value is -6
A silver halide photographic light-sensitive material characterized by being larger than the above. 2. A silver halide photographic light-sensitive material having a coupler-containing layer on a reflective support, wherein at least one layer contains a colored coupler and the silver halide photographic light-sensitive material contains a white pigment. A silver halide photographic material comprising a layer having a ratio of 12% by weight or more. 3. A silver halide photographic material having a coupler-containing layer on a reflective support, wherein at least one layer contains a colored coupler and the silver halide photographic material has the following general formula (I): A silver halide photographic light-sensitive material comprising a compound represented by the formula: Embedded image [In the formula, R ₀ , R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a substituent. ] 4. A silver halide photographic material having a coupler-containing layer on a reflective support, wherein at least one layer contains a colored coupler and the silver halide photographic material has the following general formula [II]: A silver halide photographic light-sensitive material comprising a compound represented by the formula: Embedded image [In the formula, R ₁₁ represents a hydrogen atom or a substituent, and R ₁₂ represents a substituent. m represents the number of substituents R _12. When m is 0, R
₁₁ represents an electron-withdrawing group having a Hammett's substituent constant σ _P of 0.20 or more. When m is 1 or 2 or more, at least one of R ₁₁ and R ₁₂ has a Hammett's substituent constant σ _P of 0. .20
It represents the above electron-withdrawing group. Z ₁ represents a nonmetallic atomic group necessary for forming a nitrogen-containing 5-membered heterocyclic ring which may be condensed with a benzene ring or the like. R ₁₃ represents a hydrogen atom or a substituent, Z ₂ is condensed with the pyrazole ring together with —NH—,
Represents a group of non-metallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring, and the 6-membered ring may have a substituent, and may be fused with a benzene ring or the like in addition to the pyrazole ring. Good. R ₁₄
And R ₁₅ each have a Hammett's substituent constant σ _P of 0.2
Represents 0 or more electron withdrawing groups. Where σ of R ₁₄ and R ₁₅
The sum of the _P values is 0.65 or more. Z ₃ represents a group of nonmetal atoms necessary to form a nitrogen-containing 5-membered heterocyclic ring, and the 5-membered ring may have a substituent. R ₁₆ and R ₁₇ are each
Represents a hydrogen atom or a substituent, Z ₄ represents a group of non-metallic atoms necessary for forming a nitrogen-containing 6-membered heterocyclic ring, and the 6-membered ring may have a substituent. X ₁ , X ₂ , X ₃ and X ₄ each represent a hydrogen atom or a group capable of leaving by a coupling reaction with an oxidized form of a color developing agent. ] 5. The silver halide photographic material according to claim 1, wherein A ≦ 0.04. Here, A represents an increase in green, blue or red light transmission density of the silver halide photographic light-sensitive material which is increased by containing the colored coupler.