JPH08272058A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide color photographic sensitive material containing a finely dispersed emulsion less in cource particles and superior in storage stability, and improved in lightfastness of image dyes and white background by specifying contents in photographicconstituent layers. CONSTITUTION: The silver halide color photographic sensitive material has on a support the photographic constituent layers comprising at least one silver halide emulsion layer containing a cyan dye-forming coupler, at least one silver halide emulsion layer containing a magenta dye-forming coupler, and at least one silver halide emulsion layer containing a yellow dye-forming coupler, and at least one nonphotosensitive layer, and at least one of the photographic constituent layers contains at least one kind of ultraviolet absorber and at least one of compounds represented by formulae I and II in which Q is a nonmetallic atomic group necessary to form a 5-, 6-, or 7-membered ring together with the N atom; each of R11 and R12 is an alkyl or aryl or alkoxy group; and each of R21 and R22 and X1 is an H atom or the like.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide color photographic light-sensitive material, and more specifically, it contains a UV absorber-containing emulsion dispersion having excellent emulsion dispersibility and storage stability, and a dye image after image formation. Relates to a silver halide color photographic light-sensitive material having excellent light resistance.

[0002]

2. Description of the Related Art In a silver halide color photographic light-sensitive material, a dye image formed by a reaction between an oxidation product of an aromatic primary amine developing agent and a dye-forming coupler is not only stored in a dark place but also in a bright place for a long time. It is hoped that it will not discolor even when stored in. In recent years, an ultraviolet absorber has been added to a photographic light-sensitive material for the purpose of improving fastness to a dye image and light on a white background, but the light fastness of an image formed from a yellow, magenta and cyan coupler is still insufficient. Absent. Therefore, it has been investigated to improve the light fastness of the ultraviolet absorber itself so that the ultraviolet absorber works effectively in the photographic light-sensitive material for a long period of time. For example, a method of preventing the deterioration or disappearance of the ultraviolet absorber by dissolving the ultraviolet absorber in a high boiling point organic solvent selected from phthalic acid ester or phosphoric acid ester is disclosed in JP-A-58-2097.
No. 35 is proposed. However, the stability of the ultraviolet absorber has not been sufficiently improved, and therefore, the light fastness of the image dye is not sufficient.

As another means for improving the light fastness of an ultraviolet absorber, a method of impregnating a polymer latex with an ultraviolet absorber is disclosed in British Patent No. 2,016,017A, but this method is sufficient. In addition, there is the drawback that in order to improve the light fastness, many polymer latices have to be used for the UV absorber. Further, there is disclosed a method of improving the light fastness of the ultraviolet absorber by emulsifying and dispersing the ultraviolet absorber together with a specific hydrophobic polymer.
It is described in JP-A-3-264748 and JP-A-4-191851. However, in the production of the above emulsified dispersion, these methods have a problem that it takes time to dissolve with an auxiliary solvent, and it is difficult to emulsify and disperse due to the high solution viscosity, resulting in coarse particles, and as a result, the color developability is lowered. Also, problems such as poor coating properties are likely to occur.
As a countermeasure, it is not preferable to use a large amount of an auxiliary solvent in order to reduce the solution viscosity because it causes a new environmental problem. In order to further improve the light fastness of image dyes and white backgrounds, a photographic light-sensitive material having a fine and excellent storage stability of an emulsion dispersion of a UV absorber that enables improvement of the photostability of the UV absorber is desired. It is rare.

[0004]

SUMMARY OF THE INVENTION Therefore, the object of the present invention is to provide an emulsified dispersion containing few coarse particles, fine particles, and excellent storage stability, and to improve the light fastness of an image dye and a white background. It is to provide a silver color photographic light-sensitive material.

[0005]

The objects of the present invention have been achieved by the following silver halide photographic light-sensitive materials. That is, (1) at least one layer of silver halide emulsion containing a cyan dye-forming coupler, at least one layer of silver halide emulsion containing a magenta dye-forming coupler, and at least one layer of halogen containing a yellow dye-forming coupler on a support. In a silver halide color photographic light-sensitive material having a photographic constituent layer consisting of a silver halide emulsion layer and at least one non-photosensitive layer, at least one photographic constituent layer in the same layer,
A compound represented by the general formula (I), the general formula (II) or the general formula (III), and an ultraviolet absorber selected from the compounds represented by the general formula (A) or the general formula (B); A silver halide color photographic light-sensitive material comprising at least one kind.

Formula (I)

[Chemical 12]

General formula (II)

[Chemical 13]

General formula (III)

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In the general formula (I), R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a nitro group,
It represents a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acylamino group, a carbamoyl group, a sulfo group, an alkylthio group or an arylthio group.
R ₁ and R ₂ and R ₃ and R ₄ may be connected to each other to form a 5- or 6-membered ring. R in the general formula (II)
₅ and R ₆ each represent a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group or an acyl group, and X is-.
Represents CO- or -COO-, m is an integer of 1 to 5, n is an integer of 1 to 4, and p is an integer of 1 to 4. In the general formula (III), A, B and C each represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a heterocyclic group. However, at least one of A, B, and C represents the general formula (IIIa).

General formula (IIIa)

[Chemical 15]

In the general formula (IIIa), R ₇ and R ₈ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group.

General formula (A)

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In the general formula (A), Q is a group of non-metal atoms necessary for forming a 5- to 7-membered ring with a nitrogen atom. R ₁₁ represents a substituted or unsubstituted alkyl group, aryl group or alkoxy group.

General formula (B)

[Chemical 17]

In the general formula (B), R ₂₁ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R ₂₂ represents a substituted or unsubstituted alkyl group, aryl group or alkoxy group. R ₂₃ represents a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, an alkoxy group, an acylamino group or a sulfonamide group. X ₁ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group, (2) the compound represented by the general formula (A) or the general formula (B) is further represented by the following general formula ( A silver halide color photographic light-sensitive material as described in the item (1), which is represented by A-1) or the general formula (B-1).

General formula (A-1)

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In formula (A-1), R ₁₁ and R ₁₂ each independently represent the same group as R _{11 in} formula (A).

General formula (B-1)

[Chemical 19]

In the general formula (B-1), R ₂₁ and R ₂₄ each independently represent the same group as R ₂₁ in the general formula (B). R ₂₂ and R ₂₅ each independently represent the same group as R _{22 in} formula (B). X ₁ represents X ₁ and the same group of the general formula (B), (3) the general formula (A) or the general formula in the same layer and the photographic component layer containing a compound represented by (B), formula (M
The silver halide color photographic light-sensitive material according to item (1) or (2), which contains at least one magenta coupler represented by formula (a) or (Mb).

General formula (Ma)

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General formula (Mb)

[Chemical 21]

(Wherein R ₃₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group or a heterocyclic oxy group, and R ₃₂ represents an aryl group or an alkyl group, X represents a hydrogen atom or a group capable of splitting off in a coupling reaction with an oxidized product of a developing agent, and further, via R ₃₁ , R ₃₂ or X,
You may form a multimer of a dimer or more. ), And (4)
At least one fluorescent brightening agent represented by the general formula (L) in the same layer as the photographic constituent layer containing the compound represented by the general formula (A) or the general formula (B) or a layer closer to the support than the photographic constituent layer. Are included (1), (2)
Alternatively, the silver halide color photographic light-sensitive material according to the item (3).

General formula (L)

[Chemical formula 22]

(In the formula, R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ represent a hydrogen atom or a substituent. A represents a nitrogen atom or a methine group.)

The ultraviolet absorber used in the present invention will be described below. In formula (I), R _{1 to} R ₄ are each a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group,
It represents an acylamino group, a carbamoyl group, a sulfo group, an alkylthio group or an arylthio group. R ₁ and R ₂ and R ₃ and R ₄ may be connected to each other to form a 5- or 6-membered ring. The ring may be a saturated ring or an unsaturated ring, and may be a hydrocarbon ring or a hetero ring. General formula (II)
R ₅ and R ₆ are each a hydrogen atom, an alkyl group,
Represents an alkoxy group, an aryloxy group or an acyl group, X represents —CO— or —COO—, and m is 1 to
Is an integer of 5, n is an integer of 1 to 4, and p is 1 to 4
Is an integer. These substituents of general formula (I) or (II) also include those substituted with any substituent. As a substituent, a hydroxyl group, a halogen atom (for example, a fluorine atom,
Chlorine atom, bromine atom, etc.), alkyl group having 1 to 12 carbon atoms (eg, methyl, ethyl, butyl, trifluoromethyl, hydroxyoctyl, epoxymethyl, etc.), alkoxy group having 1 to 18 carbon atoms (eg, methoxy, Ethoxy, butoxy, cyclohexyloxy, benzyloxy, etc.), an aryl group having 6 to 18 carbon atoms (eg, phenyl, 4-methylphenyl), an aryloxy group having 6 to 18 carbon atoms (eg, phenoxy, m-methylphenoxy, etc.) ), An alkoxycarbonyl group (eg, ethoxycarbonyl, 2-methoxyethoxycarbonyl, etc.), an aryloxycarbonyl group (eg, phenoxycarbonyl, p-methylphenoxycarbonyl, etc.), an alkylthio group having 1 to 18 carbon atoms (eg, methylthio, Butylthio, etc.) Bamoiru group (e.g. methylcarbamoyl, etc. butylcarbamoyl) represents the like.

2 represented by the general formula (I) used in the present invention
The-(2'-hydroxyphenyl) benzotriazole-based UV absorber may be solid or liquid at room temperature. Specific examples of the liquid include Japanese Examined Patent Publication Nos. 55-36984 and 5
It is described in, for example, JP-A-5-125787 and JP-A-58-214152. R _{1 of the} ultraviolet absorber represented by the general formula (I)
For details of the atoms and groups represented by R ₄ to R ₄ , see JP-A-5-
8-221844, 59-46646, 59-
No. 109055, Japanese Patent Publication No. 36-10466, No. 42-
No. 26187, No. 48-5496, No. 48-4157.
2, U.S. Pat. Nos. 3,754,919 and 4,220,
No. 711 and the like. The details of the groups represented by R ₅ and R ₆ of the benzophenone-based ultraviolet absorber represented by the general formula (II) are described in JP-B-48-30493 (US Pat. No. 3,698,907) and JP-A-48-31255. Etc.

In the general formula (III), A, B, and C are each independently a substituted or unsubstituted alkyl group, preferably an aryl group, an alkoxy group, an aryloxy group, or a heterocyclic group having 1 to 20 carbon atoms. Represents a ring group (eg pyridyl).
Examples of the substituent include the same as those described in the general formula (I) and the general formula (II). Of the groups A, B, and C, the groups other than the group of the general formula (IIIa) are preferably a substituted or unsubstituted aryl group or alkoxy group.

R ₇ and R ₈ in the general formula (IIIa) are each independently a hydrogen atom, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.) or a substituted or unsubstituted carbon atom of 1-18. Alkyl group (eg, methyl, trifluoromethyl, cyclohexyl, glycidyl, etc.), C6
To 18 substituted or unsubstituted aryl groups (eg, phenyl, tolyl, etc.), substituted or unsubstituted alkoxy groups having 1 to 20 carbon atoms (eg, methoxy, butoxy,
2-butoxyethoxy, 3-butoxy-2-hydroxypropyloxy, etc., a substituted or unsubstituted aryloxy group having 6 to 18 carbon atoms (eg, phenoxy, p-
(Such as methylphenoxy). R ₇ or R ₈ is preferably a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, and the substitution position is preferably the para position of the carbon atom bonded to the triazine ring. General formula of the invention
The compound (III) can be synthesized according to the method described in JP-A-46-3335 and European Patent No. 520938A1. Specific examples of the ultraviolet absorber used in the present invention are shown below, but the present invention is not limited thereto.

[0029]

[Chemical formula 23]

[0030]

[Chemical formula 24]

[0031]

[Chemical 25]

[0032]

[Chemical formula 26]

[0033]

[Chemical 27]

[0034]

[Chemical 28]

[0035]

[Chemical 29]

[0036]

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[0037]

[Chemical 31]

[0038]

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[0039]

[Chemical 33]

In the present invention, the ultraviolet absorber is preferably used in either the light-sensitive silver halide emulsion layer or the non-light-sensitive layer, but particularly preferably in the silver halide emulsion layer farthest from the support. It is preferably added to the upper layer. The compound represented by the general formula (I), (II), or (III) may be used alone or in combination with an ultraviolet absorber having another structure, but is preferably the general formula (I), (II), or It is preferable to use a mixture of two or more compounds selected from the structure (III), more preferably three or more, and it is further preferable that at least one of them is a liquid at room temperature. The coating amount of the ultraviolet absorber is preferably such that the absorbance at 360 nm is 0.6 or more, more preferably 1.0 or more, still more preferably 1.5 or more. A high boiling point organic solvent may be used when the ultraviolet absorber is dispersed in the hydrophilic colloid. These high boiling point organic solvents may be liquid, waxy or solid at room temperature, but have a boiling point of 180 ° C. or higher and a melting point of 150 ° C. or lower, preferably a boiling point of 200 ° C. or higher and a melting point of 100 ° C. or lower. belongs to.

Although the structure is not limited as long as the above conditions are satisfied, preferred high boiling organic solvents are phosphoric acid esters, phosphonic acid esters, benzoic acid esters, phthalic acid esters, fatty acid esters, carbonic acid esters. Examples thereof include amides, amides, ethers, halogenated hydrocarbons, alcohols and paraffins. Among these, phosphoric acid esters, phosphonic acid esters, phthalic acid esters, benzoic acid esters, and fatty acid esters are particularly preferable. The refractive index of the high boiling point organic solvent is preferably 1.50 or less, more preferably 1.43.
The above is 1.48 or less. By using those in this range, the refractive index of the phase containing the ultraviolet absorbent of the present invention becomes close to the refractive index of the binder such as gelatin, so-called haze is suppressed from occurring, and the density of the highest color density portion of yellow decreases. It is preferable in that such problems as described above are unlikely to occur.

The preferred range of the non-color forming compound represented by formula (A) or (B) of the present invention will be described in more detail. In the general formula (A), Q is a group of non-metal atoms necessary for forming a 5- to 7-membered ring with a nitrogen atom. Specifically, in addition to nitrogen atom, carbon atom, oxygen atom,
A ring formed by one or more of a sulfur atom and a phosphorus atom, and examples thereof include piperidine, piperazine, morpholine, and thiomorpholine. Also,
The ring formed by Q may be substituted. R ₁₁ is a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms.

In the general formula (B), R ₂₂ is the general formula (A).
Represents the same group as R _{11 in} . R ₂₁ represents a hydrogen atom or an alkyl group having 1 to 24 carbon atoms. R ₂₃ represents a hydrogen atom, a halogen atom (for example, a fluorine atom, a bromine atom, a chlorine atom), an alkyl group or an alkoxy group having 1 to 24 carbon atoms, an acylamino group or a sulfonamide group having 2 to 36 carbon atoms. X ₁ is a hydrogen atom or a substituent, and examples of such a substituent include a halogen atom, an alkyl group,
Alkenyl group, alkynyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, acyloxy group, hydroxy group, amino group, acylamino group, sulfonamide group, ureido group, urethane group, acyl group, carboxyl group, alkoxycarbonyl Group, carbamoyl group, alkylthio group, arylthio group, sulfoxide group, sulfonyl group, sulfonyloxy group, sulfamoyl group, nitro group, cyano group, silyl group, phosphoryl group,
And so on.

In the general formula (A), Q is preferably a nonmetallic atom group forming a 6-membered ring with a nitrogen atom, and R
₁₁ is preferably substituted or unsubstituted alkyl. In the general formula (B), R ₂₂ is preferably a substituted or unsubstituted alkyl group, and R ₂₃ is preferably an alkoxy group or an acylamino group. The compound of the general formula (A) or the general formula (B) is more preferably each of the general formula (A
-1) or general formula (B-1). General formula (A
In -1), R ₁₁ represents an alkyl group, an aryl group, or an alkoxy group, preferably a substituted or unsubstituted alkyl group having 4 to 24 carbon atoms. More preferably, it is an unsubstituted alkyl group or an alkyl group substituted with an ester group, an amide group, a sulfonyl group, a phosphoryl group, an alkoxy group or an aryloxy group. Of these, a branched alkyl group is most preferable. Particularly preferred is a case where a branched alkyl group at the α-position or a branched alkyl group is bonded.

In the general formula (B-1), R ₂₁ and R ₂₄
Each represents a hydrogen atom or an alkyl group, and R ₂₂ and R ₂₅ each represent an alkyl group, an aryl group or an alkoxy group. R ₂₁ and R ₂₄ are preferably hydrogen atoms or methyl groups, and R ₂₂ and R ₂₅ preferably have 4 carbon atoms.
To 24 substituted or unsubstituted alkyl groups. R ₂₂
And R ₂₅ is more preferably a branched alkyl group. Specific examples of the compound represented by formula (A) or (B) are shown below, but the invention is not limited thereto.

[0046]

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[0047]

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[0048]

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[0049]

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[0050]

[Chemical 38]

[0051]

[Chemical Formula 39]

[0052]

[Chemical 40]

The addition amount of the compound represented by the general formula (A) or (B) is preferably 0.1 to 10 parts by weight, more preferably 0.1 part by weight with respect to 1 part by weight of the ultraviolet absorber used in the same layer. ~ 2 parts by weight. If the ultraviolet absorber represented by the general formula (I), (II) or (III) and the compound represented by the general formula (A) or (B) of the present invention are in the same layer, a dye-forming coupler-containing layer and a Addition to any of the dye-forming coupler-free layers is preferable because the effects of the present invention are exhibited. The method of adding the compound represented by the general formula (A) or (B) to the layer containing the ultraviolet absorber represented by the general formula (I), (II) or (III) is as follows. A method is preferred in which an emulsified dispersion of a hydrophilic colloid of the compound represented by the formula (1) is prepared and added to the layer containing the ultraviolet absorber. General formula (A)
Alternatively, in order to prepare a hydrophilic colloid of the compound represented by (B), it is possible to use a solvent selected from the high-boiling organic solvents preferably used for emulsion dispersion of the ultraviolet absorber. After dissolving the ultraviolet absorber represented by the general formula (I), (II) or (III) and the compound represented by the general formula (A) or (B) in the above-mentioned high boiling point organic solvent, It is more preferable to emulsify and disperse in order to exert the effect of the present invention. When added to the coupler-containing layer, the emulsion dispersion of the coupler and the emulsion dispersion of the compound represented by the general formula (A) or (B) may be separately added to the same emulsion layer. From the viewpoint of improving the image fastness, it is most preferable to dissolve the ultraviolet absorber and the compound represented by the general formula (A) or (B) in the same high boiling point organic solvent and then simultaneously emulsify and disperse them. When the ultraviolet absorber represented by the general formula (I), (II) or (III) and the compound represented by the general formula (A) or (B) of the present invention are added to the same layer as the dye-forming coupler, The effect of the present invention is exhibited in any of the yellow coupler-containing layer, the magenta coupler-containing layer, and the cyan coupler-containing layer, but when used in the magenta coupler-containing layer, the effect of light resistance on a white background is remarkable, and is particularly preferable. . Further, as a magenta coupler, from the viewpoint of hue, image fastness, color developability, etc., the above-mentioned general formulas (Ma) and (M
A coupler represented by -b) is preferred.

The magenta coupler represented by formula (Ma) or (Mb), which is preferably used in the invention, will be described in detail below. In formula (M-a) or (M-b), R ₃₁ represents a hydrogen atom or a substituent, and a preferable substituent is an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group,
Examples thereof include an alkoxy group, a cycloalkyloxy group, an aryloxy group and a heterocyclic oxy group, and particularly preferably 2
A tertiary or tertiary alkyl group, a cycloalkyl group or an alkenyl group is used. R ₃₁ represents a substituted or unsubstituted aryl group or a substituted or unsubstituted alkyl group, preferably a substituted aryl group or a substituted alkyl group, and the substituent is preferably the following general formula (M-I The same groups as R _{2 in (} ) are mentioned. X represents a hydrogen atom or a group capable of splitting off in a coupling reaction with an oxidized product of a developing agent. Further, a dimer or higher multimer can be formed via R ₃₁ , R ₃₂ or X.

Among the magenta couplers of the general formulas (Ma) and (Mb), when the compound of the present invention is used in combination, any desired sufficient performance can be obtained, but a magenta color image is obtained. From the viewpoint of fastness, the coupler represented by formula (Ma) is more preferably used.

Among the magenta couplers represented by the general formula (Ma), the magenta coupler represented by the general formula (MI) is more preferable in terms of color forming property.

General formula (MI)

Embedded image

(Wherein R ₁ is the following general formula (Q-1),
It represents a group represented by (Q-2) or (Q-3).
R ₂ and R ₃ represent a substituent, and n represents 0-4.
When n is 2 or more, plural R ₃ may be the same or different. X represents a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. ) General formula (Q-1) -C (R 4) (R 5) -R 6 ( wherein, R ₄ is an alkyl group, a cycloalkyl group, a heterocyclic group or aryl group, R ₅ and R ₆ Represents a substituent, and R ₄ , R ₅ , and R ₆ are bonded to each other to form a substituent
A 7-membered single ring or condensed ring may be formed. ) General formula (Q-2) -CH (R 7) -R 8 ( wherein, R ₇ represents an alkyl group, a cycloalkyl group, an aryl group or a heterocyclic group, .R R ₈ represents a substituent ₇ And R ₈ may combine with each other to form a 5- to 7-membered ring.)

General formula (Q-3)

Embedded image

(In the formula, R ₉ and R ₁₀ represent a substituent,
m represents 0 to 4. When m is 2 or more, a plurality of R _10's may be the same or different. )

The compound represented by formula (MI) will be described in detail below.

R ₂ is an alkyl group (preferably having a carbon number of 1 to
32 is a linear or branched alkyl group, for example,
Methyl, ethyl, propyl, isopropyl, butyl, t
-Butyl, 1-octyl, tridecyl), a cycloalkyl group (preferably a cycloalkyl group having 3 to 32 carbon atoms, for example, cyclopropyl, cyclopentyl, cyclohexyl), an alkenyl group (preferably having 2 to 32 carbon atoms).
An alkenyl group of, for example, vinyl, allyl, 3-buten-1-yl), an aryl group (preferably having 6 to 3 carbon atoms).
2 aryl groups such as phenyl, 1-naphthyl,
2-naphthyl), heterocyclic group (preferably having 1 to 3 carbon atoms)
2 is a 5- to 8-membered heterocyclic group, for example, 2-thienyl, 4-pyridyl, 2-furyl, 2-pyrimidinyl, 1
-Pyridyl, 2-benzothiazolyl, 1-imidazolyl, 1-pyrazolyl, benzotriazol-2-yl), cyano group, halogen atom (for example, fluorine atom,
Chlorine atom, bromine atom), hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably having 1 to 3 carbon atoms)
2 alkoxy groups, such as methoxy, ethoxy,
1-butoxy, 2-butoxy, isopropoxy, t-butoxy, dodecyloxy), cycloalkyloxy group (preferably cycloalkyloxy group having 3 to 32 carbon atoms, for example, cyclopentyloxy, cyclohexyloxy), aryloxy group (Preferably having 6 to 32 carbon atoms
An aryloxy group of, for example, phenoxy, 2-naphthoxy), a heterocyclic oxy group (preferably having 1 to 3 carbon atoms).
2 heterocyclic oxy groups, for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy, 2-furyloxy), a silyloxy group (preferably a silyloxy group having 1 to 32 carbon atoms, for example, trimethylsilyl Oxy, t-butyldimethylsilyloxy, diphenylmethylsilyloxy),

Acyloxy group (preferably having 2 to 3 carbon atoms)
2 acyloxy groups, such as acetoxy, pivaloyloxy, benzoyloxy, dodecanoyloxy),
Alkoxycarbonyloxy group (preferably having 2 to 2 carbon atoms)
32 alkoxycarbonyloxy groups, for example, ethoxycarbonyloxy, t-butoxycarbonyloxy), cycloalkyloxycarbonyloxy groups (preferably cycloalkyloxycarbonyloxy groups having 4 to 32 carbon atoms, for example, cyclohexyloxycarbonyloxy). ), An aryloxycarbonyloxy group (preferably an aryloxycarbonyloxy group having 7 to 32 carbon atoms, for example, phenoxycarbonyloxy), a carbamoyloxy group (preferably a carbamoyloxy group having 1 to 32 carbon atoms, for example, N , N-dimethylcarbamoyloxy, N-butylcarbamoyloxy), a sulfamoyloxy group (preferably a sulfamoyloxy group having 1 to 32 carbon atoms, for example, N, N-diethylsulfamoyloxy, N Propylsulfamoyloxy), an alkanesulfonyloxy group (preferably an alkanesulfonyloxy group having 1 to 32 carbon atoms, for example, methanesulfonyloxy, hexadecanesulfonyloxy), an arenesulfonyloxy group (preferably having 6 to 32 carbon atoms). An arenesulfonyloxy group, for example, benzenesulfonyloxy),

Acyl group (preferably an acyl group having 1 to 32 carbon atoms, such as formyl, acetyl, pivaloyl,
Benzoyl, tetradecanoyl), an alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 32 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, octadecyloxycarbonyl), a cycloalkyloxycarbonyl group (preferably having 2 to 32 carbon atoms). A cycloalkyloxycarbonyl group of, for example, cyclohexyloxycarbonyl), an aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 32 carbon atoms such as phenoxycarbonyl), a carbamoyl group (preferably having a carbon number of 1 to 32). A carbamoyl group,
For example, carbamoyl, N, N-dibutylcarbamoyl, N-ethyl-N-octylcarbamoyl, N-propylcarbamoyl), an amino group (preferably having 32 carbon atoms)
The following amino groups include, for example, amino, methylamino,
N, N-dioctylamino, tetradecylamino, octadecylamino), anilino group (preferably having 6 to 6 carbon atoms)
32 anilino groups, for example, anilino, N-methylanilino), a heterocyclic amino group (preferably having 1 to 3 carbon atoms).
2 heterocyclic amino groups such as 4-pyridylamino), carbonamido groups (preferably carbonamido groups having 2 to 32 carbon atoms such as acetamide, benzamide, tetradecanamide), ureido groups (preferably having 1 carbon atom). ~ 32 ureido groups, for example, ureido,
N, N-dimethylureido, N-phenylureido),
Imido group (preferably an imide group having 10 or less carbon atoms, such as N-succinimide, N-phthalimide), an alkoxycarbonylamino group (preferably an alkoxycarbonylamino group having 2 to 32 carbon atoms, for example, methoxycarbonylamino, ethoxy). Carbonylamino, t-butoxycarbonylamino, octadecyloxycarbonylamino), an aryloxycarbonylamino group (preferably an aryloxycarbonylamino group having 7 to 32 carbon atoms, for example, phenoxycarbonylamino),

Sulfonamide group (preferably having a carbon number of 1 to
32 sulfonamide groups, for example, methanesulfonamide, butanesulfonamide, benzenesulfonamide, hexadecanesulfonamide), sulfamoylamino groups (preferably sulfamoylamino groups having 1 to 32 carbon atoms, for example, N , N-dipropylsulfamoylamino, N-ethyl-N-dodecylsulfamoylamino), an azo group (preferably an azo group having 1 to 32 carbon atoms,
For example, phenylazo), an alkylthio group (preferably an alkylthio group having 1 to 32 carbon atoms, for example, ethylthio, octylthio), an arylthio group (preferably an arylthio group having 6 to 32 carbon atoms, for example, phenylthio), a heterocyclic thio group. A group (preferably a heterocyclic thio group having 1 to 32 carbon atoms, for example, 2-benzothiazolylthio,
2-pyridylthio, 1-phenyltetrazolylthio),
Alkylsulfinyl group (preferably an alkylsulfinyl group having 1 to 32 carbon atoms, for example, dodecanesulfinyl), arenesulfinyl (preferably 6 to 6 carbon atoms)
32 arenesulfinyl groups, for example, benzenesulfinyl), alkanesulfonyl groups (preferably alkanesulfonyl groups having 1 to 32 carbon atoms, such as methanesulfonyl and octanesulfonyl), arenesulfonyl groups (preferably 6 to 32 carbon atoms). Arenesulfonyl group of, for example, benzenesulfonyl, 1-naphthalenesulfonyl), sulfamoyl group (preferably having 32 carbon atoms).
In the following sulfamoyl group, for example, sulfamoyl,
N, N-dipropylsulfamoyl, N-ethyl-N-
Dodecylsulfamoyl), a sulfo group, and a phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl).

R ₃ represents a group having the same meaning as R ₂ .

In the group represented by the general formula (Q-1),
R ₁₄ is a linear or branched alkyl group or cycloalkyl group having 1 to 32 carbon atoms, or 6 to 32 carbon atoms.
Represents an aryl group or a heterocyclic group, and specific examples of these groups include an alkyl group represented by R ₂ , a cycloalkyl group,
The same as those mentioned in the description of the heterocyclic group or the aryl group. R ₅ and R ₆ represent groups having the same meaning as R ₂ .
Any two of R ₄ , R ₅ and R ₆ may combine with each other to form a 5- to 7-membered monocyclic ring or condensed ring.

In the group represented by the general formula (Q-2), R ₇ has the same meaning as the group represented by R ₄ in the general formula (Q-1), and R ₈ has the same meaning as R ₂ . Represents a group. R ₇ and R ₈ may combine with each other to form a 5- to 7-membered ring.

In the general formula (Q-3), R ₉ and R
₁₀ represents a group having the same meaning as R ₂ .

X represents a hydrogen atom or a group capable of splitting off upon reaction with an oxidized product of a developing agent. Specifically, the releasable group is a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a carbamoyloxy group, a sulfonyloxy group, a carbonamido group, a sulfonamide group, a carbamoylamino group, a heterocyclic group, an arylazo group, an alkylthio group. , An arylthio group, a heterocyclic thio group and the like.
The preferred range and specific examples of these groups are the same as those mentioned in the description of the group represented by R ₂ . In addition to these, X may be a bis-type coupler in which two molecules of 4-equivalent couplers are bonded via aldehydes or ketones, and X is a photographically useful development accelerator, development inhibitor, desilvering accelerator or leuco dye. It may be a group or a precursor thereof.

The groups represented by R ₁ , R ₂ , R ₃ and X may further have a substituent, and a preferable substituent is a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group or an aryl group. , Heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, heterocyclic oxy group, silyloxy group, acyloxy group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group, Carbamoyloxy group, sulfamoyloxy group, alkanesulfonyloxy group, arenesulfonyloxy group, carboxyl group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, Hetero Amino group, carbonamido group, alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group, sulfonamide group, sulfamoylamino group, imide group, alkylthio group, arylthio group, heterocyclic thio group, sulfinyl group, sulfo group , An alkanesulfonyl group, an arenesulfonyl group, a sulfamoyl group, and a phosphonyl group.

The compound represented by formula (M-I) may form a dimer or higher polymer or polymer with the substituents R ₁ , R ₂ , R ₃ and X.

The preferred range of the compound represented by formula (MI) is described below. In formula (Q-1), R ₄ is preferably an alkyl group. R ₅ and R ₆
Is an alkyl group, cycloalkyl group, aryl group, hydroxyl group, alkoxy group, aryloxy group, amino group, anilino group, carbonamido group, ureido group, sulfonamide group, sulfamoylamino group, imide group, alkylthio group or An arylthio group is preferred, an alkyl group, a cycloalkyl group or an aryl group is more preferred, and an alkyl group is most preferred.

In the general formula (Q-2), R ₇ is preferably an alkyl group, a cycloalkyl group or an aryl group,
A secondary or tertiary alkyl group or a cycloalkyl group is more preferable. R ₈ is preferably an alkyl group, a cycloalkyl group or an aryl group, more preferably an alkyl group or a cycloalkyl group.

In the general formula (Q-3), R ₉ and R
₁₀ is a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an amino group, an anilino group, a carboxylic group. Amido group, alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group, sulfonamide group, sulfamoylamino group, imide group, alkylthio group, arylthio group, heterocyclic thio group, sulfinyl group, alkanesulfonyl group, arenesulfonyl group Group, sulfamoyl group,
Phosphonyl group is preferred, halogen atom, alkyl group,
Cycloalkyl group, aryl group, alkoxy group, aryloxy group, amino group, anilino group, carbonamido group, ureido group, sulfonamide group, sulfamoylamino group, alkylthio group or arylthio group is more preferable, and alkyl group, cyclo An alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group or an arylthio group is particularly preferable. 0-3 are preferable and, as for m, 1 or 2 is more preferable. Further, the substitution position of R ₉ is more preferably the ortho position of the phenyl group.

R ₁ is the general formula (Q-1) or (Q-3)
Is more preferably a group represented by the general formula (Q-
1) is more preferred, and it is more preferred that R ₄ , R ₅ and R _{6 in the} group represented by general formula (Q-1) are both alkyl groups, and R ₁ is t. −
Most preferably, it is a butyl group. Preferred specific examples of the group represented by R ₁ are shown below, but the present invention is not limited thereto.

[0077]

[Chemical 43]

[0078]

[Chemical 44]

[0079]

Embedded image

R ₂ is an alkoxy group, an aryloxy group,
Acyloxy group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkanesulfonyloxy group, arenesulfonyloxy group, acyl group, alkoxycarbonyl group, cycloalkyl Oxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group,
Sulfonamide group, sulfamoylamino group, imide group, alkylthio group, arylthio group, heterocyclic thio group, alkanesulfonyl group, arenesulfonyl group or sulfamoyl group is preferable, and alkoxy group, aryloxy group, acyl group, alkoxycarbonyl group. , Cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group, sulfonamide group, sulfamoylamino group, imide Further preferred are groups, alkylthio groups, arylthio groups or sulfamoyl groups. The substitution position of R ₂ is preferably meta or para with respect to the carbon atom bonded to the pyrazolotriazole ring, and more preferably para.

R ₃ is a fluorine atom, a chlorine atom, a bromine atom,
Alkyl group, cycloalkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, carboxyl group, acyl group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group A carbamoyl group,
Amino group, anilino group, carbonamido group, alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group, sulfonamide group, sulfamoylamino group, imide group, alkylthio group, arylthio group,
Heterocyclic thio group, sulfinyl group, sulfo group, alkanesulfonyl group, arenesulfonyl group, sulfamoyl group and phosphonyl group are preferable. n is preferably 0 to 3,
0 or 1 is more preferable.

X is preferably a hydrogen atom, a chlorine atom, a bromine atom, an aryloxy group, an alkylthio group, an arylthio group, a heterocyclic thio group or a heterocyclic group, more preferably a chlorine atom or an aryloxy group, and most preferably a chlorine atom. . Preferred specific examples of the group represented by X are shown below, but the present invention is not limited thereto.

[0083]

Embedded image

[0084]

[Chemical 47]

From the viewpoint of the effect of the present invention, among the compounds represented by the general formula (MI), the compound represented by the following general formula (M-II) is preferable, and the following general formula (M-III) is preferable. Compounds represented by are more preferable.

[0086]

Embedded image

In the formula, R ₂ , R ₃ , n and X have the same meanings as R ₂ , R ₃ , n and X in formula (M-I).

[0088]

[Chemical 49]

In the formula, R ₁₁ and R ₁₂ represent a hydrogen atom or a substituent, A represents —CO— or —SO ₂ —, and R
₁₃ represents an alkyl group, an aryl group, an alkoxy group, an alkylamino group or an anilino group, R ₁₄ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkanesulfonyl group or an arenesulfonyl group, and X represents a hydrogen atom or It represents a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent. R ₁₃ and R ₁₄ may combine with each other to form a 5- to 7-membered ring.

In the general formula (M-III), R ₁₁ and R
₁₂ is preferably hydrogen atom, fluorine atom, chlorine atom, bromine atom, alkyl group, cycloalkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, carboxyl group, acyl Group, alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, amino group, anilino group, carbonamido group, alkoxycarbonylamino group, aryloxycarbonylamino group, ureido group, sulfonamide group, sulfa Moylamino group, imide group, alkylthio group, arylthio group, heterocyclic thio group, sulfinyl group, sulfo group, alkanesulfonyl group, arenesulfonyl group, sulfamoyl group and phosphonyl group are preferable. R ₁₃ is preferably an alkyl group or an aryl group, and R ₁₄ is preferably a hydrogen atom or an alkyl group. A is more preferably -CO-. X
Is a hydrogen atom, chlorine atom, bromine atom, aryloxy group,
An alkylthio group, an arylthio group, a heterocyclic thio group or a heterocyclic group is preferable, a chlorine atom or an aryloxy group is more preferable, and a chlorine atom is most preferable.

Specific examples of the pyrazolotriazole magenta coupler represented by formula (Ma) or (Mb) that can be used in the present invention are shown below, but the present invention is not limited thereto.

[0092]

Embedded image

[0093]

[Chemical 51]

[0094]

Embedded image

[0095]

Embedded image

[0096]

[Chemical 54]

[0097]

[Chemical 55]

[0098]

[Chemical 56]

[0099]

[Chemical 57]

[0100]

Embedded image

[0101]

Embedded image

[0102]

Embedded image

[0103]

[Chemical formula 61]

[0104]

Embedded image

[0105]

[Chemical formula 63]

[0106]

[Chemical 64]

[0107]

Embedded image

[0108]

[Chemical formula 66]

[0109]

Embedded image

[0110]

[Chemical 68]

In order to further improve the fastness to light, the combined use of the compound represented by the general formula (L) is particularly effective. Next, the compound represented by formula (L) will be described. A represents a methine group or a nitrogen atom. R
₄₁ , R ₄₂ , R ₄₃ and R ₄₄ may be the same or different. R _{41 to} R ₄₄ are hydrogen atom, halogen atom, alkyl group (eg ethyl group, 2-ethylamino-ethyl group), aryl group (eg phenyl group), alkylamino group (eg methylamino group, ethylamino group, propyl group). Amino group, diethylamino group, β-hydroxyethylamino group, di-β-hydroxyethylamino group, β-sulfoethylamino group), arylamino group (for example, anilino group, o-, m- or p-sulfoanilino group, o
-, M- or p-chloroanilino group, o-, m- or p-anisino group, o-, m- or p-toluidino group, o-, m- or p-carboxyanilino group, hydroxyanilino group, Sulfonaphthylamino group, o-, m
-Or p-aminoanilino group, o-acetamino-anilino group etc.), heterocyclic group (eg morpholinyl group, piperidyl group etc.), alkylthio group (eg methylthio group, ethylthio group etc.), arylthio group (eg phenylthio group, tolylthio group) Etc.), alkyloxy group (eg methoxy group, ethoxy group etc.), aryloxy group (eg phenoxy group, naphthoxy group, o-troxy group, p-sulfophenoxy group etc.), heterocyclic thio group (eg benzothiazoylthio group) Group, benzimidazoylthio group, phenyltetrazolylthio group, etc.) and cyclohexylamino group. The alkyl part of these groups,
The cycloalkyl moiety, aryl moiety and heterocyclic moiety may be substituted. The substituent may be the same as R _{41 to} R ₄₄ , but other preferable ones are —SO ₃
M, -OM, -CO ₂ M is used (M is a hydrogen atom,
Represents a metal atom such as Na, K and Li. ) Next, specific examples of the compound represented by formula (L) are shown below.
It is not limited to these.

[0112]

[Table 1]

[0113]

[Table 2]

[0114]

[Table 3]

These compounds of the general formula (L) can be added to any of the layers constituting the silver halide light-sensitive material of the present invention, and in a preferred embodiment, they are silver halide photographic light-sensitive materials. It is a non-photosensitive hydrophilic colloid layer among constituent layers of the material. The non-photosensitive hydrophilic colloid layer is preferably a layer containing the ultraviolet absorber of the present invention or a layer closer to the support (for example, an intermediate layer). The compound represented by the general formula (L) of the present invention may be used alone or in combination of two or more kinds. The addition amount can be used in a wide range, but usually 10 to 300 mg / m
² , preferably 10 to 200 mg / m ² , and more preferably 20 to 150 mg / m ² .

In the present invention, it is preferable to use a compound capable of capturing the compound represented by the general formula (L) and enhancing the whitening effect (hereinafter referred to as a capturing agent) in combination. As capture agents, Japanese Examined Patent Publication Nos. 43-13498 and 43-22882,
US Pat. Nos. 3,052,544 and 3,666,4
70, 3,167,429, 3,168,
N-vinylpyrrolidone-based polymers described in the respective specifications of No. 403 and No. 3,252,801, US Pat. Nos. 2,448,507, and 2,448,508,
Pyridine-based polymers described in US Pat. No. 2,721,852, morpholine-based polymers described in US Pat. No. 3,341,332, US Pat. No. 3,006,762. The oxazolidine-based polymer, polyvinyl alcohol-based polymer and the like described in the specification can be used. In particular, poly-N-vinylpyrrolidone having a structure of the following repeating unit or a copolymer derived from N-vinylpyrrolidone and an ethylenically unsaturated monomer is preferable.

[0117]

[Chemical 69]

The above-mentioned scavenger can be added to any layer of the silver halide color photographic light-sensitive material according to the present invention. In a preferred embodiment, it is one of the constituent layers of the silver halide color photographic light-sensitive material. A non-photosensitive hydrophilic colloid layer containing the compound of formula (L). The amount of the capture agent added is preferably 1 to 200 mg / m ² ,
10 to 100 mg / m ² is more preferable. The preferred molecular weight range of the capture agent is 4,000 to 600,000, more preferably 5,000 to 200,000. Specific examples of the ethylenically unsaturated monomer include vinyl monomers such as those described in US Pat. No. 5,057,408, columns 33 to 34 (for example, acrylic acid and its ester, methacrylic acid and its ester). , Maleic acid and its monoalkyl esters, vinyl esters (vinyl acetate, vinyl propionate, etc.), acrylamides, methacrylamides, olefins, styrenes, vinyl ethers and the like.

The color light-sensitive material of the present invention is constituted by coating at least one yellow color forming silver halide emulsion layer, magenta color forming silver halide emulsion layer and cyan color forming silver halide emulsion layer on a support. can do. In general color photographic paper, color reproduction by the subtractive method can be performed by including a color coupler which forms a dye having a complementary color relationship with the light to which the silver halide emulsion is exposed. In a general color photographic paper, silver halide emulsion grains are spectrally sensitized by the blue-sensitive, green-sensitive and red-sensitive spectral sensitizing dyes in the order of the color-forming layers described above, and on the support in the order described above. It can be constructed by coating. However, the order may be different from this. In other words, from the viewpoint of rapid processing, it is preferable that the photosensitive layer containing the largest silver halide grains having the average grain size comes to the uppermost layer, or from the viewpoint of storage stability under light irradiation, the lowermost layer is the magenta color photosensitive layer. In some cases it may be preferable to do so. Further, the light-sensitive layer and the color-developing hue may not have the above correspondence, and at least one infrared-sensitive silver halide emulsion layer can be used.

The support used in the present invention may be any support which can be coated with a photographic emulsion layer such as glass, paper and plastic film, but the most preferred is a reflection type support. The "reflective support" used in the present invention refers to one which enhances the reflectivity to make the dye image formed on the silver halide emulsion layer clear, and such a reflective support is a support. Those coated with a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate, or calcium sulfate dispersed therein, or those using the hydrophobic resin itself containing a dispersed light-reflecting substance as a support. Is included. For example, polyethylene coated paper, polyethylene terephthalate coated paper, polypropylene type synthetic paper, a transparent support provided with a reflective layer, or in combination with a reflective material, such as a glass plate, polyethylene terephthalate, a polyester film such as cellulose triacetate or cellulose nitrate, Examples include polyamide film, polycarbonate film, polystyrene film, vinyl chloride resin, and the like. The reflective support used in the present invention is a paper support whose both surfaces are coated with a water resistant resin layer, and it is preferable that at least one of the water resistant resin layers contains white pigment fine particles. The white pigment particles are preferably contained in a density of 12% by weight or more, more preferably 14% by weight.
That is all. As the light-reflecting white pigment particles, it is preferable to sufficiently knead the white pigment in the presence of a surfactant, and it is preferable to use pigment particles whose surfaces are treated with a divalent to tetravalent alcohol. It is preferable that the white pigment fine particles are uniformly dispersed in the reflective layer without forming aggregates of particles, and the size of the distribution is determined by the occupation area ratio (%) (Ri) of the fine particles projected on a unit area. It can be determined by measuring. The coefficient of variation of the occupied area ratio (%) is Ri
Can be obtained by the ratio s / R of the standard deviation s of Ri to the average value (R) of In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine particles of the pigment is 0.15 or less,
Furthermore, 0.12 or less is preferable. 0.08 or less is particularly preferable.

In the present invention, the silver halide grains are 9
It is preferable to use silver chloride, silver chlorobromide or silver chloroiodobromide grains in which 5 mol% or more is silver chloride. In particular, in the present invention, in order to accelerate the development processing time, a silver chlorobromide or silver chloride containing substantially no silver iodide can be preferably used. The term "substantially free of silver iodide" as used herein means that the silver iodide content is 1 mol% or less, preferably 0.2 mol% or less. On the other hand, for the purpose of enhancing high illuminance sensitivity, spectral sensitization sensitivity, or enhancing stability over time of a light-sensitive material, 0.01 to 3 mol% on the emulsion surface as described in JP-A-3-84545. In some cases, high silver chloride grains containing silver iodide are preferably used. The halogen composition of the emulsion may be different or the same between grains, but if an emulsion having the same halogen composition among grains is used, it is easy to make the properties of each grain uniform. Regarding the halogen composition distribution inside the silver halide emulsion grains, the so-called uniform structure grains having the same composition in any part of the silver halide grains, or the core inside the silver halide grains and the shell surrounding it. (shell)
Particles having a so-called laminated structure having a different halogen composition with [one or more layers], or a structure having a portion having a different halogen composition in a non-layer form inside or on the surface of the particle (edges, corners or surfaces of the particles when present on the surface of the particle) Particles having a structure in which portions having different compositions are bonded to each other can be appropriately selected and used. In order to obtain high sensitivity, it is advantageous to use either of the latter two rather than the particles having a uniform structure, and it is also preferable from the viewpoint of pressure resistance. When the silver halide grains have the structure as described above, the boundary between different portions in the halogen composition is an unclear boundary because a mixed crystal is formed due to the composition difference even if the boundary is clear. It may also be one that positively has a continuous structural change.

The high silver chloride emulsion used in the present invention preferably has a structure having a silver bromide localized phase in the inside and / or on the surface of the silver halide grain in the form of layer or non-layer as described above. The halogen composition of the localized phase preferably has a silver bromide content of at least 10 mol%, more preferably more than 20 mol%. The silver bromide content of the silver bromide localized layer is analyzed using an X-ray diffraction method (for example, described in “Chemical Society of Japan, New Experimental Chemistry Lecture 6, Structural Analysis” Maruzen). can do. And these localized phases are the inside of the particle, the edge of the particle surface,
It can be on a corner or on a surface, but one preferred example is one that is epitaxially grown on the corner of the grain. It is also effective to further increase the silver chloride content of the silver halide emulsion for the purpose of reducing the replenishment amount of the developing solution. In such a case, an almost pure silver chloride emulsion having a silver chloride content of 98 mol% to 100 mol% is also preferably used.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain and the number average thereof is taken) is 0. 1 μm to 2 μm is preferable. Further, the particle size distribution thereof is preferably a so-called monodisperse coefficient of variation of 20% or less (standard deviation of particle size distribution divided by average particle size), preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating. The shape of silver halide grains contained in a photographic emulsion is regular, such as cubic, tetradecahedral or octahedral.
Those having a (regular) crystal form, those having an irregular (eg regular) crystal form such as spheres and plates, or those having a composite form thereof can be used. It may also be a mixture of materials having various crystal forms. In the present invention, 50% or more, preferably 7% or more of the particles having the above-mentioned regular crystal form are used in the present invention.
It is preferable to contain 0% or more, more preferably 90% or more. In addition to these, an emulsion in which tabular grains having an average aspect ratio (diameter in terms of circle / thickness) of 5 or more, preferably 8 or more exceeds 50% of all grains as a projected area can also be preferably used.

The silver salt (bromide) bromide emulsion used in the present invention is P.Gl.
Chimie et Phisique Photographique (Paul by afkides
Montel, 1967), GF Duffin, Photograp
hicEmulsion Chemistry (Focal Press, 1966)
,) By VL Zelikman et al Making and Coating Phot
It can be prepared using the method described in, for example, ographic Emulsion (Focal Press, Inc., 1964). 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 any one of a one-sided mixing method, a simultaneous mixing method, and a combination thereof. You may use. It is also possible to use a method of forming grains in an atmosphere in which silver ions are excessive (so-called reverse mixing method). 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 nearly uniform grain size can be obtained. The localized phase of the silver halide grain of the present invention or its substrate preferably contains different metal ions or complex ions thereof. The preferred metal is selected from metal ions or metal complexes belonging to Group VIII and Group IIb of the Periodic Table, and lead ions and thallium ions. Iridium mainly in the localized phase,
Ions selected from rhodium or iron or complex ions thereof, and mainly used as a substrate in combination with metal ions selected from osmium, iridium, rhodium, platinum, ruthenium, palladium, cobalt, nickel, iron or complex ions thereof be able to. Further, the type and concentration of the metal ion can be changed depending on the localized phase and the substrate. Plural kinds of these metals may be used. In particular, iron and iridium compounds are preferably present in the silver bromide localized phase.

These metal ion-providing compounds are used in a gelatin aqueous solution which becomes a dispersion medium when silver halide grains are formed,
Of the silver halide grains of the present invention by means such as adding in an aqueous solution of a halide, in an aqueous solution of silver salt or other aqueous solution, or in the form of silver halide fine particles containing metal ions in advance and dissolving the fine particles. It is contained in the localized phase and / or other particle portion (matrix). The metal ions used in the present invention can be contained in the emulsion grains either before, during or immediately after grain formation. This can be changed depending on the position of the metal ion contained in the particle.

The silver halide emulsion used in the present invention is
Usually, it is chemically and spectrally sensitized. Regarding the chemical sensitization method, chemical sensitization using a chalcogen sensitizer (specifically, sulfur sensitization represented by the addition of an unstable sulfur compound, selenium sensitization with a selenium compound, tellurium sensitization with a tellurium compound is performed. Noble metal sensitization typified by gold sensitization, reduction sensitization and the like can be used alone or in combination. As the compound used for the chemical sensitization, those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column are preferably used. The effect of the constitution of the light-sensitive material of the present invention is more remarkable than when the gold-sensitized high silver chloride emulsion is used. The emulsion used in the present invention is a so-called surface latent image type emulsion in which a latent image is mainly formed on the grain surface. To the silver halide emulsion used in the present invention, various compounds or their precursors are added for the purpose of preventing fog during the production process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. be able to. As specific examples of these compounds, those described on pages 39 to 72 of the above-mentioned JP-A No. 62-215272 are preferably used. Furthermore, the 5-arylamino-1,2,3,4-thiatriazole compound described in EP 0,447,647 (wherein the aryl residue has at least one electron-withdrawing group) is also preferably used. To be

Spectral sensitization is carried out for the purpose of imparting spectral sensitivity in a desired light wavelength region to the emulsion of each layer in the light-sensitive material of the present invention. In the light-sensitive material of the present invention, blue, green,
Examples of spectral sensitizing dyes used for spectral sensitization in the red region include, for example, Heterocyclic compounds-Cyanine by FM Hamer.
dyes andrelated compounds (John Wiley & Sons [New
[York, London], 1964). As specific examples of compounds and spectral sensitization methods, those described in JP-A-62-215272, page 22, upper right column to page 38 are preferably used. Further, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a particularly high silver chloride content, JP-A 3-1 is known.
The spectral sensitizing dye described in No. 23340 is very preferable from the viewpoint of stability, strength of adsorption, temperature dependence of exposure and the like. In the case of efficiently spectrally sensitizing the infrared region in the light-sensitive material of the present invention, JP-A-3-15049, page 12, upper left column to 2
Page 1, lower left column, or JP-A-3-20730, page 4, lower left column to page 15, lower left column, European Patent No. 0,420,011 4
P. 21 line to p. 6 line 54, EP 0,420,012
No. 4, p. 12, line 10 to p. 33, European Patent 0,443,
The sensitizing dyes described in US Pat. No. 466 and US Pat. No. 4,975,362 are preferably used.

To incorporate these spectral sensitizing dyes in a silver halide emulsion, they may be dispersed directly in the emulsion, or water, methanol, ethanol, propanol, methyl cellosolve, 2,2,2. It may be added to the emulsion by dissolving it in a solvent such as 3,3-tetrafluoropropanol alone or in a mixed solvent. Also, Japanese Patent Publication No.
No. 3389, No. 4427555, No. 57-2208
As described in US Pat. No. 9,822,135 and US Pat.
An aqueous solution or a colloidal dispersion in which a surfactant coexists as described in No. 006,025 may be added to the emulsion. Further, after being dissolved in a solvent which is substantially immiscible with water, such as phenoxyethanol, it may be dispersed in water or a hydrophilic colloid and added to the emulsion. As described in JP-A Nos. 53-102733 and 58-105141, they may be directly dispersed in a hydrophilic colloid and the dispersion may be added to the emulsion. The time of addition to the emulsion may be any stage of emulsion preparation known to be useful so far. In other words, before preparing the silver halide emulsion grains, during grain formation, immediately after grain formation, before entering the washing step, before chemical sensitization, during chemical sensitization, immediately after chemical sensitization, until the emulsion is cooled and solidified. You can choose from either. Most commonly, after the completion of chemical sensitization,
It is carried out before the application, but is disclosed in US Pat. No. 3,62.
It is also possible to add spectral sensitization simultaneously with chemical sensitization by adding it at the same time as the chemical sensitizer as described in JP-A-58-113.
It can be carried out prior to chemical sensitization as described in No. 928, or it can be added to initiate spectral sensitization before the completion of silver halide grain precipitation. Furthermore, the spectral sensitizing dyes may be added separately as taught in U.S. Pat. No. 4,225,666, i.e., a portion prior to chemical sensitization and the balance after chemical sensitization. Additions are also possible and can be at any time during silver halide grain formation including the method taught in U.S. Pat. No. 4,183,756. Of these, it is particularly preferable to add a sensitizing dye before the step of washing the emulsion with water or before the chemical sensitization.

The addition amount of these spectral sensitizing dyes is wide depending on the case, and is 0.5 per mol of silver halide.
The range of × 10 ^-6 mol to 1.0 × 10 ^-2 mol is preferable.
More preferably, 1.0 × 10 ^-6 mol to 5.0 × 10 ^-3
It is in the molar range. In the present invention, particularly when a sensitizing dye having a spectral sensitizing sensitivity in the red region to the infrared region is used, the compounds described in JP-A-2-157749, page 13, lower right column to page 22, lower right column, may be used in combination. preferable. By using these compounds, the storability and processing stability of the light-sensitive material and the supersensitizing effect can be specifically enhanced. Above all, it is particularly preferable to use the compounds of the general formulas (IV), (V) and (VI) in the same patent in combination. These compounds are used in an amount of 0.5 × 10 ^-5 mol to 1 mol of silver halide.
5.0 × 10 ⁻² mol, preferably 5.0 × 10 ⁻⁵ mol
An amount of 5.0 × 10 ⁻³ mol is used, and 0.1 times to 10000 times, preferably 0.5 times to 5 times per mol of the sensitizing dye.
There is an advantageous usage amount in the range of 000 times.

The light-sensitive material of the present invention is used not only in a printing system using a general negative printer but also in a solid state laser using a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a semiconductor laser as an excitation light source, and a nonlinear laser. It is preferably used for digital scanning exposure using monochromatic high-density light such as a second harmonic generation light source (SHG) combined with an optical crystal. Compact system,
In order to make it inexpensive, it is preferable to use a semiconductor laser, or a second harmonic generation light source (SHG) that is a combination of a semiconductor laser or a solid-state laser and a nonlinear optical crystal. In particular, in order to design an apparatus which is compact, inexpensive, has a long life and high stability, it is preferable to use a semiconductor laser, and it is desirable to use a semiconductor laser as at least one of the exposure light sources. When such a scanning exposure light source is used, the spectral sensitivity maximum of the photosensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source used. A solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal can halve the oscillation wavelength of the laser, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the light-sensitive material can be provided in the normal three regions of blue, green and red. The device is inexpensive and highly stable,
In order to use a semiconductor laser as a light source to make it compact, it is preferable that at least two layers have a spectral sensitivity maximum at 670 nm or more. this is,
This is because the inexpensive and stable III-V group semiconductor lasers available at present have emission wavelengths only in the red to infrared regions. However, at the laboratory level, II-VI in the green and blue regions
Oscillation of group-based semiconductor lasers has been confirmed, and it is fully expected that these semiconductor lasers can be stably used at low cost if the manufacturing technology of the semiconductor lasers is improved. In such a case, it becomes less necessary for at least two layers to have a spectral sensitivity maximum at 670 nm or more.

In such scanning exposure, the time for which the silver halide in the light-sensitive material is exposed is the time required for exposing a certain minute area. As this minute area, the minimum unit for controlling the light quantity from each digital data is generally used and is called a pixel. Therefore, the exposure time per pixel changes depending on the size of this pixel. The size of this pixel depends on the pixel density and is practically 50 to 2000 dpi. When the exposure time is defined as the time for exposing the pixel size when the pixel density is 400 dpi, the preferable exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less.
In the light-sensitive material according to the present invention, a hydrophilic colloid layer is added to a hydrophilic colloid layer for the purpose of preventing irradiation or halation and improving safety of safelight.
Water-soluble dyes (in particular, oxonol dyes and cyanine dyes), which can be decolorized by the treatment, described on pages 27 to 76 of 7,490A2 can be added. Some of these water-soluble dyes deteriorate the color separation and safelight safety when the amount used is increased. As a dye that can be used without deteriorating color separation, European Patent EP 0,53
9,978, JP-A-5-127325 and JP-A-5-12
The water-soluble dyes described in 7324 are preferred.

In the present invention, a colored layer which can be decolorized by treatment can be used in place of the water-soluble dye or in combination with the water-soluble dye. The coloring layer that can be decolorized by the treatment used may be in direct contact with the emulsion layer, or may be disposed so as to be in contact with the emulsion layer via an intermediate layer containing a treatment color mixing inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided in the lower layer (support side) of the emulsion layer that develops a primary color of the same kind as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to selectively install only a part of them. It is also possible to provide a colored layer that is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is the wavelength with the highest optical density in the wavelength range used for exposure (visible light range from 400 nm to 700 nm in normal printer exposure, wavelength of scanning exposure light source used in scanning exposure). The optical density value in is preferably 0.2 or more and 3.0 or less. More preferably 0.5 or more and 2.5 or less,
Particularly, 0.8 or more and 2.0 or less are preferable.

In order to form the above colored layer, a conventionally known method can be applied. For example, JP-A-2-28224
No. 4, page 3, upper right column, dyes described on page 8;
No. 7931, page 3, upper right column to page 11, lower left column, a method of incorporating the same in a hydrophilic colloid layer in the form of a solid fine particle dispersion, a method of mordanting an anionic dye with a cationic polymer, and a dye of halogen Method of adsorbing to fine particles such as silver halide and fixing in a layer, JP-A-1-239544
Method using colloidal silver as described in No. As a method for dispersing the fine powder of the pigment in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less, but is substantially water-soluble at least at pH 8 or more is particularly preferable. Kaihei 2-308
244, pp. 4-13. Further, for example, a method of mordanting an anionic dye on a cationic polymer is described on pages 18 to 26 of JP-A-2-84637. Regarding the method for preparing colloidal silver as a light absorber, US Pat. Nos. 2,688,601 and 3;
459,563. Among these methods, the method of incorporating fine powder dyes, the method of using colloidal silver and the like are preferable. As the binder or protective colloid that can be used in the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic colloids can be used alone or together with gelatin. As a preferable gelatin, it is preferable to use low calcium gelatin having a calcium content of 800 ppm or less, more preferably 200 ppm or less. Further, in order to prevent various molds and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, it is preferable to add an antifungal agent as described in JP-A-63-271247.

When the light-sensitive material of the present invention is exposed to a printer, it is preferable to use the band stop filter described in US Pat. No. 4,880,726. As a result, light color mixture is removed, and color reproducibility is significantly improved. The exposed light-sensitive material can be subjected to a conventional color development process, but in the case of the color light-sensitive material of the present invention, it is preferable to perform bleach-fixing after color development for the purpose of rapid processing.
Particularly when the above high silver chloride emulsion is used, the pH of the bleach-fixing solution is preferably about 6.5 or less, more preferably about 6 or less for the purpose of promoting desilvering. Silver halide emulsions and other materials (additives etc.) and photographic constituent layers (layer arrangement etc.) applied to the light-sensitive material according to the present invention, and processing methods and processings applied for processing this light-sensitive material. As additives, the following patent publications, particularly European Patent No. 0,355,
Those described in the specification of 660A2 (JP-A-2-139544) are preferably used.

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[Table 4]

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[Table 5]

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[Table 6]

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[Table 7]

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[Table 8]

Cyan, magenta, or yellow couplers are included in the loadable latex polymer (eg, US Pat. No. 4,203,716) in the presence (or absence) of the high boiling organic solvents listed in the table above. It is also preferable that the polymer is soaked or dissolved with a water-insoluble polymer and an organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers that can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15 and International Publication WO88 / 007.
The homopolymers or copolymers described on pages 12 to 30 of the No. 23 specification can be mentioned. It is more preferable to use a methacrylate-based or acrylamide-based polymer, especially an acrylamide-based polymer in terms of color image stability and the like.

In the light-sensitive material according to the present invention, it is preferable to use a color image storability improving compound as described in European Patent No. 0,277,589A2 together with a coupler. In particular, it is preferably used in combination with a pyrazoloazole coupler, a pyrrolotriazole coupler, or an acylacetamide type yellow coupler. That is, the compound and / or the color development process in the above-mentioned European Patent Specification which chemically bonds with an aromatic amine-based developing agent remaining after the color development process to form a chemically inactive and substantially colorless compound. Use of the compounds in the above-mentioned European patent specification simultaneously or alone to form a chemically inert and substantially colorless compound by chemically bonding with an oxidized product of an aromatic amine type color developing agent which remains afterwards. However, it is preferable to prevent the occurrence of stains and other side effects due to the formation of a coloring dye due to the reaction of the residual color developing agent in the film or the oxidant thereof with the coupler during storage after processing.

Further, as a cyan coupler, there is disclosed in JP-A-2-
No. 33144, a diphenylimidazole-based cyan coupler, a European Patent 0,333,185A2, a 3-hydroxypyridine-based cyan coupler, and a cyclic active methylene-based coupler described in JP-A-64-32260. Cyan coupler, EP 0,456,
226A1 specification, pyrrolopyrazole type cyan coupler, EP 0,484,909, pyrrolo imidazole type cyan coupler, EP 0,4
88,248 and 0,491,197A1
The use of pyrrolotriazole type cyan couplers as described in the specification is preferred. Of these, use of a pyrrolotriazole type cyan coupler is particularly preferable. Examples of the magenta coupler used in the present invention also include 5-pyrazolone-based magenta couplers as described in the known documents in the above table. Examples of 5-pyrazolone magenta couplers include WO92 / 18901 and WO92 / 1.
Arylthio-eliminating 5-pyrazolone-based magenta couplers described in No. 8902 and WO92 / 18903 are preferable in terms of image storability and little change in image quality due to processing.

As the yellow coupler, known acylacetanilide type couplers are preferably used. Among them, a pivaloyl acetanilide type coupler having a halogen atom or an alkoxy group at the ortho position of the anilide ring is preferably used.
European Patent 0,447,969A, JP-A-5-107
701, JP-A-5-113642 and the like, acylacetanilide type couplers in which the acyl group is a 1-substituted cycloalkanecarbonyl group, EP 0,482,
The malondianilide type couplers described in 552A, EP 0,524,540A and the like are preferably used. Further, a group that a pivaloyl acetanilide type yellow coupler, an acyl acetanilide type yellow coupler in which an acyl group is a 1-substituted cycloalkanecarbonyl group, or a malondianilide type yellow coupler reacts with an oxidant of a developing agent to leave. In the case of having, the leaving group may be any of the known groups as described above,
The molecular weight of the leaving group is preferably 250 or less, for example, N-
A benzyl-ethoxy-N-hydantoyl group or the like can be used. More preferably, a leaving group having a molecular weight of 150 or less is used, and for example, a 4,4-dimethyl-N-hydantoyl group can be used. As the method for processing the color light-sensitive material of the present invention, in addition to the method described in the above table, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-207250. No. 97355, page 5, upper left column, line 17 to page 18, lower right column, line 20 are preferable.

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EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 300 g of the compound (A-14) of the present invention, 450 g of an ultraviolet absorber (UV-1), magenta coupler (ExM) 4
5 g, color image stabilizer (Cpd-2) 40 g, (Cpd-
5) 40 g, (Cpd-6) 30 g, (Cpd-8) 1
00g, high boiling organic solvent (Solv-4 and Solv-5
Weight ratio of 2: 1 mixture) 1700 ml, ethyl acetate 90
0 ml was heated and dissolved at 50 ° C., and this solution was emulsified and dispersed in 5000 g of a 20 wt% gelatin aqueous solution containing 600 ml of 10% sodium dodecylbenzenesulfonate aqueous solution using a high-speed emulsification stirrer (dispersion blade diameter 65 mm,
Emulsified at 5000 rpm for 20 minutes). After completion of the emulsification, water was added and mixed well to obtain an emulsified dispersion (Sample No. 4) in a total amount of 17,000 g (Table 9). Further, as shown in Table 9, the sample No. was changed except that the added compound was changed. Emulsified Dispersion Sample No. 1 to 9 were prepared (emulsion formulation A). In Emulsion Formulation A in Table 9, the addition amount of L-11 was 350 g per 17,000 g of the emulsified dispersion, and the addition amount of additives other than L-11 (Cpd-1, A-11, B-5 or B-8) was It is 300 g.

Next, in order to examine the storage stability of the emulsified dispersion, the particle size stability of the emulsion and the number of coarse particles were evaluated as follows, and the results are shown in Table 10. (Evaluation 1) Particle size immediately after emulsification and after refrigerated storage The average particle size immediately after emulsification and one month after refrigerated storage (4 ° C.) was measured with a Coulter submicron particle analyzer model N4 manufactured by Coulter Etronics. (Evaluation 2) Number of coarse particles after refrigerated storage To 50 g of the emulsified dispersion after refrigerated storage, 200 g of a 10% aqueous gelatin solution was added and dissolved / mixed at 40 ° C., and 5.0 ml of the resulting mixture was 100 cm ² Was applied on a transparent glass dry plate of. 1c under an optical microscope after natural drying
The number of coarse particles having a diameter of 20 μm or more existing per m ² was measured, and an average value at 5 points was calculated.

When the number of coarse particles in the emulsified dispersion is remarkably increased, the light-sensitive material using the emulsified dispersion (color print obtained by processing the emulsion) has many defects and is unacceptable for viewing. Further, in general, a coupler-containing dispersion having a small particle size of the emulsified dispersion can obtain a high color density, and an ultraviolet-absorbing agent-containing dispersion has an increased UV blocking ability and is expected to have improved color images and light resistance of a white background. As shown in Table 10, the emulsified dispersions (Nos. 3 to 6 and 9) of the present invention are the emulsion dispersions (No. 7) containing no ultraviolet absorber, the general formula (A) and the general formula (B). Fine particles were obtained as compared with the emulsified dispersion containing no compound (Nos. 1, 2, and 8), the increase in size was small even during cold storage, and the number of coarse particles was also small.

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[Table 9]

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[Table 10]

Preparation of Multilayer Color Printing Paper Sample (Sample No.
K101) After the corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene, a gelatin subbing layer containing sodium dodecylbenzene sulfonate was provided, and various photographic constitution layers were further applied to form a layer constitution shown below. A multilayer color photographic paper (K101) was produced. The coating liquid was prepared as follows.

Silver chlorobromide emulsion B (cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B having a grain size of 0.39 μm (Ag molar ratio). Variation of grain size distribution) Coefficients are 0.10 and 0.0 respectively
8. In each size emulsion, 0.8 mol% of AgBr was locally contained in a part of the surface of the grain based on silver chloride) was prepared. This emulsion contains the green sensitizing dyes D and E shown below.
F is added. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion No. 1 and this silver chlorobromide emulsion B were mixed and dissolved to prepare a coating solution for the third layer having the composition shown below. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the first layer, the second layer, and the fourth to seventh layers were prepared in the same manner as the third layer coating solution. 1-Oxy-3,5-dichloro-s-triazine sodium salt was used as a gelatin hardening agent for each layer. Moreover, the total amount of Cpd-12, Cpd-13, Cpd-14, and Cpd-15 was 15.0 mg / m ² , 6 in each layer.
0.0 mg / m ² , 5.0 mg / m ² and 10.0 m
It was added so as to be g / m ² .

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

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(1.4 × 10 ⁻⁴ mol was added to the large-sized emulsion and 1.7 × 10 ⁻⁴ mol was added to the small-sized emulsion per mol of silver halide.) Green Sensitive emulsion layer

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(Sensitizing dye D per mol of silver halide was 3.0 × 10 ^-4 mol for large size emulsion, 3.6 × 10 ^-4 mol for small size emulsion, and Sensitizing dye E per mol of silver halide was 4.0 × 10 ⁻⁵ mol for large size emulsion and 7.0 for small size emulsion.
^{X10 -5} mol, and sensitizing dye F per mol of silver halide was 2.0 x 10 ^-4 mol for a large size emulsion and 2.8 x 10 ^-4 for a small size emulsion. Mol added. ) Red-sensitive emulsion layer

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(5.0 × 10 ⁻⁵ mol was added to the large-sized emulsion and 8.0 × 10 ⁻⁵ mol was added to the small-sized emulsion per mol of silver halide.)

Further, the following supersensitizer was added to the red-sensitive emulsion layer in an amount of 2.6 × 10 ^-3 mol per mol of silver halide.

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For the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1- (5-methylureidophenyl)-
5-Mercaptotetrazole to silver halide 1
3.5 × 10 ⁻⁴ mol, 3.0 × 10 ⁻³ mol per mol,
2.5 × 10 ^-4 mol was added. Further, 4-hydroxy-6-methyl-1,
3,3a, 7-Tetrazaindene was added at 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively.

To prevent irradiation, the following dyes (the figures in parentheses represent the coating amount) were added to the emulsion layer.

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[Chemical 74]

(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents the coating amount in terms of silver.

Support Polyethylene laminated paper [Polyethylene on the first layer side contains a white pigment (TiO ₂ ) and a bluish dye (ultraviolet)]

First Layer (Blue Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 3: 7 mixture of large size emulsion A having an average grain size of 0.88 μm and small size emulsion A of 0.70 μm (silver molar ratio) The coefficient of variation of the grain size distribution is 0.08 and 0.10, respectively. In each size emulsion, 0.3 mol% of silver bromide is locally contained in a part of the grain surface based on silver chloride. 0.24 Gelatin 1.33 Yellow coupler (ExY) 0.61 Color image stabilizer (Cpd-1) 0.08 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.08 Solvent (Solv-1) 0.22

Second layer (color mixing prevention layer) Gelatin 1.09 Color mixing inhibitor (Cpd-4) 0.11 Solvent (Solv-1) 0.07 Solvent (Solv-2) 0.25 Solvent (Solv-3) 0.19 Solvent (Solv-7) 0.09

Third Layer (Green Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 3 mixture of large size emulsion B having an average grain size of 0.55 μm and small size emulsion B of 0.39 μm (Ag mol) The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and 0.8 mol% of AgBr was locally contained in a part of the grain surface of the silver chloride-based grain in each size emulsion. 11 Gelatin 1.19 Magenta coupler (ExM) 0.12 Ultraviolet absorber (UV-1) 0.12 Color image stabilizer (Cpd-2) 0.01 Color image stabilizer (Cpd-5) 0.01 Color image Stabilizer (Cpd-6) 0.01 Color image stabilizer (Cpd-8) 0.01 Solvent (Solv-4) 0.30 Solvent (Solv-5) 0.15

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.77 Color mixing inhibitor (Cpd-4) 0.08 Solvent (Solv-1) 0.05 Solvent (Solv-2) 0.18 Solvent (Solv-3) 0.14 Solvent (Solv-7) 0.06

Fifth Layer (Red Sensitive Emulsion Layer) Silver chlorobromide emulsion (cubic, 1: 4 mixture of large size emulsion C having an average grain size of 0.50 μm and small size emulsion C of 0.41 μm (Ag mol The coefficient of variation of the grain size distribution was 0.09 and 0.11, and 0.8 mol% of AgBr was locally contained in a part of the grain surface of silver chloride as a base in each size emulsion). 18 Gelatin 0.80 Cyan coupler (ExC) 0.28 UV absorber (UV-3) 0.19 Color image stabilizer (Cpd-1) 0.24 Color image stabilizer (Cpd-6) 0.01 Color image Stabilizer (Cpd-8) 0.01 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-10) 0.01 Solvent (Solv-1) 0.01 Solvent (Solv-6) 0 .21

Sixth layer (UV absorbing layer) Gelatin 0.64 UV absorbing agent (UV-2) 0.45 Stabilizing agent (Cpd-16) 0.05 Solvent (Solv-8) 0.05

Seventh layer (protective layer) Gelatin 1.01 Acrylic modified copolymer of polyvinyl alcohol (Degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-11) 0.01

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[Chemical 75]

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[Chemical 76]

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[Chemical 81]

Then, sample No. An equal weight of the emulsified dispersion of the third layer of K101 shown in Table 9 (No. 2).
~ 9) except that the same sample K102 ~ 109
Was produced. The obtained sensitometers (Fuji Photo Film Co., Ltd., FWK type, light source color temperature 3200 °)
K) was used to give a gradation exposure of a three-color separation filter for sensitometry. The exposure at this time was performed so that the exposure amount was 250 CMS in the exposure time of 0.1 seconds. The exposed sample was processed using a paper processor using a liquid having the following processing steps and processing liquid composition.

Treatment process Temperature Time Replenisher ^* Tank capacity Color development 35 ℃ 45 seconds 161ml 10 liters Bleach fixing 35 ℃ 45 seconds 218ml 10 liters Rinse (1) 35 ℃ 30 seconds −5 liters Rinse (2) 35 ℃ 30 Second-5 liters Rinse (3) 35 ℃ 30 seconds 360 ml 5 liters Dry 80 ℃ 60 seconds * Replenishment amount per 1 m ^{2 of} light-sensitive material (Rinse was a three-tank countercurrent system from (3) to (1))

The composition of each processing liquid is as follows. Color developer Tank solution Replenisher Water 800 ml 800 ml Ethylenediaminetetraacetic acid 3.0 g 3.0 g 4,5-Dihydroxybenzene-1,3-disulfonic acid disodium salt 0.5 g 0.5 g Triethanolamine 12.0 g 12.0 g Potassium chloride 2.5 g -Potassium bromide 0.01 g-Potassium carbonate 27.0 g 27.0 g Optical brightener (WHITEX 4, manufactured by Sumitomo Chemical Co., Ltd.) 1.0 g 2.5 g Sodium sulfite 0.1 g 0.2 g Disodium-N, N-bis (sulfonate ethyl) hydroxylamine 5.0 g 8.0 g N-Ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 7.1 g Water was added to 1000 ml 1000 ml pH (25 ° C / in potassium hydroxide and sulfuric acid) 10.05 10.45

Bleach-fixing solution (tank solution and replenisher are the same) Water 600 ml Ammonium thiosulfate (700 g / l) 100 ml Ammonium sulfite 40 g Ethylenediaminetetraacetic acid iron (III) ammonium 55 g Ethylenediaminetetraacetate iron 5 g Ammonium bromide 40 g Sulfuric acid (67%) 30 g Water was added to 1000 ml pH (25 ° C / acetic acid and ammonia water) 5.8

Rinse solution (same as tank solution and replenisher solution) Sodium chlorinated isocyanurate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5

Each of the samples treated as described above was measured for yellow, magenta and cyan reflection densities with a TCD type densitometer manufactured by Fuji Photo Film Co., Ltd., and light fastness was tested in the following manner. (Light fastness) Sunlight irradiation for 60 days (using an underglass outdoor stall) Fastness is the percentage of the density (D) after the test for the initial density (D ₀ ) = 1.0 for yellow, magenta, and cyan, respectively. Expressed in (%). The minimum yellow density (D _min ) of the white background portion was measured before and after the light irradiation test. The results are shown in Table 10.

From the results of Table 10, the ultraviolet absorber UV-1
And samples (No. K103 to K106, K10) using the additive compound represented by the general formula (A) or the general formula (B).
9) is a comparative example (No. K101, 102, 107, 1).
08), the light resistance of yellow and magenta is improved, and the yellow coloring of the white background is small, which is excellent. Further, the sample (No. K109) in which L-11 was used in combination with UV-1 and A-14 was another sample (No. K10).
1 to K108), the color image residual rate after light irradiation is higher.

Example 2 150 g of the compound (A-14) of the present invention, 1100 g of an ultraviolet absorber (UV-2), 150 g of (Cpd-16),
100 ml of a high boiling organic solvent (Solv-8) and 300 ml of ethyl acetate were dissolved by heating at 50 ° C., and this solution was added with a 10% sodium dodecylbenzenesulfonate aqueous solution of 700 m
1 emulsified and dispersed in 5000 g of 20% by weight gelatin aqueous solution containing a high-speed stirring emulsifier (dispersion blade diameter 65 m
emulsified at 5000 rpm for 20 minutes). After the completion of emulsification, water was added and mixed well to obtain an emulsified dispersion (Sample No. 16) in a total amount of 12000 g (Table 11). Further, as shown in Table 11, the sample No. was changed except that the type of additive compound and the type and amount of ultraviolet absorber were changed. Emulsified Dispersion Sample No. 10 to 25 were prepared (emulsion formulation B).
In the emulsified formulation B in Table 11, the addition amount of L-11 was 240 g per 12000 g of the emulsion, and the addition amount of additives other than L-11 (Cpd-1, A-11, B-5 or B-8).
Is 150 g. In order to investigate the storage stability of the emulsified dispersion, the particle size stability and the number of coarse particles of the emulsified dispersion were evaluated in the same manner as in Example 1, and the results are shown in Table 12.

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[Table 11]

As shown in Table 12, the emulsified dispersions (Nos. 14 to 18, 21, 23 and 25) of the present invention are emulsified dispersions containing no compound of the general formula (A) or the general formula (B). Fine particles were obtained as compared with (Nos. 10 to 13, 19, 20, 22, and 24), the increase in size was small even during refrigerated storage, and the number of coarse particles was also small.

Then, sample No. The emulsified dispersion of the sixth layer of K101 in equal weight is shown in Table 11 (No.
Samples (K
110-K125) were produced. The above sample (K110
To K125) were exposed and processed in the same manner as in Example 1 to evaluate the light fastness of yellow, magenta, cyan and a white background. The obtained results are shown in Table 12. Samples using the ultraviolet absorber UV-2 and the additive compound represented by the general formula (A) or the general formula (B) (K114 to K118,
K121, K123, and K125 are comparative examples (K110).
~ K113, K119, K120, K122, K12
Compared to 4), yellow, magenta, and cyan were excellent in light resistance, and the white background had less yellow coloring. UV-2 and A-1
The sample (K121) in which L-11 was used in combination with No. 4 had a higher residual color image after light irradiation than the other samples (K110 to K120). L-11 is a fluorescent whitening agent
When replaced with 0 or L-14, the same effect as L-11 was obtained.

[0191]

[Table 12]

[0192]

INDUSTRIAL APPLICABILITY According to the present invention, a silver halide photograph having an emulsion dispersion containing few coarse particles, fine and excellent in storage stability, and having improved color images after color processing and light fastness on a white background A photosensitive material can be obtained.

Claims (4)

[Claims] 1. A support having at least one cyan dye forming coupler-containing silver halide emulsion layer, and at least one layer.
Silver halide color photographic light-sensitive material having a photographic constituent layer consisting of one layer of magenta dye-forming coupler-containing silver halide emulsion layer, at least one layer of yellow dye-forming coupler-containing silver halide emulsion layer and at least one non-photosensitive layer In the same layer of at least one of the above-mentioned photographic constituent layers, in the general formula (I), general formula (II)
A silver halide color photographic light-sensitive material containing at least one kind of an ultraviolet absorber selected from the compounds represented by and at least one kind of the compound represented by the general formula (A) or (B). material. General formula (I) General formula (II) General formula (III): In formula (I), R ₁ , R ₂ , R ₃ and R ₄ are each a hydrogen atom, a halogen atom, a nitro group, a hydroxyl group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acylamino group, a carbamoyl group or a sulfo group. Represents a group, an alkylthio group or an arylthio group. R ₁ and R ₂ and R ₃ and R ₄ may be connected to each other to form a 5- or 6-membered ring. Formula (II) in R _5, R ₆ are each a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group or an acyl group, X represents -CO- or -COO-, m is an integer of from 1 to 5 And n
Is an integer of 1 to 4 and p is an integer of 1 to 4. In the general formula (III), A, B and C each represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group or a heterocyclic group. However, at least one of A, B, and C represents the general formula (IIIa). General formula (IIIa): In formula (IIIa), R ₇ and R ₈ each represent a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group. General formula (A) In general formula (A), Q is a group of non-metal atoms necessary for forming a 5- to 7-membered ring with a nitrogen atom. R ₁₁ represents an alkyl group, an aryl group or an alkoxy group. General formula (B): In the general formula (B), R ₂₁ represents a hydrogen atom or an alkyl group, and R ₂₂ represents an alkyl group, an aryl group or an alkoxy group. R ₂₃ represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an acylamino group or a sulfonamide group. X ₁ represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or an aryloxy group. 2. The compound represented by the general formula (A) or the general formula (B) is further represented by the following general formula (A-1) or the general formula (B-1). 1. A silver halide color photographic light-sensitive material as described in 1. General formula (A-1): In formula (A-1), R ₁₁ and R ₁₂ each independently represent the same group as R _{11 in} formula (A). General formula (B-1): In formula (B-1), R ₂₁ and R ₂₄ each independently represent the same group as R _{21 in} formula (B). Also R ₂₂ and R ₂₅
Each independently represents the same group as R _{22 in} formula (B). X ₁ represents the same group as X _{1 in} formula (B). 3. A magenta coupler represented by the general formula (Ma) or (Mb) in the same layer as a photographic constituent layer containing a compound represented by the general formula (A) or (B). 3. The silver halide color photographic light-sensitive material according to claim 1, wherein at least one kind is contained. General formula (Ma): General formula (Mb): (In the formula, R ₃₁ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group or a heterocyclic oxy group, and R ₃₂ represents an aryl group. Represents a group or an alkyl group, X represents a hydrogen atom or a group capable of splitting off in a coupling reaction with an oxidized product of a developing agent, and further represents a dimer or higher multimer through R ₃₁ , R ₃₂ or X. It may be formed.) 4. A fluorescent whitening agent represented by the general formula (L) in the same layer as the photographic constituent layer containing the compound represented by the general formula (A) or the general formula (B) or in a layer closer to the support than the photographic layer. 4. The silver halide color photographic light-sensitive material according to claim 1, 2 or 3, which contains at least one agent. General formula (L) (In the formula, R ₄₁ , R ₄₂ , R ₄₃ and R ₄₄ represent a hydrogen atom or a substituent. A represents a nitrogen atom or a methine group.)