JPH06194794A - Silver halide color photographic material - Google Patents

Abstract

PURPOSE:To provide a silver halide color photographic material with high sensitivity, little photographic fog, and excellent latent image storing property by containing a specified formalin scavenger in a photographic constituting layer and a specified compound in an emulsifier layer, respectively. CONSTITUTION:At least one kind of formalin scavengers represented by the formula I is contained in a photographic constituting layer, and at least one kind of compounds represented by the formula II is contained in an emulsion layer. In the formulae I, II, R1 represents hydrogen atom, an alkyl group, an aryl group, or an alkoxyl group, R2 represents hydrogen atom, an alkyl group, or an acyl group, and X represents -CH2-. Z1 represents oxygen atom, sulfur atom, or selenium atom, V1-V4 each represent hydrogen atom or a halogen atom, and V1 and V2, V2 and V3, V3 and V4 each may be mutually bonded, respectively, to form a ring. R21-R25 each represent hydrogen atom, a halogen atom, or a hydroxyl group, and the mutually adjacent groups of R21-R24 may be bonded to each other to form a 5-membered to 6-membered ring.

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 has high sensitivity and little fog.
It also relates to a silver halide color photographic light-sensitive material having improved latent image storability.

[0002]

2. Description of the Related Art It is well known that silver halide photographic light-sensitive materials (hereinafter, also simply referred to as "light-sensitive materials") are affected by the action of various harmful gases. In particular, formalin (formaldehyde) reacts with various constituent compounds such as couplers to cause undesired changes such as a decrease in color density and contamination.

In order to prevent such deterioration of photographic characteristics, a technique has been developed in which a light-sensitive material contains a compound (formalin scavenger) which reacts with formalin and changes it into a harmless substance. For example, JP-A-50-87028
No. 57-133450, No. 58-150950, U.S. Pat.
No. 7, No. 3,652,278, No. 3,811,891, No. 4,003,748,
4,411,987, 4,414,309, 4,418,142, 4,4
64,463, U.S. Defense Patent 900,028, West German Patent 3,223,699
Issue 3,227,961, Issue 3,227,962, Research Disclosure (hereinafter referred to as RD) 101
No. 33, etc.

However, these compounds have the drawback that the fog density increases when they are added to the photographic material in an amount sufficient to obtain a sufficient effect.

On the other hand, in general, most of the light-sensitive materials have a so-called defect that the latent image formed by exposure regresses with time, which is a great obstacle to high sensitivity.

Therefore, many techniques for preventing latent image regression have been known in the past. For example, British Patent 1,308,
777, 1,335,923, 1,353,527, 1,378,354
Issue, 1.386,630, 1,387,654, 1,389,089,
1,391,672, 1,390,237, 1,394,371, 1,4
12,294, 1,458,197, U.S. Patents 3,881,939, 4,
397,942, JP-A-47-37922, 49-17720, 57-22
No. 234, No. 57-158840, No. 58-90634, No. 58-152235, etc., a method using a compound containing a sulfur, oxygen or nitrogen atom in a silver halide emulsion, or JP-A-57-104.
The method of adding the sulfinic acid derivative described in Nos. 927 and 62-21145, and the method of using various organic compounds are RD17.
No. 643. However, these methods also often cause unfavorable adverse effects such as generation of fog and a large decrease in sensitivity.

The fog caused by these latent image stabilizers is, for example, the addition of 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, benzimidazole, 2,5-dimercapto-1,3,4-thiadiazole and the like. However, it has a drawback that it requires a large amount to prevent fog and reduces sensitivity.

Therefore, there has been a strong demand for the development of a new technique having high sensitivity and improving latent image storability.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide color photographic light-sensitive material having high sensitivity, less fog and excellent latent image storability.

[0010]

The above objects of the present invention have been achieved by the following. That is, in a silver halide color photographic light-sensitive material having a photographic constituent layer including a photographic constituent layer containing a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer on a support, at least one of the photographic constituent layers has the following general composition. At least one of the formalin scavengers represented by formulas (I) to (V), and at least one compound represented by the following general formula (VI) or (VII) in at least one silver halide emulsion layer: A silver halide color photographic light-sensitive material containing one kind.

[0011]

[Chemical 8]

In the formula, R ₁ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an acylamino group or an amino group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group or a carbamoyl group. Represents an amino group or an amidino group. R ₁ and R ₂ may combine with each other to form a ring. X is -CH ₂ - represents a or -NH-.

[0013]

[Chemical 9]

In the formula, R ₃ , R ₄ and R ₅ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group or an acyl group, and R ₆ and R ₇ each represent a hydrogen atom or an alkyl group. Represents

[0015]

[Chemical 10]

In the formula, R ₈ represents a hydrogen atom, an alkyl group or an aryl group. R ₈ may form a naphthalene ring together with a phenyl ring. n represents an integer of 2 or more.

[0017]

[Chemical 11]

In the formula, R ₉ represents a hydrogen atom or a substituent,
R ₁₀ represents a hydrogen atom or a substituent.

[0019]

[Chemical 12]

Where R₁₁And R₁₂Is a hydrogen atom or
Represents a substituent, R₁₃Represents a hydrogen atom or an alkyl group,
Z is a hydrogen atom, an alkyl group, an aryl group, -SO₂R₁₄Or
-SO ₂N (R₁₄) (R₁₅) Is represented. R₁₄Is an alkyl group, aryl
Represents a group or a heterocyclic group, R₁₅Is R₁₃Is synonymous with. or,
R₁₃And Z may combine with each other to form a ring.

[0021]

[Chemical 13]

In the formula, Z ₁ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or a —N (R ₂₆ ) — group. V ₁ , V ₂ ,
V ₃ and V ₄ each represent a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group or a cyano group. However, V ₁ and V ₂ , V ₂ and V ₃ , V
₃ and V ₄ may combine with each other to form a benzene ring. R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an aryl group or an amino group. In addition, adjacent groups of R _{21 to} R ₂₅ may be bonded to each other to form a 5- or 6-membered ring. R
₂₆ represents a substituted or unsubstituted alkyl group or aryl group.

[0023]

[Chemical 14]

In the formula, Z ₂ has the same meaning as Z ₁ , and V ₁₁ ,
V ₁₂ , V ₁₃ and V ₁₄ are respectively V ₁ , V ₂ , V ₃ and V ₄
And R ₃₁ , R ₃₂ , R ₃₃ , R _34, and R ₃₅ have the same meanings as R ₂₁ , R ₂₂ , R ₂₃ , R _24, and R ₂₅ , respectively.
R ₃₆ represents a substituted or unsubstituted alkyl group or aryl group. X represents a charge-balancing counterion, and m represents a valence that neutralizes 0 or more charges.

[0025]

DETAILED DESCRIPTION OF THE INVENTION First, the above general formulas (I) to (V)
The formalin scavenger represented by will be described.

In the general formula (I), R ₁ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an acylamino group or an amino group, and R ₂ represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl. Represents a group, a carbamoyl group, an amino group or an amidino group. R ₁ and R ₂ may combine with each other to form a ring. In addition, these groups may be further substituted (for example, hydroxyl group, carboxyl group,
Amino group, ureido group, nitro group, halogen atom, etc.). X is -CH ₂ - represents a or -NH-.

In the general formula (II), R ₃ , R ₄ and R ₅
May be the same or different and each is a hydrogen atom, an alkyl group (methyl, ethyl, propyl, i-propyl, butyl, hydroxymethyl, 2-hydroxyethyl, methoxymethyl, chloromethyl, carboxymethyl, cyanoethyl, etc. ), An alkenyl group (allyl, 2-butenyl, 2-
Each group such as chloroallyl), aralkyl group (each group such as benzyl, phenethyl, p-methoxybenzyl), aryl group (phenyl, p-tolyl, p-methoxyphenyl, o-chlorophenyl, m-hydroxyphenyl, etc.) ) Or an acyl group (acetyl, propionyl, trifluoroacetyl,
Chloroacetyl, acryloyl, methacryloyl, etc.).

R ₆ and R ₇ each represent a hydrogen atom or an alkyl group (for example, the same groups as those mentioned for R _{3 to} R ₅ can be mentioned).

The compounds represented by the general formula (II) are R _{3 to} R ₅
A polymer having a polymer attached to a polymer chain (for example, a polyethylene chain or a polypropylene chain) via the group Furthermore, in this case, -CO as a linking group -, - COO -, - CONH- and including those connecting the group and the polymer chain of the R ₃ to R _5.

In the general formula (III), R ₈ is a hydrogen atom,
It represents an alkyl group or an aryl group. R ₈ may form a naphthalene ring together with a phenyl ring. These alkyl groups and aryl groups include those having a substituent. n represents an integer of 2 to 4.

In the general formula (IV), R ₉ represents a hydrogen atom or a substituent. As the substituent, for example, an alkyl group,
Examples thereof include an aryl group, a cycloalkyl group, an acyl group, a carbamoyl group, a sulfamoyl group and an alkoxycarbonyl group, and these groups may further have a substituent (for example, a carboxyl group, a sulfo group, a hydroxyl group, an amino group, etc.). Good.

R ₁₀ represents a hydrogen atom or a substituent. As the substituent, for example, an alkyl group, an aryl group, a cyano group,
Examples thereof include a carbamoyl group, a carboxyl group, an alkoxycarbonyl group, an acyl group, a haloalkyl group, a nitro group, a sulfamoyl group, an alkylsulfamoyl group and an alkylsulfonyl group.

In the general formula (V), R ₁₁ and R ₁₂ represent a hydrogen atom or a substituent, R ₁₃ represents a hydrogen atom or an alkyl group, Z represents a hydrogen atom, an alkyl group, an aryl group,
It represents SO ₂ R ₁₄ or —SO ₂ N (R ₁₄ ) (R ₁₅ ). R ₁₄ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₅ represents the above R ₁₃
Is synonymous with. R ₁₃ and Z may be bonded to each other to form a ring.

Examples of the substituent represented by R ₁₁ include a linear or branched alkyl group having 1 to 18 carbon atoms (eg, methyl,
Each group such as ethyl and dodecyl), a cycloalkyl group having 5 to 7 carbon atoms (each group such as cyclopentyl and cyclohexyl), an aryl group (each group such as phenyl and naphthyl), a 5-membered or 6-membered heterocycle A group (for example, pyridyl, pyrimidyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, furyl, thienyl, thiazolyl, piperidino, etc.) or -SO ₂ R ₁₆ , -SO ₂ N (R ₁₆ ) (R ₁₇ ), -CO
R ₁₆ , -CON (R ₁₆ ) (R ₁₇ ), -COOR ₁₆ , -CONHNHR ₁₈ , -C
_{(= NH) NH 2, -CSNHR} 18, -CSNHNHR 18 ( wherein R ₁₆ represents an alkyl group, an aryl group, or a heterocyclic group, R ₁₇ represents a hydrogen atom or an alkyl group, R ₁₈ represents a hydrogen atom, Which represents an alkyl group, an aryl group or a heterocyclic group).

These substituents may further have a substituent, and examples of these substituents include an alkyl group, an alkoxy group, an acylamino group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group and a nitro group. Examples thereof include a group, a cyano group, a hydroxyl group, a carboxyl group, a sulfo group and a halogen atom, and among these, a sulfo group, a carboxyl group and a hydroxyl group are most preferable.

R ₁₁ is preferably a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an acyl group, a carbamoyl group or an alkoxycarbonyl group.

Examples of the substituent represented by R ₁₂ include a linear or branched alkyl group having 1 to 18 carbon atoms (eg, methyl,
Each group such as ethyl and undecyl), a cycloalkyl group having 5 to 7 carbon atoms (such as groups such as cyclopentyl and cyclohexyl), an aryl group (such as groups such as phenyl and naphthyl), an alkoxy group (such as methoxy and ethoxy) Each group), an aryloxy group (for example, a phenoxy group, etc.),
An alkoxycarbonyl group (eg methoxycarbonyl,
Each group such as ethoxycarbonyl), aryloxycarbonyl group (such as phenoxycarbonyl group), carbamoyl group (such as dimethylcarbamoyl, diethylcarbamoyl, etc.), acyl group (such as acetyl, benzoyl, etc.), amino group , An alkylamino group (for example, each group such as methylamino, dimethylamino, etc.), an arylamino group (for example, anilino group, etc.), an acylamino group (for example, each group for acetylamino, benzamide, etc.), a sulfonamide group (for example, methanesulfonamide, Each group such as benzenesulfonamide), carbamoylamino group (eg, dimethylcarbamoylamino group, etc.), sulfamoylamino group (eg, dimethylsulfamoylamino group, etc.),
Examples thereof include an alkoxycarbonylamino group (eg, groups such as methoxycarbonylamino and ethoxycarbonylamino), a cyclic amino group (eg, groups such as morpholino, piperidino, and pyrrolidino), a carboxyl group or a cyano group.

These substituents may further have substituents, and examples of these substituents include the same ones as described for R ₁₁ . R ₁₂ is a hydrogen atom,
Alkyl group, alkoxy group, alkoxycarbonyl group,
Carboxyl group, acylamino group, carbamoylamino group, sulfonamide group, sulfamoylamino group, alkoxycarbonylamino group are preferable, and particularly preferable are alkyl group, acylamino group, carbamoylamino group, sulfonamide group, alkoxycarbonylamino group. Is.

Examples of the alkyl group represented by R ₁₂ include
Examples thereof include a linear or branched alkyl group having 1 to 18 carbon atoms. These further include halogen atom, alkoxy group, aryloxy group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonyl group, nitro group, cyano group, hydroxyl group, carboxyl group, sulfo group, amino group, alkyl group. It may be substituted with an amino group, a dialkylamino group or the like.

Z is a hydrogen atom, an alkyl group, an aryl group,
-SO ₂ R ₁₃ or _{-SO 2 N (R 14) (} R 15) (R 14 represents an alkyl group, an aryl group or a heterocyclic group, R ₁₅ is a is same meaning as the R ₁₃₎ represent, these Examples include methyl group, ethyl group, butyl group, methoxymethyl group, cyanoethyl group, phenyl group, methylsulfonyl group, ethylsulfonyl group,
A butylsulfonyl group, a benzenesulfonyl group, a dimethylsulfamoyl group, a diethylsulfamoyl group and the like can be mentioned. Z is preferably an alkyl group or an alkylsulfonyl group.

Typical examples of the compounds represented by formulas (I) to (V) are shown below, but the invention is not limited thereto.

[0042]

[Chemical 15]

[0043]

[Chemical 16]

[0044]

[Chemical 17]

[0045]

[Chemical 18]

[0046]

[Chemical 19]

[0047]

[Chemical 20]

[0048]

[Chemical 21]

[0049]

[Chemical formula 22]

[0050]

[Chemical formula 23]

Most of the above compounds are commercially available compounds, and the non-commercially available compounds can be easily synthesized according to the methods described in the following patents and literatures.

Compounds I-7 and I-8 are commercially available from Bulletin of the Chemical Society of Japan (Bull
etin of the Chemical Soiety of Japan) Volume 39, 1559 ~
1567, 1734-1738 (1966), Hemische
Volume 54, B. Demi Berichte (Chemische der Berichte)
1802-1833, 2441-2479 (1921), Beilstein Handbuch der Organischen Chemie H 9
It can be easily synthesized according to the method described on page 8 (1921).

Compound I-13 is an oligomer or polymer having 1 repeating unit. l is an integer of 2 or more.

Compound I-19 can be synthesized by the method described in Beilstein Handbuk der Organichen Chemie (supra), 1st Supplement, Vol. 4, p. 354, Vol. 3, p. 63.

Compounds II-1 and II-11 are described in British Patent 717,
287, US Pat. Nos. 2,731,472, 3,187,004, H. Pauly, Hemische der Berichte (C
hem.Ber.) 63B, 2063 (1930), FB Slezak (FBSlezak), Journal of Organic Chemistry (J.Org.Chem.) 27, 2181 (1962), Jay.
J. Nematollahl, Journal of the
Organic Chemistry (J.Org.Chem.) 28, 2378 (1
963) and the like.
Further, alkyluril, acylation, hydroxymethylation, alkoxymethylation, halomethylation and the like of glycoluril can be carried out by a conventional method to obtain alkyl, acyl, hydroxymethyl, alkoxymethyl and halomethyl derivatives, respectively.

Compounds IV-1 to IV-30 are disclosed in JP-A-51-77327.
No. 62-273527, British Patent No. 585,780 and the like.

Compounds V-1 to V-24 are berichte der.
Deutschen Chemichen Gesellschaft (Berichte
der Deutschen Chemischen gesellschaft) 57, 332 (1
924), Annalen der Chemie 52, 622 (19)
36), 397, 119 (1913), 568, 227 (1950), Journal of the American Chemical Society, 73.
It can be easily synthesized according to the method described in 4,664 (1951) and the like.

The formalin scavenger according to the present invention comprises a layer containing a magenta coupler in the case of a light-sensitive material in which a photographic constituent layer is present above a layer containing a magenta coupler in a silver halide color photographic light-sensitive material. And / or at least one layer of the photographic constituent layer located on the upper side of the magenta coupler-containing layer may contain one kind or a combination of two or more kinds. Also, a known formalin scavenger may be used in combination. As the most preferable layer containing these formalin scavengers, a layer closest to the outside air of the light-sensitive material, for example, a protective layer is effective.

The above-mentioned photographic constitutional layer in the present invention means, for example, a silver halide emulsion layer having a photosensitivity which is optically or chemically sensitized to form a light-sensitive material, and a non-light-sensitive layer. The intermediate layer, the ultraviolet absorbing layer, the yellow filter layer, the protective layer and other auxiliary layers are included.

The formalin scavenger according to the present invention can be added to and contained in these layers by dissolving it in a suitable solvent such as water or methanol in the coating solution for forming the layers. Well, the addition timing may be any stage. For example, when it is added to the silver halide emulsion, it may be added at any time during its production process, but it is generally desirable to add it immediately before coating.

The amount of addition is 1 for color photographic light-sensitive material.
It is preferably 0.01 to 5.0 g per m ² .

Next, the compound represented by formula (VI) or (VII) will be described.

The substituent represented by V ₁ , V ₂ , V ₃ and V ₄ is preferably used as a halogen atom (eg chlorine), an aryl group (eg phenyl), an alkyl group (preferably having 1 carbon atom). ~ 7, particularly preferably 1-4),
An alkoxy group (preferably having 1 to 6 carbon atoms, particularly preferably 1 to 2) and an alkoxycarbonyl group (eg ethoxycarbonyl). It is also preferable that two adjacent substituents are condensed to form a benzene ring.

A cyano group is also preferably used when Z ₁ is = NR ₂₆ .

The substituent represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ is preferably a halogen atom (eg chlorine), a hydroxyl group, an alkyl group having 1 to 4 carbon atoms and An alkoxy group and an amino group (for example, dimethylamino, diethylamino, etc.), which are also preferable when two adjacent substituents are condensed to form a ring (fused benzene ring, methylenedioxy group, etc.).

The alkyl group represented by R ₂₆ is preferably an alkyl group having 1 to 6 carbon atoms (eg, methyl, ethyl, propyl, etc.), and the alkyl group may have a substituent.

Examples of the substituent include an alkoxy group, an alkylthio group, an aryloxy group, an aryl group, a hydroxyl group, a cyano group, a vinyl group, a halogen atom, a carbamoyl group, a sulfamoyl group, a sulfonyl group, an alkoxycarbonyl group and a carboxyl group. Is mentioned.

In the compound represented by the general formula (VII), V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ are V ₁ , V ₂ , V ₃ and V ₄
And R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ and R
₃₅ has the same meaning as R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ , respectively. Further, R ₃₆ has the same meaning as R ₂₆ .

Specific examples of the compound represented by the general formula (VI) or (VII) used in the present invention are shown below.
The present invention is not limited to these.

[0070]

[Chemical formula 24]

[0071]

[Chemical 25]

[0072]

[Chemical formula 26]

[0073]

[Chemical 27]

[0074]

[Chemical 28]

[0075]

[Chemical 29]

[0076]

[Chemical 30]

[0077]

[Chemical 31]

[0078]

[Chemical 32]

[0079]

[Chemical 33]

[0080]

[Chemical 34]

[0081]

[Chemical 35]

General formula (VI) or (VI used in the present invention
The compound represented by I) is preferably used in an amount capable of improving latent image storability, and particularly, used in a ratio of 1 × 10 ⁻³ to 1 × 10 ⁻² mol per mol of silver halide in the emulsion. Is preferred.

The compound represented by the general formula (VI) or (VII) can be dispersed directly in the emulsion, and a suitable solvent (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or these compounds can be used. It can also be dissolved in a mixed solvent and added to the emulsion. In addition, the sensitizing dye may be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding the sensitizing dye.

In the present invention, it is preferable to use a 1- (pentachlorophenyl) -3-anilino-5-pyrazolone compound as the magenta coupler.

In a preferred embodiment of the color light-sensitive material of the present invention, the magenta coupler is a photographic constituent layer of at least one green-sensitive silver halide emulsion layer and a formalin scavenger represented by formulas (I) to (V). At least one of
The compound represented by formula (VI) or (VII) is contained in at least one of the silver halide emulsion layers.

The silver halide used in the light-sensitive material of the present invention is a conventional silver halide emulsion containing silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, silver chloride and the like. Any of the above can be used.

The silver halide grain used in the silver halide emulsion has a layered structure in which the silver halide composition is different between the inside and the surface layer of the grain even if it has a uniform silver halide composition distribution within the grain. May be

The silver halide grain may be a grain in which a latent image is mainly formed on the surface, or may be a grain in which a latent image is mainly formed inside the grain.

The silver halide emulsion may have any grain size distribution. An emulsion having a wide grain size distribution (referred to as a polydisperse emulsion) may be used, or an emulsion having a narrow grain size distribution (referred to as a monodisperse emulsion) may be used alone or in combination of several kinds. Further, a polydisperse emulsion and a monodisperse emulsion may be mixed and used.

As the silver halide emulsion, two or more kinds of silver halide emulsions formed separately may be mixed and used.

The silver halide grains used in the present invention are
Chemical sensitization can be performed by a sulfur sensitizing method, a selenium sensitizing method, a reduction sensitizing method, a noble metal sensitizing method, or the like. Further, a dye known as a sensitizing dye in the photographic industry can be used to perform spectral sensitization in a desired wavelength range.

Antifoggants, stabilizers and the like can be added to the silver halide emulsion.

It is advantageous to use gelatin as the binder (or protective colloid) used in the emulsion of the light-sensitive material, but other than that, gelatin derivatives, graft polymers of gelatin and other polymers, proteins and sugars. Hydrophilic colloids such as derivatives, cellulose derivatives, and synthetic hydrophilic polymeric substances such as homopolymers or copolymers can also be used.

The photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material of the present invention are hardened by using a hardener alone or in combination. Examples of hardening agents that can be used include aldehyde-based and aziridine-based (for example, PB Report 19,921, U.S. Patents 2,950,197, 2,964,404, 2,983,611, and 3,2).
71,175, JP-B-46-40898, JP-A-50-91315, etc.), epoxy-based (for example, US Pat. No. 3,047,394).
No. 1, West German Patent No. 1,085,663, British Patent No. 1,033,518, Japanese Patent Publication No. 48-35495), vinyl sulfone system (for example, PB Report 19920, West German Patent Nos. 1,100,942, 2,337,41).
No. 2, No. 2,545,722, No. 2,635,518, No. 2,742,308,
No. 2,749,260, British Patent 1,251,091, Japanese Patent Application No. 45-54236
No. 48-110996, U.S. Patent Nos. 3,539,644 and 3,490,91.
No. 1 etc.), acryloyl type (eg Japanese Patent Application No. 4)
8-27949, those described in U.S. Pat. No. 3,640,720), carboxyl-activated systems (eg WO-2357, U.S. Pat. No. 2,938,8)
No. 92, No. 3,331,609, No. 4,043,818, No. 4,061,499
No. 46-38715, 55-38655, 58-32699,
JP-A-55-155346, 56-110762, 60-225148,
No. 61-100743, those described in No. 62-264044), triazine-based (for example, West German Patents 2,410,973, 2,553,915,
US Pat. No. 3,325,287, those described in JP-A-52-12722), polymer type (for example, British patent 822,061, US patent
3,623,878, 3,396,029, 3,226,234, Japanese Patent Sho 4
7-18578, 47-18579, 47-48896), other maleimide-based, acetylene-based, methanesulfonic acid ester-based, N-methylol-based hardening agents can be used alone or in combination. . Examples of useful combination techniques include West German Patents 2,447,587, 2,505,746, and 2,514,24.
5, U.S. Patents 4,047,957, 3,832,181, 3,840,3
70, JP-A-48-43319, 50-63062, 52-127329
And the combinations described in JP-B-48-32364.

Among these, in particular, for example, US Pat.
9,644, JP-A-48-74832, 49-24435, 52-2105
No. 9, 52-77076, 53-41221, 53-57257, 63-
It is preferable to use the hydrophilized vinyl sulfone compound described in No. 241539 because more excellent storage stability can be obtained.

Further, the silver halide emulsion may contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer.

A coupler is used in the light-sensitive material of the present invention. Further, a development accelerator, a bleaching accelerator, a developer, a silver halide solvent, a toning agent, by coupling with a competing coupler having an effect of color correction and an oxidized product of a developing agent,
Compounds that release photographically useful fragments such as hardeners, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers and desensitizers can be used.

As the yellow dye-forming coupler, known acylacetanilide type couplers can be preferably used. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

As the cyan dye forming coupler, a phenol or naphthol type coupler is generally used.

To incorporate the coupler into the light-sensitive material,
Known techniques used in ordinary couplers can be applied. It is preferable that the coupler is dissolved in a high boiling point solvent, if necessary in combination with a low boiling point solvent, dispersed in the form of fine particles and added to the silver halide emulsion. At this time, if necessary, a hydroquinone derivative, an ultraviolet absorber, an anti-fading agent, etc. may be used in combination.

The light-sensitive material of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or in the emulsion layers, dyes which may be bleached or bleached from the light-sensitive material during development processing may be contained.

Matting agents, lubricants, image stabilizers, ultraviolet absorbers, fluorescent whitening agents, surfactants, development accelerators, development retarders and bleaching accelerators can be added to the light-sensitive material.

The photographic emulsion layer and other layers of the light-sensitive material are baryta paper or paper laminated with α-olefin polymer or the like, and a paper support from which the α-olefin layer can be easily peeled off from the paper support, a flexible material such as synthetic paper. Reflective support, cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride,
It can be provided on a reflective support coated with a film made of a semi-synthetic or synthetic polymer such as polyethylene terephthalate, polycarbonate, or polyamide, and a white pigment, or a rigid body such as glass, metal, or pottery. Or 120-160
It can also be provided on a thin reflective support of μm.

When the light-sensitive material of the present invention contains a coupler, in order to obtain a dye image, generally known color photographic processing is carried out after exposure.

In the present invention, the color development may be immediately followed by a processing solution having a bleaching ability and a processing solution having a fixing ability, but a processing solution having a bleaching ability and a fixing ability (so-called bleach-fixing). Liquid). As the bleaching agent used for the bleaching, a metal complex salt of an organic acid is used.

After the fixing process, a washing process is usually performed. Further, a stabilizing treatment may be performed as an alternative to the water washing treatment, or both may be used in combination.

[0107]

EXAMPLES Hereinafter, specific examples of the present invention will be described, but the embodiments of the present invention are not limited thereto.

Example 1 A multilayer color photographic light-sensitive material sample 1 was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

The addition amount in the multilayer color photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified.
The silver halide and colloidal silver are shown in terms of silver, and the sensitizing dye is shown in the number of moles per mole of silver.

First layer: Antihalation layer (HC) Black colloidal silver 0.15 Ultraviolet absorber (UV-1) 0.20 Colored cyan coupler (CC-1) 0.02 High boiling point solvent (Oil-1) 0.20 High boiling point solvent (Oil-) 2) 0.20 Gelatin 1.6 Second layer: Intermediate layer (IL-1) Gelatin 1.3 Third layer: Low sensitivity red sensitive emulsion layer (RL) Silver iodobromide emulsion (Em-1) 0.4 Silver iodobromide emulsion (Em- 2) 0.3 sensitizing dye (S-1) 3.2 × 10 ^-4 sensitizing dye (S-2) 3.2 × 10 ^-4 sensitizing dye (S-3) 0.2 × 10 ^-4 cyan coupler (C-1) 0.50 Cyan coupler (C-2) 0.13 Colored cyan coupler (CC-1) 0.07 DIR compound (D-1) 0.01 High boiling point solvent (Oil-1) 0.55 Gelatin 1.0 Fourth layer: High-sensitivity red-sensitive emulsion layer (RH) Iodine Silver bromide emulsion (Em-3) 0.9 Sensitizing dye (S-1) 1.7 × 10 ^-4 Sensitizing dye (S-2) 1.6 × 10 ^-4 Sensitizing dye (S-3) 0.1 × 10 ^-4 Cyan coupler (C-2) 0.23 Colored cyan coupler (CC-1) 0.03 DIR compound (D-1) 0.02 High boiling point solvent (Oil-1) 0.25 Gelatin 1.0 Fifth layer: intermediate layer (IL-2) gelatin 0.8 Sixth layer: low-sensitivity green sensitive emulsion layer (GL) Silver iodobromide emulsion (Em-1) 0.6 Silver iodobromide emulsion (Em-2) 0.2 Increase Sensitizing dye (S-4) 6.7 × 10 ^-4 Sensitizing dye (S-5) 0.8 × 10 ^-4 Magenta coupler (MA) 0.47 Colored magenta coupler (CM-1) 0.10 DIR compound (D-3) 0.02 High boiling point solvent (Oil-2) 0.70 Gelatin 1.0 Seventh layer: High sensitivity green sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 0.9 Sensitizing dye (S-6) 1.1 × 10 ^-4 sensitized dye (S-7) 2.0 × 10 -4 sensitizing dye (S-8) 0.3 × 10 -4 magenta coupler (M-A) 0.15 colored magenta coupler (CM- ) 0.04 DIR compound (D-3) 0.04 high boiling point solvent (Oil-2) 0.35 gelatin 1.0 8th layer: yellow filter layer (YC) yellow colloidal silver 0.1 additive (SC-1) 0.12 high boiling point solvent (Oil-2) ) 0.15 gelatin 1.0 9th layer: low-sensitivity blue-sensitive emulsion layer (BL) silver iodobromide emulsion (Em-1) 0.25 silver iodobromide emulsion (Em-2) 0.25 sensitizing dye (S-9) 5.8 × 10 ^-4 Yellow coupler (Y-1) 0.60 Yellow coupler (Y-2) 0.32 DIR compound (D-2) 0.01 High boiling solvent (Oil-2) 0.18 Gelatin 1.3 10th layer: High-sensitivity blue-sensitive emulsion layer (BH) Silver iodobromide emulsion (Em-4) 0.5 Sensitizing dye (S-10) 3.0 × 10 ^-4 Sensitizing dye (S-11) 1.2 × 10 ^-4 Yellow coupler (Y-1) 0.18 Yellow coupler (Y- 2) 0.10 High boiling point solvent (Oil-2) 0.05 Gelatin 1.0 11th layer: 1st protective layer (PRO-1) Silver iodobromide emulsion Em-5) 0.3 Ultraviolet absorber (UV-1) 0.07 Ultraviolet absorber (UV-2) 0.1 High boiling point solvent (Oil-1) 0.07 High boiling point solvent (Oil-3) 0.07 Gelatin 0.8 12th layer: Second protection Layer (PRO-2) Alkali-soluble matting agent (average particle size 2 μm) 0.13 Polymethylmethacrylate (average particle size 3 μm) 0.02 Gelatin 0.5 In each layer, in addition to the above composition, a coating aid SU-2, Dispersion aid SU-1, hardener H-1, dyes AI-1, AI-
2 was added appropriately.

The emulsions used in the above samples are as follows, and all are internal high iodine type monodisperse emulsions.

Em-1: Average silver iodide content 7.5 mol%
Average grain size 0.55 μm Grain shape octahedron Em-2: Average silver iodide content 2.5 mol% Average grain size 0.36
μm Grain shape octahedron Em-3: average silver iodide content 8.0 mol% average grain size 0.84
μm Grain shape octahedron Em-4: average silver iodide content 8.5 mol% average grain size 1.02
μm Grain-shaped octahedron Em-5: average silver iodide content 2.0 mol% average grain size 0.08
μm The additives used are as follows.

SU-1: Sodium tri-i-propylnaphthalene sulfonate SU-2: Dioctyl sodium sulfosuccinate SC-1: 2-sec-octadecyl-5-methylhydroquinone and 2-sec-hexadecylhydroquinone : 3 mixture H-1: bis (vinylsulfonylmethyl) ether Oil-1: di (2-ethylhexyl) phthalate Oil-2: tricresyl phosphate

[0114]

[Chemical 36]

[0115]

[Chemical 37]

[0116]

[Chemical 38]

[0117]

[Chemical Formula 39]

[0118]

[Chemical 40]

[0119]

[Chemical 41]

In addition, the formalin scavenger shown in Table 1 was added to the eleventh silver halide emulsion layer of Sample 1 in an amount of 1 m ²
0.3 g per sample was added, Samples 2 and 3 were added, the formalin scavenger shown in Table 1 was added to the 11th layer, and the latent image keeping improver of the present invention was added to all the silver halide emulsion layers. Samples 4 to 15 with 1 × 10 -5 mol added per mol
It was created.

The samples 1 to 15 thus prepared were exposed to white light through a step wedge for sensitometry and then processed by the following processing steps.

The processed sample is measured by green light,
The fog and sensitivity of the green-sensitive emulsion layer were determined. The sensitivity is
The value was calculated from the reciprocal of the exposure amount required to give the density of fog + 0.3, and the relative value is shown with the sensitivity of Sample 1 being 100.

Treatment step (38 ° C.) Treatment time Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water wash 3 minutes 15 seconds Settling 6 minutes 30 seconds Water wash 3 minutes 15 seconds Stabilization 1 minute 30 seconds Dry The composition of the processing liquid used in each processing step is as follows.

<Color developer> 4-amino-3-methyl-N-ethyl-N- (β-hydroxyethyl) aniline / sulfate 4.75 g anhydrous sodium sulfite 4.25 g hydroxylamine / 1/2 sulfate 2.0 g anhydrous Potassium carbonate 37.5 g Sodium bromide 1.3 g Nitrilotriacetic acid trisodium salt (monohydrate) 2.5 g Potassium hydroxide 1.0 g Water is added to make 1 liter, and the pH is adjusted to 10.05.

<Bleach> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100.0 g Ethylenediaminetetraacetic acid diammonium salt 10.0 g Ammonium bromide 150.0 g Glacial acetic acid 10.0 cc Add water to make 1 liter, and use ammonia water to adjust pH =
Adjust to 6.0.

<Fixer> Ammonium thiosulfate 175.0 g Anhydrous sodium sulfite 8.5 g Sodium metasulfite 2.3 g Water is added to make 1 liter, and pH is adjusted to 6.0 with acetic acid.

<Stabilizing Solution> Water 900 cc p-Octylphenol ethylene oxide 10 mol adduct 2.0 g Dimethylolurea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzisothiazolin-3-one 0.1 g Siloxane (UC-L-77) 0.1g Ammonia water 0.5cc Add water to make 1 liter, then use ammonia water or 50%
Adjust to pH = 8.5 with sulfuric acid.

Next, four sets of samples 1 to 15 were prepared, and 1/100
After performing wedge exposure for one second, one set is stored for 3 days under the conditions of 55 ° C and 55% RH, another set is stored for 30 days at 23 ° C and 55% RH, and the remaining two sets are in the freezer. The latent image storability was evaluated by carrying out the above-mentioned development processing by storing the sample as a control for storage.

The latent image storability was shown as a relative value with the control sensitivity of each sample being 100. The results are shown in Table 1.

[0130]

[Table 1]

From the results shown in Table 1, it is understood that Samples 4 to 15 of the present invention are superior in latent image storability to Comparative Samples 1 to 3 with no increase in fog density and no decrease in sensitivity.

Further, the latent image preservation improving agent of Sample 4 of the present invention was used as VI.
-17, VI-20, VI-27, VI-45, VI-51, VII-8, VII
When the samples replaced with -17, VII-19, and VII-30 were treated in the same manner, the effect of the present invention was obtained.

[0133]

According to the present invention, a silver halide color photographic light-sensitive material having high sensitivity, low fog and significantly improved latent image storability can be obtained.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a photographic constituent layer containing a blue-sensitive, green-sensitive and red-sensitive silver halide emulsion layer on a support, and at least one of the photographic constituent layers. Containing at least one of the formalin scavengers represented by the following general formulas (I) to (V), and at least one of the silver halide emulsion layers is represented by the following general formula (VI) or (VII) A silver halide color photographic light-sensitive material containing at least one compound. [Chemical 1] [In the formula, R ₁ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an acylamino group or an amino group, and R ₂
Represents a hydrogen atom, an alkyl group, an aryl group, an acyl group, an alkoxycarbonyl group, a carbamoyl group, an amino group or an amidino group. R ₁ and R ₂ may combine with each other to form a ring. X is -CH ₂ - represents a or -NH-. ] [Chemical 2] [In the formula, R ₃ , R ₄ and R ₅ each represent a hydrogen atom, an alkyl group, an alkenyl group, an aralkyl group, an aryl group or an acyl group, and R ₆ and R ₇ each represent a hydrogen atom or an alkyl group. . ] [Chemical 3] [In the formula, R ₈ represents a hydrogen atom, an alkyl group or an aryl group. R ₈ may form a naphthalene ring together with a phenyl ring. n represents an integer of 2 or more. ] [Chemical 4] [In the formula, R ₉ represents a hydrogen atom or a substituent, and R ₁₀ represents a hydrogen atom or a substituent. ] [Chemical 5] [In the formula, R ₁₁ and R ₁₂ each represent a hydrogen atom or a substituent, R ₁₃ represents a hydrogen atom or an alkyl group, Z is a hydrogen atom, an alkyl group, an aryl group, —SO ₂ R ₁₄ or —SO. ₂ N
Represents (R ₁₄ ) (R ₁₅ ). R ₁₄ represents an alkyl group, an aryl group or a heterocyclic group, and R ₁₅ has the same meaning as R ₁₃ . R ₁₃ and Z may be bonded to each other to form a ring. ] [Chemical 6] [In the formula, Z ₁ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or a —N (R ₂₆ ) — group. V ₁ , V ₂ , V ₃ and V ₄
Each represents a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group, an alkoxy group, an alkoxycarbonyl group, a carboxyl group, a hydroxyl group or a cyano group. However, V ₁ and V ₂ , V ₂ and V ₃ , V ₃ and V ₄ are
They may be bonded to each other to form a benzene ring. R ₂₁ ,
R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ each represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group, an aryl group or an amino group. In addition, adjacent groups of R _{21 to} R ₂₅ may be bonded to each other to form a 5- or 6-membered ring. R ₂₆ represents a substituted or unsubstituted alkyl group or aryl group. ] [Chemical 7] [In the formula, Z ₂ has the same meaning as Z ₁ , and V ₁₁ , V ₁₂ , V ₁₃ and V ₁₄ have the same meanings as V ₁ , V ₂ , V ₃ and V ₄ , respectively,
R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ and R ₃₅ are respectively R ₂₁ and R
It is synonymous with ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ . R ₃₆ represents a substituted or unsubstituted alkyl group or aryl group. X represents a charge-balancing counterion, and m represents a valence that neutralizes 0 or more charges. ]