JPH06186706A - Silver halide color photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and storage stability of raw stock and retention stability of a latent image and to reduce fog by incorporating a specified coupler and a specified non-color development compound in at least one of blue-sensitive layers. CONSTITUTION:At least one of the blue-sensitive layers contains at least one of the couplers represented by formula I and at least one of the compounds represented by formula II and the like. In formulae I and II, R1 is a univalent substituent except H; Q is a nonmetallic atomic group necessary to form a 3-, 4-, or 5-member hydro carbon ring or such 3-5 member hetero ring having one of N, S, O and P together with the C atom; R2 is H, alkyl, or the like; Y is H or the like; Z1 is O, S, or the like; each of V21-V24 is H, halogen, aryl, or the like; and each of R21-R25 H, halogen, hydroxy, or the like, or a group necessary to condense with its adjacent substituent to form a 5- or 6-member 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 particularly to a silver halide color photographic light-sensitive material having high sensitivity, low fog and improved raw storability and latent image storability. It is about.

[0002]

BACKGROUND OF THE INVENTION Couplers used in silver halide color photographic light-sensitive materials (hereinafter, also simply referred to as color light-sensitive materials) are conventional four-color couplers that require four molecules of silver to form one molecule of dye. In place of the equivalent coupler, silver for forming one molecule of dye by introducing an appropriate substituent at the coupling position (active site) of the coupler which reacts with the oxide of the developing agent is formed by 2 atoms. I made it 2
Equal couplers are becoming more popular.

In recent years, the demand for couplers has become more and more stringent with the progress of color light-sensitive materials, and further improvements in, for example, photographic properties, color developability and raw storability are strongly desired.

Among these, as an example of a yellow coupler having good color reproducibility and high color development, for example, an alkoxy group at the 2-position of the anilide portion as described in JP-A-63-123047 is used. A yellow coupler having an acylamino group introduced at the 5-position is disclosed. However, the coupler has an essentially high pKa, and has not reached a satisfactory level in terms of color developability.

Conventionally, as a means for improving color development,
Introducing a heteroatom into the acyl moiety of the acylacetanilide mother nucleus is described in Research Disclosure (R
D) 15737, JP-B-49-17734, JP-A-50-130442,
It is disclosed in US Pat. No. 3,778,277. Further, introduction of a cycloalkane-1-carbonyl group into an acyl moiety is disclosed in US Pat. No. Re 27,848, JP-A-47-26133 and JP-A-4-218042. However, these couplers have problems such as high fog and poor raw storage stability, although the color developability is improved.

On the other hand, in general, most of silver halide photographic light-sensitive materials have a defect that the latent image formed by exposure is regressed with time, that is, so-called latent image regression, and high sensitivity is achieved. However, it is a major obstacle.

Therefore, many techniques for preventing latent image regression have been known in the past, for example, British Patent 1,308,77.
No. 7, No. 1,335,923, No. 1,353,527, No. 1,378,354,
1,386,630, 1,387,654, 1,389,089, 1,3
91,672, 1,390,237, 1,394,371, 1,412,29
4, 1,458,197, U.S. Patents 3,881,939, 4,397,9
42, JP-A-47-37922, 49-17720, 57-22234
No. 57-158840, No. 58-90634, No. 58-152235, and the like, a method using a compound containing a sulfur, oxygen, or nitrogen atom in a silver halide emulsion, or JP-A-57-104927. Issue 62-
Research Disclosure (RD) 17643 discloses a method of adding a sulfinic acid derivative and a method of using various organic compounds in No. 21145.

However, in any of these methods, there are many cases in which an unfavorable adverse effect such as generation of fog and large deterioration of sensitivity is brought about.

Fog caused by these latent image stabilizers is, for example, 5-methylbenzotriazole, 1-phenyl-5-mercaptotetrazole, benzimidazole or 2,5-dimercapto-1,3,4-thiadiazole. Although it is known that addition is prevented, it has a drawback that sensitivity is reduced because the amount required for preventing fog is large.

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

[0011]

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

[0012]

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 silver halide emulsion layer comprising a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support, at least one of the blue-sensitive layers has the following general composition. A silver halide color photographic light-sensitive material containing at least one coupler represented by the formula [Y-I] and at least one non-color-forming compound represented by the following general formula [II] or the following general formula [III]. Depends on the material.

[0014]

[Chemical 4]

In the formula, R ₁ represents a monovalent substituent excluding a hydrogen atom, Q forms a 3- to 5-membered hydrocarbon ring with C, or a hetero atom selected from N, S, O and P. It represents a group of non-metal atoms necessary for forming a 3- to 5-membered heterocycle containing at least one atom in the ring. R ₂ represents a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an amino group or a halogen atom, R ₃ represents a group which can be substituted on the benzene ring, Y represents a hydrogen atom, or an aromatic primary amine. It represents a group capable of splitting off by a coupling reaction with an oxidized product of a developing agent (hereinafter referred to as splitting group).

[0016]

[Chemical 5]

In the formula, Z ₁ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or ═NR ₂₆ . V ₂₁ , V ₂₂ , V
₂₃ and V ₂₄ represent a hydrogen atom, a halogen atom, an aryl group, an alkyl group, a substituted alkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxy group, a hydroxy group and a cyano group. However, V ₂₁ and V ₂₂ , V ₂₂ and V ₂₃ , V ₂₃ and V ₂₄ may be condensed to form a benzene ring. R ₂₁ , R ₂₂ ,
R ₂₃ , R ₂₄ , and R ₂₅ are each a hydrogen atom, a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an amino group, or a group capable of condensing an adjacent substituent to form a 5- or 6-membered ring. Represent R ₂₆ is a substituted or unsubstituted alkyl group,
Represents an aryl group.

[0018]

[Chemical 6]

Where Z₂Is Z₁Is synonymous with V₃₁，
V₃₂, V₃₃, V₃₄Are each V_{twenty one}, V_{twenty two}, V _{twenty three}, V_{twenty four}Synonymous with
Is. R₃₁, R₃₂, R₃₃, R₃₄, R₃₅Are each R_{twenty one}, R
_{twenty two}, R_{twenty three}, R_{twenty four}, R_{twenty five}Is synonymous with. R₃₆Is a substitution or
It represents an unsubstituted alkyl group or an aryl group. X is charge balance
Represents a counter ion, and k represents a value for neutralizing a charge of 0 or more.
You

Examples of R ₃ are halogen atom, alkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, aryloxycarbonyl group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, Alkylsulfonyl group, ureido group, sulfamoylanomyl group, alkoxycarbonylamino group, alkoxysulfonyl group, acyloxy group, nitro group, heterocyclic group, cyano group, acyl group, acyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group Examples of the leaving group include a heterocyclic group bonded to the coupling active position at a nitrogen atom, an aryloxy group, an arylthio group, an acyloxy group, an alkylsulfonyloxy group, an arylsulfonyloxy group, a heterocyclic oxy group, a halogen. There is a child.

When the substituent in the formula [Y-I] is or contains an alkyl group, the alkyl group may be linear, branched or cyclic unless otherwise specified.
Alkyl groups which may be substituted or may contain unsaturated bonds (eg methyl, isopropyl, t-butyl, cyclopentyl, t-pentyl, cyclohexyl, 2-ethylhexyl, 1,1,3,3-tetramethylbutyl , Dodecyl, hexadecyl, allyl, 3-cyclohexenyl, oleyl,
Benzyl, trifluoromethyl, hydroxymethylmethoxyethyl, ethoxycarbonylmethyl, phenoxyethyl).

When the substituent in the formula [Y-I] is an aryl group or contains an aryl group, the aryl group may be an optionally substituted monocyclic or condensed ring aryl group ( For example phenyl, 1-naphthyl,
p-tolyl, o-tolyl, p-chlorophenyl, 4-methoxyphenyl, 8-quinolyl, 4-hexadecyloxyphenyl,
Pentafluorophenyl, p-hydroxyphenyl, p-cyanophenyl, 3-pentadecylphenyl, 2,4-di-t-pentylphenyl, p-methanesulfonamidophenyl, 3,
4-dichlorophenyl) is meant.

When the substituent in the formula [Y-I] is a heterocyclic group or contains a heterocyclic group, the heterocyclic group is selected from O, N, S, P, Se and Te unless otherwise specified. And a 3- to 8-membered optionally substituted monocyclic or condensed-ring heterocyclic group containing at least one hetero atom in the ring (for example, 2-furyl, 2-pyridyl, 4-pyridyl, 1-pyrazolyl, 1 -Imidazolyl, 1-benzotriazolyl, 2-benzotriariazolyl, succinimide, phthalimide, 1-benzyl-2,4
-Imidazolidinedione-3-yl).

The substituents preferably used in the formula [YI] will be described below.

In the formula [Y-I], R ₁ is preferably a halogen atom, a cyano group, or a monovalent group having a total carbon number (hereinafter abbreviated as C number) 1 to 30 which may be substituted (for example, C number). An alkyl group, an alkoxy group) or a monovalent group having 6 to 30 carbon atoms (eg, an aryl group, an aryloxy group), and the substituent thereof is, for example, a halogen atom, an alkyl group, an alkoxy group, a nitro group, an amino group. , Carbonamide group, sulfonamide group, and acyl group.

In the formula [Y-I], Q is preferably a C number 3 which may be substituted with any of 3 to 5 members together with C.
~ 30 hydrocarbon rings or at least one N, S, O,
It represents a group of non-metallic atoms necessary for forming a heterocycle having a C number of 2 to 30 containing a heteroatom selected from P in the ring. Also,
The ring formed by Q together with C may contain an unsaturated bond in the ring. Examples of the ring formed by Q together with C include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclopropene ring, a cyclobutene ring, a cyclopentene ring, an oxetane ring, an oxolane ring, a 1,3-dioxolane ring, a thietane ring, a thiolane ring and a pyrrolidine. There is a ring. Examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an acyl group, an alkoxy group, an aryloxy group, a cyano group, an alkoxycarbonyl group, an alkylthio group and an arylthio group.

In the formula [Y-I], R ₂ is preferably a halogen atom, an optionally substituted C 1-30 alkoxy group, a C 6-30 aryloxy group, or a C 1-30 alkyl. Represents a group or an amino group having 0 to 30 carbon atoms, and examples of the substituent thereof include a halogen atom, an alkyl group, an alkoxy group, and an aryloxy group.

In the formula [Y-I], R ₃ is preferably a halogen atom, an optionally substituted alkyl group having 1 to 30 C atoms,
An aryl group having a C number of 6 to 30, an alkoxy group having a C number of 1 to 30,
C2-30 alkoxycarbonyl group, C7-30 aryloxycarbonyl group, C1-30 carbonamido group, C1-30 sulfonamide group, C1-30 carbamoyl group, C Number 0 to 30 sulfamoyl group, C number 1 to
30 alkyl sulfonyl group, C 6-30 aryl sulfonyl group, C 1-30 ureido group, C 0-30 sulfamoylanomyl group, C 2-30 alkoxycarbonylamino group, C number 1 to 30 heterocyclic groups, C1 to C30 acyl groups, C1 to C30 alkylsulfonyloxy groups, and C6 to C30 arylsulfonylkioxy groups, the substituents of which are halogen, for example. Atom, alkyl group, aryl group, heterocyclic group, alkoxy group, aryloxy group, heterocyclic oxy group, alkylthio group, arylthio group, heterocyclic thio group, alkylsulfonyl group, arylsulfonyl group, acyl group, carbonamido group, Sulfonamide group, carbamoyl group, sulfamoyl group, alkoxycarbonylamino group, sulfamoylamino group, ureido group, cyano group, nitro group An acyloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyloxy group, an arylsulfonyloxy group.

In the formula [Y-I], the substitution position of R ₃ is

[0030]

[Chemical 7]

In the formula [Y-I], Y preferably represents a heterocyclic group or an aryloxy group bonded to the coupling active position with a nitrogen atom.

When Y represents a heterocyclic group, Y is preferably an optionally substituted 5- to 7-membered monocyclic or condensed-ring heterocyclic group, examples of which include succinimide, maleimide, phthalimide, Diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, indazole, benzimidazole, benzotriazole, imidazolidine-
2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolidin-2-one, oxazolidin-2-one, thiazolidin-2-one, benzimidazoline
-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6-dioxypurine, paraban Acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6-pyridazone-2-pyrazone, 2-amino-1,3,4-thiazolidine, 2- Imino-1,3,
4-thiazolidin-4-one and the like, and these heterocycles may be substituted. Examples of the substituents of these heterocycles include halogen atom, hydroxyl group, nitro group, cyano group, carboxyl group, sulfo group, alkyl group, aryl group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkyl group. Sulfonyl group, arylsulfonyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyl group, acyloxy group, anomi group, carbonamide group, sulfonamide group, carbamoyl group, sulfamoyl group, ureido group, alkoxycarbonylamino group, sulfamoyl group There is an amino group. When Y represents an aryloxy group, Y preferably has a C number of 6
It represents an aryloxy group of ˜30 and may be substituted with a group selected from the substituent group mentioned when Y is a heterocycle. Examples of the substituent of the aryloxy group include a halogen atom, a cyano group, a nitro group, a carboxyl group, a trifluoromethyl group, an alkoxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group and an arylsulfonyl group. A group or a cyano group is preferable.

Substituents particularly preferably used in formula [Y-I] will be described below.

R ₁ is particularly preferably a halogen atom,
It is an alkyl group and most preferably a methyl group. Q
Is particularly preferably a group of non-metal atoms whose ring formed with C forms a 3- to 5-membered hydrocarbon ring, for example,

[0035]

[Chemical 8]

R ₂ is particularly preferably a chlorine atom, a fluorine atom, an alkyl group having a C number of 1 to 6 (eg methyl, trifluoromethyl, ethyl, isopropyl, t-butyl), C
An alkoxy group of the number 1 to 8 (for example, methoxy, ethoxy,
Methoxyethoxy, butoxy), or an aryloxy group having 6 to 24 C atoms (for example, phenoxy, p-tolyloxy,
p-methoxyphenoxy), most preferably a chlorine atom, a methoxy group or a trifluoromethyl group.

R ₂ is particularly preferably a halogen atom,
It is an alkoxy group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonamido group, a sulfonamide group, a carbamoyl group or a sulfamoyl group, most preferably an alkoxy group, an alkoxycarbonyl group, a carbonamido group or a sulfonamide group.

Y is particularly preferably the following formula [Y-II],
It is a group represented by [Y-III] or [Y-IV].

[0039]

[Chemical 9]

Represents Where R ₄ , R ₅ , R ₈ and R ₉
Is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group,
Aryloxy group, alkylthio group, arylthio group,
R 10 represents an alkylsulfonyl group, an arylsulfonyl group or an amino group, R ₆ and R ₇ represent a hydrogen atom, an alkyl group, an aryl group, an alkylsulfonyl group, an arylsulfonyl group or an alkoxycarbonyl group, and R ₁₀
And R ₁₁ represents a hydrogen atom, an alkyl group or an aryl group. R ₁₀ and R ₁₁ may combine with each other to form a benzene ring. R ₄ and R ₈ , R ₅ and R ₉ , R ₆ and R ₇ or R ₆
And R ₅ may combine with each other to form a ring (for example, cyclobutane, cyclohexane, cycloheptane, cyclohexene, pyrrolidine, piperidine).

Among the heterocyclic groups represented by the formula [Y-II], particularly preferred one is Z in the formula [Y-II].

[0042]

[Chemical 10]

Is a heterocyclic group which is The C number of the heterocyclic group represented by the formula [Y-II] is 2 to 30, preferably 4 to 20,
More preferably, it is 5-16.

[0044]

[Chemical 11]

In the formula [Y-III], R ₁₂ and R ₁₃
At least one of halogen atom, cyano group, nitro group, trifluoromethyl group, carboxyl group, alkoxycarbonyl group, carbonamido group, sulfonamide group, carbamoyl group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group or acyl group. The other group may be a hydrogen atom, an alkyl group or an alkoxy group. R ₁₄ is R ₁₂ or R ₁₃
Represents a group having the same meaning as, and m represents an integer of 0 to 2. The C number of the aryloxy group represented by the formula [Y-III] is 6
-30, preferably 6-24, more preferably 6-15.

[0046]

[Chemical 12]

In the formula [Y-IV], W represents a nonmetal atom group necessary for forming a pyrrole ring, a pyrazole ring, an imidazole ring or a triazole ring together with N. here

[0048]

[Chemical 13]

The ring represented by may have a substituent, and preferred examples of the substituent include a halogen atom, a nitro group, a cyano group, an alkoxycarbonyl group, an alkyl group,
An aryl group, an amino group, an alkoxy group, an aryloxy group or a carbamoyl group. The C number of the heterocyclic group represented by the formula [Y-IV] is 2 to 30, preferably 2 to 24, more preferably 2 to 16.

Y in the formula [Y-I] is most preferably a group represented by the formula [Y-II].

The coupler represented by the formula [Y-I] has a substituent R ₁ , Q, Y, or

[0052]

[Chemical 14]

In the above, a dimer or a multimer having more than two valences may be bonded to each other to form a multimer.
In this case, the number of carbon atoms shown in each of the above substituents may be out of the specified range.

Specific examples of the yellow coupler represented by the formula [Y-I] are shown below.

[0055]

[Chemical 15]

[0056]

[Chemical 16]

[0057]

[Chemical 17]

[0058]

[Chemical 18]

[0059]

[Chemical 19]

[0060]

[Chemical 20]

[0061]

[Chemical 21]

[0062]

[Chemical formula 22]

[0063]

[Chemical formula 23]

[0064]

[Chemical formula 24]

[0065]

[Chemical 25]

[0066]

[Chemical formula 26]

[0067]

[Chemical 27]

The yellow coupler of the present invention represented by the formula [Y-I] can be synthesized by the following synthetic route.

[0069]

[Chemical 28]

Here, compound a was prepared according to J. Chem. Soc. (C). 1968.
2548, J.Am.Chem.Soc, 1934, 56 , 2710, Synthesis, 1971,25
8, J.Org.Chem, 1978, 4 3,1729 , is synthesized by the method described in CA, 1960, 6 6,18533y like.

Hereinafter, the compounds b, c, d, e and f can be synthesized by a conventionally known method.

The yellow coupler represented by the general formula [Y-I] of the present invention is 1.0 to 1.0 per mol of silver halide.
It can be used in a range of × 10 ^-3 mol. Preferably
5.0 × 10 ^-1 ~ 5.0 × 10 ^-2 mol, more preferably 4.0
It is in the range of × 10 ^{-1 to} 2.0 × 10 ^-2 mol.

Two or more kinds of yellow couplers represented by the general formula [YI] of the present invention can be used in combination.
Other known couplers can be used in combination.

The coupler represented by the general formula [Y-I] of the present invention can be introduced into the color light-sensitive material by various known dispersion methods.

In the oil-in-water dispersion method, an organic solvent having a low boiling point (eg, ethyl acetate, butyl acetate, methyl ethyl ketone, isopropanol, etc.) is used to apply a fine dispersion, and the dispersion is substantially low in the dry film. A method in which the boiling point organic solvent does not remain may be used. When a high-boiling organic solvent is used, any of those having a boiling point of 175 ° C. or higher at atmospheric pressure (specific examples thereof will be described later) may be used, and one kind or two or more kinds may be arbitrarily mixed and used. . The ratio of the coupler of the present invention to these high-boiling point organic solvents may be in a wide range, but is in the range of 5.0 or less by weight per 1 g of the coupler. It is preferably 0 to 0.2, and more preferably 0.01 to 1.0.

Next, the compound represented by the general formula [II] or the general formula [III] will be further described.

The substituent represented by V ₂₁ , V ₂₂ , V ₂₃ and V ₂₄ is preferably used as a halogen atom (eg chlorine atom), an aryl group (eg phenyl group) and an alkyl group (preferably). 1 to 7 carbon atoms, particularly preferably 1 to 4 carbon atoms, an alkoxy group (preferably 1 to 6 carbon atoms, particularly preferably 1 to 2 carbon atoms) alkoxycarbonyl group (for example, an ethoxycarbonyl group etc.) is there.

It is also preferable that two adjacent substituents are condensed to form a benzene ring.

When Z ₃ is = NR ₂₆ , a cyano group is also preferably used.

The substituent represented by R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ is preferably a halogen atom (eg chlorine atom), a hydroxy group, or a carbon atom number of 1 to 1.
4 alkyl groups, alkoxy groups, and amino groups (eg, dimethylamino group, diethylamino group, etc.), and when two adjacent substituents are condensed to form a ring (fused benzene ring, methylenedioxy group, etc.) preferable.

The alkyl group represented by R ₂₆ is an alkyl group having 1 to 6 carbon atoms (eg, methyl group, ethyl group,
(Eg, propyl group), and the alkyl group includes those having a substituent.

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

In the compound represented by the general formula [III], V ₃₁ , V ₃₂ , V ₃₃ and V ₃₄ have the same meanings as V ₂₁ , V ₂₂ , V ₂₃ and V ₂₄ , and R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ and R ₃₅ are R ₂₁ , R ₂₂ and
It is synonymous with R ₂₃ , R ₂₄ , and R ₂₅ .

R ₃₆ has the same meaning as R ₂₆ , X represents a charge-balancing ion, and k represents a value for neutralizing a charge of 0 or more.

Specific examples of the compound represented by the general formula [II] or the general formula [III] used in the present invention are shown below.
The present invention is not limited to these.

[0086]

[Chemical 29]

[0087]

[Chemical 30]

[0088]

[Chemical 31]

[0089]

[Chemical 32]

[0090]

[Chemical 33]

[0091]

[Chemical 34]

[0092]

[Chemical 35]

[0093]

[Chemical 36]

[0094]

[Chemical 37]

[0095]

[Chemical 38]

[0096]

[Chemical Formula 39]

[0097]

[Chemical 40]

The compound represented by the general formula [II] or the general formula [III] used in the present invention is preferably used in an amount capable of improving latent image storage, and particularly, silver halide in the emulsion 1
It is preferably used in a ratio of 1 × 10 ⁻³ to 1 × 10 ⁻² mol per mol.

The compound represented by the general formula [II] or the general formula [III] used in the present invention can be directly dispersed in the emulsion, or can be dispersed in a suitable solvent (eg, methyl alcohol, ethyl alcohol, methyl cell). It can also be dissolved in a solvent such as sorb and water) or a mixed solvent thereof and added to the emulsion. In addition, the sensitizing dye can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method for adding the sensitizing dye.

In the present invention, the yellow coupler represented by the above general formula [Y-I] (hereinafter, yellow coupler Y
-I. ) And a non-color-forming compound represented by the general formula [II] or the general formula [III] (hereinafter referred to as compounds [II] and [III], respectively) are contained in at least one of the blue-sensitive silver halide emulsion layers. To be done.

In order to incorporate the yellow coupler Y-I into the silver halide emulsion layer, a conventionally known method, for example, a known high-boiling solvent such as dibutyl phthalate or tricresyl phosphate and butyl acetate, ethyl acetate or the like can be used. The yellow coupler Y-I was dissolved in a mixed solution of low boiling point solvents such as those described above or a solvent of only low boiling point solvents, and then mixed with an aqueous gelatin solution containing a surfactant, and then a high speed rotary mixer or colloid mill or ultrasonic dispersion. After emulsifying and dispersing using a machine, a method of directly adding to the emulsion can be adopted. Further, after the above emulsified dispersion is set, it may be shredded, washed with water, and then added to the emulsion.

As the silver halide emulsion used in the light-sensitive material of the present invention, any ordinary silver halide emulsion can be used. The emulsion can be chemically sensitized by a conventional method, and can be optically sensitized to a desired wavelength region by using a sensitizing dye.

An antifoggant, a stabilizer and the like can be added to the silver halide emulsion. It is advantageous to use gelatin as the binder of the emulsion.

The emulsion layer and other hydrophilic colloid layers can be hardened and can contain a plasticizer and a dispersion (latex) of a water-insoluble or sparingly soluble synthetic polymer. A coupler is used in the emulsion layer of the color photographic light-sensitive material.

Further, the development accelerator, the bleaching accelerator, the developer, the silver halide solvent, the toning agent, the hardener and the hardener can be obtained by coupling with the colored coupler, the competing coupler and the oxidized product of the developing agent, which have the effect of color correction. Compounds that release photographically useful fragments such as film agents, antifoggants, antifoggants, chemical sensitizers, spectral sensitizers, and desensitizers can be used.

The light-sensitive material may be provided with auxiliary layers such as a filter layer, an antihalation layer and an irradiation prevention layer. In these layers and / or emulsion layers,
Dyes may be included which are bleached or bleached from the light-sensitive material during the development process. For the light-sensitive material, formalin scavenger, fluorescent whitening agent, matting agent, lubricant, image stabilizer, surfactant, color antifoggant, development accelerator,
Development retarders and bleaching accelerators can be added.

As the support, paper laminated with polyethylene or the like, polyethylene terephthalate film, baryta paper, cellulose triacetate or the like can be used.

In order to obtain a dye image using the light-sensitive material of the present invention, a commonly known color photographic process can be carried out after exposure.

[0109]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these.

In all of the following examples, the addition amount in the silver halide photographic light-sensitive material is the number of grams per 1 m ² unless otherwise specified. Also, silver halide and colloidal silver are shown in terms of silver.

Example 1 A multi-layer color photographic light-sensitive material (Sample 101) was prepared by sequentially forming each layer having the composition shown below from the support side on a triacetyl cellulose film support.

First layer; antihalation layer (HC-1) Black colloidal silver 0.20 UV absorber (UV-1) 0.20 Colored coupler (CC-1) 0.05 Colored coupler (CM-1) 0.05 High boiling solvent (Oil-) 1) 0.20 gelatin 1.5 second layer; intermediate layer (IL-1) UV absorber (UV-1) 0.01 high boiling solvent (Oil-1) 0.01 gelatin 1.5 third layer; low sensitivity red-sensitive emulsion layer (RL) iodine Silver bromide emulsion (Em-1) 0.8 Silver iodobromide emulsion (Em-2) 0.8 Sensitizing dye (SD-1) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-2) 2.5 × 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-3) 0.5 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 1.0 Colored cyan coupler (CC-1) 0.05 DIR compound (D-1) 0.002 High boiling point solvent (Oil-1) 0.5 Gelatin 1.5 4th layer; High sensitivity red Sensitive emulsion layer (RH) Silver iodobromide emulsion (Em-3)
2.0 Sensitizing dye (SD-1) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (SD-2) 2.0 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (SD-3) 0.1 × 10 ^-4 (mol / silver 1 mol) Cyan coupler (C-1) 0.25 Cyan coupler (C-2) 0.05 Colored cyan coupler (CC-1) 0.015 DIR compound (D-1) 0.05 High boiling point solvent (Oil- 1) 0.2 gelatin 1.5 fifth layer; intermediate layer (IL-2) gelatin 0.5 sixth layer; low sensitivity green sensitive emulsion layer (GL) silver iodobromide emulsion (Em-1) 1.3 sensitizing dye (SD-4) 5 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (SD-5) 1 × 10 ⁻⁴ (mol / silver 1 mol) Magenta coupler (MA) 0.25 Magenta coupler (MB) 0.25 Colored magenta Coupler (CM-1) 0.01 DIR compound (D-3) 0.02 DIR compound (D-4) 0.020 High boiling point solvent (Oil 2) 0.3 Gelatin 1.0 7th layer; high-sensitivity green-sensitive emulsion layer (GH) Silver iodobromide emulsion (Em-3) 1.3 Sensitizing dye (SD-6) 1.5 × 10 -4 ( mol / 1 mol of silver), up Sensitizing dye (SD-7) 2.5 × 10 ⁻⁴ (mol / silver 1 mol) Sensitizing dye (SD-8) 0.5 × 10 ⁻⁴ (mol / silver 1 mol) Magenta coupler (MA) 0.05 Magenta coupler ( MB) 0.10 Colored magenta coupler (CM-2) 0.05 DIR compound (D-3) 0.01 High boiling point solvent (Oil-2) 0.2 Gelatin 1.0 Eighth layer; Yellow filter layer (YC) Yellow colloidal silver 0.1 Color contamination prevention Agent (SC-1) 0.1 High boiling point solvent (Oil-3) 0.1 Gelatin 0.8 Ninth layer; Low sensitivity blue-sensitive emulsion layer (BL) Silver iodobromide emulsion (Em-1) 0.25 Silver iodobromide emulsion (Em- 2) 0.25 sensitizing dye (SD-10) 7 × 10 -4 ( mol / mole of silver) yellow coupler (EY 1) 0.5 yellow coupler (EY-2) 0.1 DIR compound (D-2) 0.01 high boiling solvent (Oil-2) 0.3 gelatin 1.0 10th layer; high sensitivity blue sensitive emulsion layer (BH) silver iodobromide emulsion (Em -4) 0.4 Silver iodobromide emulsion (Em-1) 0.4 Sensitizing dye (SD-9) 1 x 10 ^-4 (mol / silver 1 mol) Sensitizing dye (SD-10) 3 x 10 ^-4 (mol / 1 mol of silver) Yellow coupler (EY-1) 0.30 Yellow coupler (EY-2) 0.05 High boiling point solvent (Oil-2) 0.15 Gelatin 1.1 11th layer; 1st protective layer (PRO-1) Fine grain silver iodobromide Emulsion (average particle size 0.08 μm, AgI content 2 mol%) 0.4 UV absorber (UV-1) 0.10 UV absorber (UV-2) 0.05 High boiling solvent (Oil-1) 0.1 High boiling solvent (Oil-3) ) 0.1 Formalin Scavenger (HS-1) 0.5 Formalin Scavenger (HS-2) 0.2 Gelatin 1.0 12th layer; 2nd protective layer (PRO-2) Surfactant (Su-1) 0.005 Alkali-soluble matting agent (average particle size 2 μm) 0.05 Polymethylmethacrylate (average particle size 3 μm) 0.05 Sliding agent (WAX) -1) 0.04 Gelatin 0.6 In addition to the above composition, each layer contains coating aid Su-2, dispersion aid Su-3, hardeners H-1 and H-2, stabilizer ST-.
1, antifoggants AF-1 and AF-2 were added.

Em-1 Average grain size 0.46 μm Average silver iodide content: 7.0 mol%, monodisperse (width of distribution: 14%) surface low silver iodide (2 mol%) core / shell type emulsion Em-2 Average grain size 0.30 μm Average silver iodide content: 2.0 mol%, monodisperse (14% distribution) surface silver bromide-containing core / shell emulsion Em-3 Average grain size 0.81 μm Average Silver iodide content: 7.0 mol%, monodisperse (width of distribution: 14%) surface low silver iodide (1.
0 mol%)-containing core / shell type emulsion Em-4 average grain size 0.95 μm average silver iodide content: 8.0 mol%, monodisperse (width of distribution: 14%) surface low silver iodide (0.
5 mol%) containing core / shell type emulsion

[0114]

[Equation 1]

[0115]

[Chemical 41]

[0116]

[Chemical 42]

[0117]

[Chemical 43]

[0118]

[Chemical 44]

[0119]

[Chemical formula 45]

[0120]

[Chemical formula 46]

[0121]

[Chemical 47]

[0122]

[Chemical 48]

Next, as shown in Table 1, in Sample 101, the yellow coupler EY-1 added to the ninth and tenth silver halide emulsion layers was replaced with an equimolar amount of the yellow coupler of the present invention. And a non-color-developing compound of the present invention shown in Table 1 which improves the latent image preservation of 1 × 10 ⁻⁴ mol per mol of silver halide as a comparative sample. Samples 104 to 115 were prepared by adding 102, 103 and the compound of the present invention in combination.

Each of the samples 101 to 115 thus produced was subjected to wedge exposure for 1/100 second using white light, and then the following development processing was performed.

Processing step (38 ° C.) Color development 3 minutes 15 seconds Bleach 6 minutes 30 seconds Water washing 3 minutes 15 seconds Settling 6 minutes 30 seconds Water washing 3 minutes 15 seconds Stabilization 1 minute 30 seconds Drying Each processing step The composition of the treatment liquid used in 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 37.5g Potassium bromide 1.3g Nitrilotriacetic acid trisodium salt (monohydrate)
2.5g potassium hydroxide
Add 1.0 g water to make 1 liter. (PH = 10.2) <Bleach> Ethylenediaminetetraacetic acid iron (III) ammonium salt 100g Ethylenediaminetetraacetic acid diammonium salt 10.0g Ammonium bromide 150.0g Glacial acetic acid 10ml Add water to make 1 liter, and use ammonia water to adjust the 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 using acetic acid.

<Stabilizer> Formalin (37% aqueous solution) 1.5 ml Conidax (manufactured by Konica Corporation) 7.5 ml Water is added to make 1 liter.

An optical densitometer PDA was used for the obtained processed sample.
-65 type (manufactured by Konica Corporation), sensitivity of blue-sensitive emulsion layer (reciprocal of exposure amount required to give minimum density +0.1)
And the fog density was measured. The sensitivity is shown as a relative value when the sensitivity of Sample 101 is 100.

Next, four sets of samples 101 to 115 were prepared, and 1/100
After performing wedge exposure in seconds, one set is 55 ℃, 55% RH
Stored under warm and humid conditions for 3 days, another set at 23 ℃, 55% RH
It was stored for 30 days, and the remaining two sets were stored in a freezer, used as a control, and developed in the same manner as above, and the latent image storability was evaluated.

The latent image storability was shown by the relative value of the sensitivity with respect to the control sensitivity of each sample being 100.

Further, in order to examine the raw preservation property, samples 101-1
15 is left under high temperature and high humidity (55 ° C, RH60%) for 3 days, and subjected to the same wedge exposure and color development processing as described above,
The fog density of the blue sensitive layer was measured, and the difference (ΔFog) in fog density from the sample before standing was determined.

The results are shown below.

[0134]

[Table 1]

From the results shown in Table 1, the samples 104 to 115 of the present invention, in comparison with the comparative samples 101 to 103, showed no increase in fog density and deterioration of sensitivity, and the latent image storability was improved and the raw storability was excellent. You can see that

[0136]

According to the present invention, it is possible to provide a silver halide color photographic light-sensitive material having high sensitivity, low fog, and improved latent image storability and raw storability.

Claims (1)

[Claims] 1. A silver halide color photographic light-sensitive material having a silver halide emulsion layer consisting of a blue-sensitive layer, a green-sensitive layer and a red-sensitive layer on a support, wherein at least one of the blue-sensitive layers has the following general composition. A silver halide containing at least one coupler represented by the formula [Y-I] and at least one compound represented by the following general formula [II] or the following general formula [III]. Color photographic light-sensitive material. [Chemical 1] (In the formula, R ₁ represents a monovalent substituent except a hydrogen atom, and Q 1
Is required to form a 3- to 5-membered hydrocarbon ring with C, or to form a 3- to 5-membered heterocycle containing at least one hetero atom selected from N, S, O and P in the ring. Represents a non-metallic atomic group. R ₂ is a hydrogen atom, an alkyl group,
An alkoxy group, an aryloxy group, an amino group or a halogen atom is represented, and Y is a hydrogen atom or a group capable of splitting off by a coupling reaction with an oxidized product of an aromatic primary amine developer. ) [Chemical 2] (In the formula, Z ₁ represents an oxygen atom, a sulfur atom, a selenium atom, a tellurium atom or = NR _26. V ₂₁ , V ₂₂ , V ₂₃ , and V ₂₄ are a hydrogen atom, a halogen atom, an aryl group, an alkyl group, and a substituent. It represents an alkyl group, an alkoxy group, an alkoxycarbonyl group, a carboxy group, a hydroxy group or a cyano group, provided that V ₂₁ and V ₂₂ , V ₂₂ and V ₂₃ , V ₂₃ and V ₂₄ are each condensed 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 hydroxy group, an alkyl group, an alkoxy group, an aryl group, an amino group, or a group capable of condensing an adjacent substituent to form a 5- or 6-membered ring. R ₂₆ represents a substituted or unsubstituted alkyl group or aryl group. ) [Chemical 3] (In the formula, Z ₂ has the same meaning as Z ₁ , and V ₃₁ , V ₃₂ , V ₃₃ , V
₃₄ is synonymous with V ₂₁ , V ₂₂ , V ₂₃ , and V ₂₄ , respectively. R ₃₁ ,
R ₃₂ , R ₃₃ , R ₃₄ and R ₃₅ are respectively R ₂₁ , R ₂₂ , R ₂₃ and
Synonymous with R ₂₄ and R ₂₅ . R ₃₆ represents a substituted or unsubstituted alkyl group or aryl group. X represents a charge-balancing counterion, and k represents a value that neutralizes 0 or more charges. )