JP2675933B2 - Silver halide color photographic materials - Google Patents

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, particularly containing a novel timing DIR coupler and an aldehyde scavenger, and having pressure resistance, color reproducibility, sharpness, graininess and desilvering property. The present invention relates to a silver halide color photographic light-sensitive material having a good image quality and less fluctuation in photographic performance during storage.

[0002]

2. Description of the Related Art A silver halide color photographic light-sensitive material, especially a color sensitive material for photographing, has high sensitivity and good pressure resistance, color reproducibility, graininess and sharpness, and the fluctuation of photographic performance during storage. There is a demand for less photosensitive material.

Means for improving color reproducibility and sharpness include, for example, JP-A Nos. 51-146828 and 60-2.
18645, 61-156127, 63-37.
No. 346, JP-A Nos. 1-280755 and 1-2197.
No. 47, No. 2-230139, European Patent Publication 3
48139, 354532 and 403019
There are known couplers which release the development-inhibiting compounds described in US Pat. Certainly, by using these timing DIR couplers, the interlayer effect and the edge effect were improved and the color reproducibility and the sharpness were improved to some extent, but the release of the development inhibitor was substantially further, or Due to unfavorable timing of release, the effect was still insufficient. Further, a photosensitive material using these couplers has a problem that the photographic performance greatly varies during storage, and the photographic performance is apt to change when the photosensitive material is bent or scratched.

On the other hand, a combination of a polymer coupler and various development inhibitor releasing compounds is disclosed in, for example, JP-A-59-36.
No. 249, No. 60-101534, No. 61-4374.
No. 7 and JP-A-1-147544, some effects such as color reproducibility, sharpness, and graininess have been obtained, but the pressure resistance and storability of the light-sensitive material are still unsatisfactory. .

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to firstly provide a light-sensitive material having excellent pressure resistance, and secondly to provide a light-sensitive material having less fluctuation in photographic performance during storage. Thirdly, to provide a light-sensitive material having high sensitivity, excellent sharpness, color reproducibility and desilvering property.

[0006]

The above object has been attained by the following silver halide color photographic light-sensitive material.

A silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer on a support and containing an aldehyde scavenger is represented by the following general formula (I) and / or the following chemical formula (4). General formula (I
A silver halide color photographic light-sensitive material comprising a compound represented by I).

[0008]

Embedded image A in the general formula (I) represents a coupler residue or a redox group, L ₁ and L ₃ represent a divalent timing group, and L ₂ represents a trivalent or higher-valent timing group. And PUG represents a photographically useful group. j
And n each independently represent 0, 1 or 2, and m is 1
Or 2 and s is a number obtained by subtracting 1 from the valence of L ₂ and represents an integer of 2 or more. Also L ₁ , L ₂ or L
_{When 3} is present in plural in the molecule, they may all be the same or different. There are multiple PUs
All G's may be the same or different.

[0009]

Embedded image A and PUG in the general formula (II) have the same meaning as in the general formula (I). L ₄ represents -OCO- group, -OSO- group, -OSO ₂ -
It represents a group - group, -OCS- group, -SCO- group, -SCS- group or -WCR ₁₁ R _12. Here, W represents an oxygen atom, a sulfur atom or a tertiary amino group (—NR ₁₃ —), and R
₁₁ and R ₁₂ each independently represent a hydrogen atom or a substituent, and R ₁₃ represents a substituent. In addition, R ₁₁ , R ₁₂ and R
Each of ₁₃ represents a divalent group and includes a case where they are linked to each other to form a cyclic structure. L ₅ is PU due to electron transfer along the conjugated system
It represents a group releasing G or a group defined by L ₄ .

The general formula (I) and the general formula (I
The coupler represented by I) will be described in detail.

In the general formula (I), A specifically represents a coupler residue or a redox group.

Examples of the coupler residue represented by A include yellow coupler residues (for example, open-chain ketomethylene type coupler residues such as acylacetanilide and malondianilide) and magenta coupler residues (for example, 5-pyrazolone type and pyrazolotriazole). Type or an imidazopyrazole type coupler residue), a cyan coupler residue (for example, phenol type, naphthol type, imidazole type or the same type as described in European Patent Publication 249,453).
Coupler residues such as pyrazolopyrimidine type described in U.S. Pat. No. 4,001) and colorless coupler residues (e.g., coupler residues such as indanone type or acetophenone type). Also, U.S. Pat. Nos. 4,315,070, 4,183,752, 4,174,969, 3,961,959, 4,171,223 or JP-A-52-82423. It may be a heterocyclic coupler residue described in No.

When A represents a redox group, the redox group is a group which can be cross-oxidized by an oxidized product of a developing agent, and examples thereof include hydroquinones, catechols, pyrogallols, 1,4-naphthohydroquinones, 1 , 2-naphthohydroquinones, sulfonamide phenols,
Hydrazides or sulfonamido naphthols are exemplified. These groups are specifically described in, for example, JP-A-61-2.
No. 30135, No. 62-251746, No. 61-27
8852, U.S. Pat. Nos. 3,364,022, 3,379,529, 3,639,417, 4,684,604 or J. Org. Che
m. , 29, 588 (1964).

In the general formula (I), L ₁ preferably includes the following.

(1) Group Utilizing Cleavage Reaction of Hemiacetal For example, US Pat. No. 4,146,396, JP-A-60-
No. 249148 and No. 60-249149, which are groups represented by the following general formula (T-1). Here, * indicates A or L of the compound represented by the general formula (I).
_It represents the position of binding to _1, and the ** mark represents the position of binding to L ₁ or L ₂ . Formula (T-1) * - ( W-CR 11 (R 12)) t - ** In formula, W is an oxygen atom, a sulfur atom or -NR ₁₃ - represents a group, R ₁₁ and R ₁₂ are a hydrogen atom Or a substituent, R ₁₃ represents a substituent, and t represents 1 or 2.
When t is 2, two -W-CR ₁₁ (R ₁₂ ) represent the same or different. When R ₁₁ and R ₁₂ represent a substituent and typical examples of R ₁₃ are R ₁₅ group and R ₁₃ respectively.
Examples thereof include a ₁₅ CO- group, an R ₁₅ SO ₂ -group, an R ₁₅ (R ₁₆ ) NCO- group and an R ₁₅ (R ₁₆ ) NSO ₂ -group. Here, R ₁₅ represents an aliphatic group, an aromatic group or a heterocyclic group, and R _15
16 represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group. R ₁₁ , R ₁₂ and R ₁₃ each represent a divalent group, and are linked to form a cyclic structure. Specific examples of the group represented by the general formula (T-1) are shown below.
A group such as Chemical formula 7 can be mentioned.

[0016]

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[0017]

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[0018]

Embedded image (2) Group that causes cleavage reaction utilizing intramolecular nucleophilic substitution reaction For example, a timing group described in US Pat. No. 4,248,292 can be mentioned. It can be represented by the following general formula. General formula (T-2) * -Nu-Link-E-** In the formula, Nu represents a nucleophilic group, an oxygen atom or a sulfur atom is an example of a nucleophilic species, E represents an electrophilic group, Nu Link is a group that can be more nucleophilically attacked to cleave the bond with **, and Link represents a linking group that sterically links Nu and E so that they can undergo an intramolecular nucleophilic substitution reaction. Specific examples of the group represented by the general formula (T-2) include those shown in the following chemical formulas 8 and 9.

[0019]

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[0020]

Embedded image (3) A group that causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system.

For example, US Pat. No. 4,409,323,
U.S. Pat. No. 4,421,845, JP-A-57-188035.
No. 58-98728, 58-209736,
No. 58-209737 and No. 58-209738, and it is a group represented by the general formula (T-3) shown in Chemical formula 10 below.

[0022]

Embedded image In the formula, * mark, ** mark, W, R ₁₁ , R ₁₂ and t have the same meanings as described for the general formula (T-1). However, R ₁₁ and R ₁₂ may combine to form a benzene ring or a heterocyclic ring. Further, R ₁₁ or R ₁₂ and W may combine with each other to form a benzene ring or a heterocycle. Z ₁ and Z ₂ each independently represent a carbon atom or a nitrogen atom, and x and y represent 0 or 1. Z ₁
Is 1 when x is a carbon atom, and x is 0 when Z ₁ is a nitrogen atom. Relationship between Z ₂ and y is the same as the relationship between Z ₁ and x. Also, t represents 1 or 2, and when t is 2, two-[Z ₁ (R ₁₁ ) _x = (X ₂ (R ₁₂ ) _y ]-
May be the same or different. The -CH ₂ adjacent to the mark ** - group may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms.

Specific examples of the general formula (T-3) are shown below.
1 to 14

[0024]

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[0025]

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[0026]

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[0027]

Embedded image (4) A group utilizing a cleavage reaction due to hydrolysis of an ester.

For example, West German Published Patent No. 2,626,315
And the following groups. In the formulas, * and ** have the same meaning as described for the general formula (T-1). General formula (T-4) * -OCO-** General formula (T-5) * -SCS-** (5) Group which utilizes the cleavage reaction of imino ketal.

For example, a linking group described in US Pat. No. 4,546,073, represented by the general formula (T
It is a group represented by -6).

[0030]

Embedded image In the formulas, *, ** and W have the same meanings as described in formula (T-1), and R ₁₄ has the same meaning as R ₁₃ . Specific examples of the group represented by formula (T-6) include groups represented by the following chemical formula 16.

[0031]

Embedded image L ₁ is preferably one represented by the general formulas (T-1) to (T-5), and particularly preferably (T-1) (T-
3) and (T-4).

In the general formula (I), j is preferably 0.
Or 1.

The group represented by L ₂ in the general formula (I) represents a trivalent or higher valent timing group, preferably represented by the following general formula (T-L ₁ ) or (T-L ₂ ). . Formula (T-L ₁₎ * -W- _{[Z 1 - (R 11) x} = Z 2 (R 12) y ] _t -C
H ₂ - ** wherein _{W, Z 1, Z 2,} R 11, R 12, x, y and t have the same meanings as described for formula (T-3). Further, the * mark represents the position at which it bonds to A- (L ₁ ) _j- in the general formula (I), and the ** mark represents the position at which it bonds to-(L ₃ ) _n -PUG. However, there are a plurality of R ₁₁ or R ₁₂
At least one of the substituted or unsubstituted methylene group - represents the (L _{3) n} -PUG with binding group.

In the general formula (T-L ₁ ), W is preferably a nitrogen atom, and more preferably W and Z.
It is the case where ₂ is bonded to form a 5-membered ring, particularly preferably the case where an imidazole or pyrazole ring is formed. General formula (T-L < ₂ >) *-N- (Z < ₃ >-**) _{2 In} formula, * mark and ** mark are synonymous with general formula (T-L < ₁ >). The Z ₃ group represents a substituted or unsubstituted methylene group, and the two Z ₃ groups may be the same or different. Further, two Z ₃ groups may combine to form a ring.

Specific examples of the general formulas (T-L ₁ ) and (T-L ₂ ) are shown in the following chemical formulas 17 to 23, but the present invention is not limited thereto.

[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

Embedded image However, the groups exemplified in the examples here may further have a substituent, and examples of such a substituent include an alkyl group (for example, methyl, ethyl, isopropyl, t-butyl, hexyl, methoxymethyl, methoxy). Ethyl, chloroethyl, cyanoethyl, nitroethyl, hydroxypropyl, carboxyethyl, dimethylaminoethyl, benzyl, phenethyl), aryl groups (eg phenyl,
Naphthyl, 4-hydroxyphenyl, 4-cyanophenyl, 4-nitrophenyl, 2-methoxyphenyl, 2,
6-dimethylphenyl, 4-carboxyphenyl, 4-
Sulfophenyl), a heterocyclic group (eg 2-pyridyl,
4-pyridyl, 2-furyl, 2-thiethyl, 2-pyrrolyl), halogen atom (eg chloro, bromo), nitro group, amecoxy group (eg methoxy, ethoxy, isopropoxy), aryloxy group (eg phenoxy),
Alkylthio group (eg methylthio, isopropylthio, t-butylthio), arylthio group (eg phenylthio), amino group (eg amino, dimethylamino,
Diisopropylamino), acylamino group (eg acetylamino, benzoylamino), sulfonamide group (eg methanesulfonamide, benzenesulfonamide), cyano group, carboxyl group, alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl), aryloxycarbonyl (Eg phenoxycarbonyl) or a carbamoyl group (eg N-ethylcarbamoyl, N-phenylcarbamoyl).

Of these, an alkyl group, a nitro group,
An alkoxy group, an alkylthio group, an amino group, an acylamino group, a sulfonamide group, an alkoxycarbonyl group, and a carbamoyl group.

In the general formula (T-L ₁ ), the —CH ₂ — group adjacent to the ** mark may be substituted with an alkyl group having 1 to 6 carbon atoms or a phenyl group.

In the general formula (I), m is preferably 1
It is.

The group represented by L ₃ in formula (I) has the same meaning as L ₁ .

In the general formula (I), n is preferably 0.
Alternatively, it is 1, and particularly preferably 0.

More specifically, the photographically useful group represented by PUG in the general formula (I) is, for example, a development inhibitor, a dye, a fogging agent, a developer, a coupler, a bleaching accelerator or a fixing accelerator. Examples of preferred photographically useful groups are described in U.S. Pat.
No. 8,962, a photographically useful group (the one represented by the general formula PUG in the patent), JP-A-62-4935.
No. 3 (in the specification, a part of a leaving group released from a coupler), US Pat. No. 4,477,563.
And a development inhibitor described in JP-A-61-201.
247 and JP-A-2-55 (the part of the leaving group released from the coupler in the specification). In the present invention, particularly preferred as a photographically useful group is a development inhibitor.

As a development inhibitor, the following chemical formulas
General formulas (INH-1) to (INH-13) shown in Chemical formula 29
Is a group represented by

[0050]

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[0051]

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[0052]

Embedded image In the formula, R ₂₁ is a hydrogen atom or a substituted or unsubstituted hydrocarbon group (eg, methyl, ethyl, propyl, phenyl)
Represents

[0053]

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[0054]

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[0055]

Embedded image In the formula, * represents a position at which the compound represented by the general formula (I) is bonded to the group represented by L ₂ or L ₃ .

Further, ** represents a position to be bonded to a substituent, and examples of the substituent include a substituted or unsubstituted aliphatic group, an aryl group and a heterocyclic group, which are decomposed in a processing solution during photographic processing. It is preferred that groups are included in these substituents.

Specific examples of the aliphatic group include methyl, ethyl, propyl, butyl, hexyl, decyl, isobutyl, t-butyl, 2-ethylhexyl, 2-methylthioethyl, benzyl, 4-methoxybenzyl, phenethyl, 1 -Methoxycarbonylethyl, propyloxycarbonylmethyl, methoxycarbonyl, phenoxycarbonyl, 2- (propyloxycarbonyl) ethyl, butyloxycarbonylmethyl, pentyloxycarbonylmethyl, 2-cyanoethyloxycarbonylmethyl, 2,2-dichloroethyloxycarbonyl Methyl, 3-nitropropyloxycarbonylmethyl, 4-
Nitrobenzyloxycarbonyl methyl, 2,5-dioxo-3,6-Jiokisadeshiru, -CO ₂ CH ₂ CO ₂
Examples thereof include groups represented by R ₁₀₀ .

R ₁₀₀ represents an unsubstituted alkyl group having 1 to 8 carbon atoms. Examples of the aryl group include phenyl, naphthyl, 4-methoxycarbonylphenyl, 4-ethoxycarbonylphenyl, 2-methylthiophenyl, 3-methoxycarbonylphenyl, 4- (2
-Cyanoethyloxycarbonyl) -phenyl.

Examples of the heterocyclic group include 4-pyridyl, 3-pyridyl, 2-pyridyl, 2-furyl, 2-
And tetrahydropyranyl.

Of these, INH is preferably (I
NH-1), (INH-2), (INH-3), (IN
H-4), (INH-9) and (INH-12), particularly preferably (INH-1), (INH-2) and (INH-3).

The substituent bonded to INH is preferably an aliphatic group or a substituted or unsubstituted phenyl group.

The compound represented by the general formula (I) is particularly preferably a compound represented by the following general formula (Ia) or (Ib). Formula _{(Ia) A- (L 1)} j -W- _{[Z 1 - (R 11) x} ) = Z 2 (R
_{12) y] t} -CH ₂ -PUG general formula _{(Ib) A-L 1 -N-} (Z 3 -PUG) symbol ₂ where the general formula (I), (T-L 1) and (T-
Synonymous with L ₂ ). In the general formula (Ia), j is preferably 0 or 1. In formulas (Ia) and (Ib), L ₁ is preferably a —OC (═O) — group, and PUG is preferably a development inhibitor.

However, when a plurality of photographically useful groups have different functions, the timing group does not utilize intramolecular nucleophilic substitution.

The function of the photographically useful group means the function exhibited by a development inhibitor, a dye, a fogging agent, a developing agent, a coupler, a bleaching accelerator or a fixing agent.

Further, it is particularly preferable that two or more PUGs released from the same compound are the same development inhibitor.

Next, the compound represented by formula (II) will be described. In the general formula (II), A and PUG have the same meaning as in the general formula (I). L ₄ is a —OCO— group, —OSO—
Group, -OSO ₂ - group, -OCS- group, -SCO- group, -
SCS- group or -WCR ₁₁ R ₁₂ - represents a group. Here, W, R ₁₁ and R ₁₂ have the same meaning as defined in formula (T-1) in the description of L ₁ of the compound represented by formula (I).

When L ₄ represents a --WCR ₁₁ R ₁₂ --group, a preferred example is when W represents an oxygen atom or a tertiary amino group, more preferably L ₄ represents --OCH _2-.
A group or W and R ₁₁ or R ₁₂ represents a group forming a ring.

[0068] The L ₄ is -WCR ₁₁ R ₁₂ - preferably -OCO- group may represent a group other than, -OSO- group, -O
SO ₂ - is a group, particularly preferably -OCO- group.

The group represented by L ₅ represents a group which releases PUG by electron transfer along the conjugated system or a group defined by L ₄ . The group which releases PUG by electron transfer along a conjugated system general formula formula within the description of the L ₁ of (I) (T
-3) has the same meaning as the group represented by. L ₅ is preferably a group which releases PUG by electron transfer along a conjugated system, and more preferably a group which can be bonded to L ₄ by a nitrogen atom.

Among the compounds represented by the general formula (II), preferred are compounds represented by the general formula (III) shown in the following chemical formula 30 or the general formula (IV) shown in the following chemical formula 31.

[0071]

Embedded image In the formula, A has the same meaning as in formula (I). R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or a substituent. R
₁₀₃ and R ₁₀₄ each independently represent a hydrogen atom or a substituent. INH represents a group having a development inhibiting ability. R
₁₀₅ represents an unsubstituted phenyl group or a primary alkyl group or a primary alkyl group substituted with a group other than an aryl group. However, at least one of R _{101 to} R ₁₀₄ is a substituent other than a hydrogen atom.

[0072]

Embedded image The compound represented by formula (III) will be described in more detail.

In the general formula (III), A has the same meaning as in the general formula (I). R ₁₀₁ and R ₁₀₂ each independently represent a hydrogen atom or a substituent. Specific examples of the substituent include an aryl group (phenyl, naphthyl, p-methoxyphenyl, p-hydroxyphenyl, p-nitrophenyl, o
-Chlorophenyl, etc.), alkyl groups (methyl, ethyl, isopropyl, propyl, tert-butyl, te
rt-amyl, isobutyl, sec-butyl, octyl, methoxymethyl, 1-methoxyethyl, 2-chloroethyl, etc.), halogen atom (fluoro, chloro, bromo, iodo), alkoxy group (methoxy, ethoxy, isopropyloxy, propyloxy) , Tert-butyloxy, isobutyloxy, butyloxy, octyloxy, 2-methoxyethoxy, 2-chloroethoxy, nitromethyl, 2-cyanoethyl, 2-carbamoylethyl, or 2-dimethylcarbamoylethyl), an aryloxy group (phenoxy, naphthoxy). , Or p-
Methoxyphenoxy, etc.), alkylthio groups (methylthio, ethylthio, isopropylthio, propylthio, t
ert-butylthio, isobutylthio, sec-butylthio, octylthio or 2-methoxyethylthio, etc.) arylthio group (phenylthio, naphthylthio, or p-methoxyphenylthio, etc.), amino group (amino, methylamino, phenylamino, dimethylamino,
Diethylamino, diisopropylamino, phenylmethylamino, etc.), carbamoyl group (carbamoyl, methylcarbamoyl, dimethylcarbamoyl, diethylcarbamoyl, diisopropylcarbamoyl, ethylcarbamoyl, isopropylcarbamoyl, tert.
-Butylcarbamoyl, phenylcarbamoyl or phenylmethylcarbamoyl etc.), sulfamoyl group (sulfamoyl, methylsulfamoyl, ethylsulfamoyl, isopropylsulfamoyl, phenylsulfamoyl, octylsulfamoyl, dimethylsulfamoyl, diethylsulfamoyl) Famoyl, diisopropylsulfamoyl, dihexylsulfamoyl, phenylmethylsulfamoyl, etc.), alkoxycarbonyl (methoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, tert-butyloxycarbonyl, tert-amyloxycarbonyl, or octyl) Oxycarbonyl, etc.), aryloxycarbonyl (phenoxycarbonyl or p-methoxyphenoxycarbo) Le etc.), an acylamino group (an acetylamino, propanoylamino, pentanoylamino, N- methyl acetylamino, or benzoylamino, etc.), a sulfonamido group (methanesulfonamido, ethanesulfonamide, pentane sulfonamide,
Benzenesulfonamide or p-toluenesulfonamide), an alkoxycarbonylamino group (methoxycarbonylamino, isopropyloxycarbonylamino, tert-butoxycarbonylamino or hexyloxycarbonylamino, etc.), an aryloxycarbonylamino group (phenoxycarbonylamino, etc.) ,
Examples thereof include a ureido group (3-methylureido, 3-phenylureido, etc.), a cyano group, a nitro group and the like.

R ₁₀₁ and R ₁₀₂ may be the same or different, but the sum of the formula weights of both is preferably less than 120. Examples of preferable substituents include an alkyl group, a halogen atom and an alkoxy group, and an alkyl group is particularly preferable.

In formula (III), the groups represented by R ₁₀₃ and R ₁₀₄ each independently represent a hydrogen atom or an alkyl group. As the alkyl group, methyl, ethyl, isopropyl, tert-butyl, isobutyl, hexyl,
Alternatively, 2-methoxyethyl and the like can be mentioned. R ₁₀₃ and R ₁₀₄ are preferably a hydrogen atom, a methyl group or an ethyl group, and particularly preferably a hydrogen atom.

In formula (III), the group represented by R ₁₀₅ represents an unsubstituted phenyl group or a primary alkyl group, or a primary alkyl group substituted with a group other than an aryl group. As the alkyl group, ethyl, propyl, butyl,
Examples thereof include isobutyl, pentyl, isopentyl, 2-methylbutyl, hexyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2-ethylbutyl, heptyl, octyl and the like. As the substituent, a halogen atom, an alkoxy group, an alkylthio group, an amino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, an acylamino group, a sulfonamide group,
Examples thereof include an alkoxycarbonylamino group, a ureido group, a cyano group, a nitro group, and a group represented by —CO ₂ CH ₂ CO ₂ R _106. Specific examples of each group include a substituent of R ₁₀₁ and R _102. Among those mentioned, those excluding a group containing an aryl group can be mentioned.

R ₁₀₆ is an unsubstituted alkyl group having 3 to 6 carbon atoms (propyl, butyl, isobutyl, pentyl,
Isopentyl, hexyl, etc.).

Further, R ₁₀₅ may be substituted with two or more kinds of substituents. The substituent of R ₁₀₅ is preferably fluoro, chloro, alkoxy group, alvamoyl group, alkoxycarbonyl group, cyano group, nitro group, or-.
CO ₂ CH ₂ CO ₂ R ₁₀₆ . Of these, particularly preferred is an alkoxycarbonyl group or -CO ₂
CH ₂ CO ₂ R ₁₀₆ group.

R ₁₀₅ is preferably a phenyl group,
Alternatively, it is a primary unsubstituted alkyl group having 2 to 6 carbon atoms, or a primary alkyl group substituted by the groups listed as the above-mentioned preferred substituents of R ₁₀₅ . Particularly preferred is a primary unsubstituted alkyl group having 3 to 5 carbon atoms or a primary alkyl group substituted with an alkoxycarbonyl group.

The group represented by INH in the general formula (III) represents a group having a development inhibiting ability, and specific examples thereof are (INH-1) to (INH-1) mentioned in the description of the PUG of the general formula (I).
(INH-13). The preferable range and the like are also the same as those in the general formula (I).

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

In the general formula (IV), A, INH, and R ₁₀₅ have the same meanings as in the general formula (III).

R ₁₁₁ , R ₁₁₂ and R ₁₁₃ each represent a hydrogen atom or an organic residue, and when two arbitrary divalent groups of R ₁₁₁ , R ₁₁₂ and R ₁₁₃ are linked together to form a ring. Good.

The case where each of R ₁₁₁ , R ₁₁₂ and R ₁₁₃ represents a hydrogen atom or a monovalent organic group will be described.

When R ₁₁₂ and R ₁₁₃ represent a monovalent organic group, the organic group is preferably an alkyl group (methyl, ethyl etc.) or an aryl group (phenyl etc.).
R ₁₁₂ and R ₁₁₃ are preferably a case where at least one is a hydrogen atom, and particularly preferably R _112.
And R ₁₁₃ is a hydrogen atom.

R ₁₁₁ represents an organic group and is preferably the following groups. Alkyl groups (eg wave methyl, isopropyl, butyl, isobutyl, tert-butyl, sec
-Butyl, neopentyl, hexyl), aryl groups (eg phenyl), acyl groups (eg acetyl, benzoyl), sulfonyl groups (eg methanesulfonyl, benzenesulfonyl), carbamoyl groups (eg ethylcarbamoyl, phenylcarbamoyl), sulfamoyl groups (eg Ethylsulfamoyl, phenylsulfamoyl), alkoxycarbonyl group (eg ethoxycarbonyl, butoxycarbonyl), aryloxycarbonyl group (eg phenoxycarbonyl, 4-methylphenoxycarbonyl), alkoxysulfonyl group (eg butoxysulfonyl, ethoxysulfonyl). , An aryloxysulfonyl group (eg, phenoxysulfonyl, 4-
Methoxyphenoxysulfonyl), cyano group, nitro group, nitroso group, thioacyl group (eg thioacetyl,
Thiobenzoyl), thiocarbamoyl group (eg ethylthiocarbamoyl), imidoyl group (eg N-ethylimidoyl), amino group (eg amino, dimethylamino, methylamino), acylamino group (eg formylamino, acetylamino, N) -Methylacetylamino), alkoxy groups (eg methoxy, isopropyloxy), or aryloxy groups (eg phenoxy)
It is.

Further, these groups may further have a substituent, and as the substituent, in addition to the groups listed as R ₁₁₁ ,
Examples thereof include a halogen atom (fluoro, chloro, bromo, etc.), a carboxyl group, a sulfo group and the like.

As R ₁₁₁ , the number of atoms other than hydrogen atoms is preferably 15 or less.

Further, R ₁₁₁ is more preferably a substituted or unsubstituted alkyl group or aryl group,
A substituted or unsubstituted alkyl group is particularly preferable.

Next, in the groups represented by R ₁₁₁ , R ₁₁₂ and R ₁₁₃ , a case where any two of these groups are combined as a divalent group to form a ring will be described.

The size of the ring formed is 4 to 8
A member ring is preferable, and a case where a 4- or 6-membered ring is formed is more preferable.

The divalent group is preferably the following groups.

-C (= O) -N (R ₁₁₄ )-, -SO _{2
-N (R 114) -, -} (CH 2) 3 -, - (CH 2) 4
_{-, - (CH 2) 5} -, - C (= O) - (CH 2)
_2- , -C (= O) -N ( _R114 ) -C (= O)-,-
_{SO 2 -N (R 114) -C} (= O) -, - C (= O) -
_{C (R 114) (R 115} ) -, - (CH 2) 2 -O-CH
_2- .

[0094] Here, R ₁₁₄ and R ₁₁₅ are as defined when the hydrogen atom or R ₁₁₁ represents a monovalent organic group, R ₁₁₄ and R ₁₁₅ may be different even in the same.

The remaining groups of R ₁₁₁ , R ₁₁₂ and R ₁₁₃ that do not participate as a divalent group represent a hydrogen atom or a monovalent organic group, and specific examples of the organic group are shown when no ring is formed. R _111, is the same as that of R _112, R _113. R
_When any two of ₁₁₁ , R ₁₁₂ and R ₁₁₃ are combined to form a ring, preferably either R ₁₁₂ or R ₁₁₃ is a hydrogen atom and the remaining R ₁₁₂ to R ₁₁₃ are R _111.
To form a ring, and more preferably, the left end of the divalent group mentioned above is bonded to the nitrogen atom of the general formula (I) and the right end thereof is bonded to a carbon atom.

Further, R ₁₁₁ , R ₁₁₂ and R ₁₁₃ preferably do not form a ring and each represents a hydrogen atom or a monovalent organic group.

In the general formulas (I) and (II), A and PU
The formula weight of the residue excluding the group represented by G is 64 or more and 240
It is preferably the following or less, more preferably 70 or more and 2
It is 00 or less, and particularly preferably 90 or more and 180 or less. If the formula weight is too small, it is difficult to achieve a substantially two-stage timing, and if the formula weight is large, the timing can be adjusted easily, but the diffusivity in the film becomes low, and the adjacent development effect ( Edge effect) and reduction of interlayer effect.

Specific examples of the compounds represented by the general formulas (I) to (IV) of the present invention are shown below in Chemical Formulas 32 to 66.
The present invention is not limited by these.

The compounds represented by the general formula (I) in which A represents a coupler residue have a number prefixed with (CA), and the compounds represented by the general formulas (II) to (IV) in which A represents a coupler residue. Is indicated by a number prefixed with (CB), and those represented by general formulas (I) to (IV) in which A represents a redox group are indicated by a number prefixed with (SA).

[0100]

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[0101]

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[0102]

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[0103]

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[0104]

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[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0115]

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[0116]

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[0117]

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[0118]

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[0119]

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[0120]

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[0121]

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[0122]

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[0123]

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[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

Embedded image The synthesis of the compounds of the present invention is described, for example, in US Pat.
7,383, 4,770,990, 4,68
4,604, 4,886,736, JP-A-60-
218645, 61-230135, JP-A-2-
37070, 2-170832, and 2-2.
The method described in 51192 or a similar method can be used.

Specific synthetic examples will be described below.

(Synthesis Example 1) Synthesis of Exemplified Compound (CA-1) The compound was synthesized by the synthetic route shown in Chemical Formula 67 below.

[0137]

Embedded image CA-1a (3.40 g) was thionyl chloride (30 ml)
After reacting at 60 ° C for 1 hour, excess thionyl chloride was distilled off under reduced pressure. This residue was added to a solution of CA-1b (7.48 g) and diisopropylethylamine (10.5 ml) in dimethylformamide (0 ° C), and the mixture was stirred for 1 hour. Then, this solution was poured into water (500 ml) and the resulting crystals were collected by filtration to obtain 9.8 g of CA-1c as crude crystals.
Obtained. The structure was confirmed by NMR.

CA-1c (3.20 g) and CA-1d
(1.38 g) of 1,2-dichloroethane (30 ml)
The reaction was carried out for 1 hour. There, CA-1e (3.20
A solution of g) in ethyl acetate (20 ml) was added under water cooling, diisopropylethylamine (4.5 ml) was added subsequently, and the mixture was stirred for 1 hour.

The reaction was stopped with 1N hydrochloric acid, and chloroform (30 ml) was added to dilute the reaction solution. After that, the reaction solution was washed with water three times, and the organic layer was dried over sodium sulfate. The oily substance obtained by distilling off the organic solvent was subjected to silica gel column chromatography (ethyl acetate-hexane = 1: 1).
Exemplified compound CA-1 was purified by 1.
20 g was obtained. The structure was confirmed by NMR. m. p. 1
33.0-134.0 ° C.

(Synthesis Example 2) Synthesis of Exemplified Compound (CA-12) It was synthesized by the compound route shown in the following Chemical Formula 68.

[0141]

Embedded image CA-12a (10.7 g) was reacted with 37% aqueous formalin solution (30 ml) in acetic acid (100 ml) at 70 ° C. for 5 hours, and the solvent was evaporated under reduced pressure. The residue was subjected to silica gel column chromatography (ethyl acetate-hexane =
CA-12b was purified to 6.4 by 2: 1).
g (yield 53%) was obtained.

Next, CA-12b (3.2 g) and CA-
12c (2.1 g) was suspended in chloroform (40 ml), zinc iodide (5.7 g) was added thereto, and the mixture was reacted at room temperature for 2 hours. Stop the reaction with 1N hydrochloric acid and chloroform 40
After diluting with ml, the reaction solution was washed twice with water. The residue obtained after drying and concentrating the organic layer with sodium sulfate was subjected to silica gel column chromatography (ethyl acetate-hexane =
Example compound (CA-1
4.1 g (yield 25%) of 2) was obtained. The structure was confirmed by NMR, mass and elemental analysis.

(Synthesis Example 3) Synthesis of Exemplified Compound (CB-2) The compound was synthesized by the synthetic route shown in Chemical Formula 69 below.

[0144]

Embedded image CB-2a (10 mmol) was added to chloroform (30 m
l) and suspended therein, thionyl chloride (20 mmol)
Is added and reacted at 50 ° C. for 1 hour, and then the solvent is distilled off. The residue obtained here was added to a solution of CB-2b (10 mmol) and diisopropylethylamine (20 mmol) in dimethylformamide (30 ml), reacted for 1 hour, and then poured into ice water (200 ml). 50 ml of chloroform
After adding and stirring, the aqueous phase was separated and the organic layer was washed with water (100 m
CB-2c was obtained by further washing twice with l), drying over sodium sulfate and concentrating.

The CB-2c thus obtained was mixed with chloroform (30
nitrophenyl chlorocarbonate (1 ml).
0 mmol) was added and reacted for 1 hour, and then CB-2d (1
A solution of 0 mmol) in ethyl acetate (50 ml) is added, diisopropylethylamine (50 mmol) is further added, and the mixture is reacted for 1 hour. The reaction was stopped by adding 1N liquid acid (10 ml) and then diluted with ethyl acetate (10 ml). The organic layer is washed with water, dried over sodium sulfate, and concentrated. The obtained residue was purified by silica gel column chromatography (eluent: ethyl acetate-hexane = 1: 3) to give 1.94 g (23% yield) of Exemplified compound CB-2.
obtain. m. p. 101.5-102.5 ° C.

(Synthesis Example 4) Synthesis of Exemplified Compound CB-3 It was synthesized according to the synthetic route shown in Chemical Formula 70 below.

[0147]

Embedded image It can be synthesized using (CB-3a) as a raw material by the same method as for the exemplified compound CB-2. Yield 31%. m.
p. 68.0-69.0 ° C.

(Synthesis Example 5) Synthesis of Exemplified Compound (CB-11) The compound was synthesized by the synthetic route shown in Chemical Formula 71 below.

[0149]

Embedded image (CB-11a) 200g and (CB-11b) 34.7
g was dissolved in ethyl acetate (500 ml), diisopropylethylamine (142 ml) was added thereto, and the mixture was stirred for 4 hours. The precipitated crystals were collected by filtration and washed with ethyl acetate to obtain 176 g (75%) of (CB-11c).

53.6 g of (CB-11c) and paraformaldehyde (27.9 g) were refluxed in a mixed solution of 1,2-dichloroethane (500 ml) and acetic acid (54 ml) under reflux.
Allowed to react for hours. After cooling to room temperature, the reaction solution was washed with water, dried over anhydrous sodium sulfate, and concentrated. The obtained residue was purified by silica gel column chromatography using chloroform as an eluent to give (CB-11d) 2
Obtained 3.2 g (41.2%).

(CB-11d) 23.2 g and (CB-1
6.78 g of 1e) was dissolved in chloroform (250 ml), 26.88 g of zinc iodide was added thereto, and the mixture was stirred for 3 hours. After adding 1N hydrochloric acid, the reaction solution was washed with water. The organic layer was dried over anhydrous sodium sulfate and concentrated, and the obtained residue was purified by silica gel column chromatography (ethyl acetate-hexane = 1: 4) to give the exemplified compound (CB
-11) was obtained in an amount of 7.0 g (23.9%). m. p. 11
7.0 to 118.5 ° C.

(Synthesis Example 6) Synthesis of Exemplified Compound (CB-13) The compound was synthesized in the same manner as in Synthesis Example 5. m. p. 61.
5-63.0 ° C.

(Synthesis Example 7) Synthesis of Exemplified Compound (CB-19) The compound can be synthesized by the same method as in Synthesis Example 2 of JP-A-60-218645. Yield 7%, m.p. p. 115
° C.

(Synthesis Example 8) Synthesis of Exemplified Compound (SA-5) The compound was synthesized by the synthetic route shown in the following Chemical Formula 72.

[0155]

Embedded image 11.6 g of SA-5a (synthesized by a method similar to that described in JP-A-61-230135) was added to 30 ml of thionyl chloride under water cooling, and the mixture was further reacted at 50 ° C. for 1 hour.
Excess thionyl chloride was distilled off under reduced pressure, and the precipitated crystals were washed with a small amount of ice-cold chloroform to give SA.
-5b was obtained as crude crystals. Then SA-5b (13.1
g) to SA-5c (7.2 g) and triethylamine 1
2.1 g of N, N-dimethylformamide (100 m
l) The solution was added at 0 ° C. and then further reacted at room temperature for 1 hour.

The reaction mixture was poured into an aqueous solution of 60 ml of 2N liquid acid and 300 ml of ice water, and 300 ml of ethyl acetate was further added and stirred. The liquid was transferred to a separatory funnel, the oil layer was taken, and washed several times with water. The organic layer was dried over anhydrous sodium sulfate,
After concentration, the residue was purified by silica gel column chromatography (ethyl acetate-hexane = 1/4 to 1/1 (V / V) was used as an eluent) to exemplify Compound S.
3.7 g of A-5 was obtained as an amorphous substance.

The compound represented by formula (I) or (II) of the present invention may be added to any layer in the light-sensitive material, but may be added to the light-sensitive emulsion layer and / or its adjacent layer. It is particularly preferable to add to the red-sensitive emulsion layer and / or the green-sensitive emulsion layer. When the same color-sensitive layer is divided into two or more layers having different sensitivities, they may be added to any of the highest sensitivity layer, the lowest sensitivity layer and the intermediate sensitivity layer.

The total amount added to the light-sensitive material is 0.
001 to 1.0 g / m ² , preferably 0.010
To 0.5 g / m ² , more preferably 0.020 to 0.4
0 g / m ² , more preferably 0.030 to 0.30 g /
m ² .

The compound (aldehyde scavenger) which reacts with and fixes the aldehyde compound used in the present invention is represented by the following general formula [A],
The compound represented by [B] has an equivalent molecular weight of 300 or less per unit of active hydrogen defined below.

[Equivalent molecular weight] = [molecular weight] ÷ [active hydrogen in molecule]

[0161]

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[0162]

Embedded image Here, R ₁₁ and R ₁₂ are a hydrogen atom, an alkyl group (eg, methyl, ethyl, n-propyl), a substituted alkyl group, an aralkyl group (eg, benzyl), a substituted aralkyl group, an aryl group (eg, phenyl, naphthyl), a substituted aryl. Group, acyl group (eg acetyl, malonyl, benzoyl, cinnamoyl), alkoxycarbonyl group (eg methoxycarbonyl, ethoxycarbonyl), carbamoyl group, alkylcarbamoyl group (eg methylcarbamoyl, ethylcarbamoyl), dialkylcarbamoyl group (eg dimethylcarbamoyl) , An arylcarbamoyl group (eg, phenylcarbamoyl), or an amino group, an alkylamino group (eg, methylamino, ethylamino), an arylamino group (eg, phenylamino,
Naphthylamino) and a halogen atom (for example, chlorine atom, bromine atom), the number of carbon atoms of R ₁₁ and R ₁₂ does not exceed 20, and R ₁₁ and R ₁₂ may form a ring. _At least one of ₁₁ and R ₁₂ is an acyl group, an alkoxycarbonyl group, a carbamoyl group, or an amino group. Here, the substituents of the alkyl group, aryl group and alkenyl group include nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (eg methoxy), aryloxy group (eg phenoxy), acyloxy group (eg acetoxy), acylamino. Group (eg acetylamino), sulfonamide group (eg methanesulfonamide), sulfamoyl group (eg methylsulfamoyl), halogen atom (eg fluorine atom, chlorine atom,
Examples thereof include a bromine atom), a carboxyl group, a carbamoyl group (eg, methylcarbamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl), and a sulfonyl group (eg, methylsulfonyl). When two or more substituents are present, they may be the same or different.

X is -CH =, -CR ₁₁ =, or -N
= Represents R ₁₃ represents an alkyl group, a substituted alkyl group, an aralkyl group (for example, a benzyl group), a substituted aralkyl group, an aryl group or a substituted aryl group, and these aryl group and substituted aryl group are a 5-membered to 7-membered ring and a condensed ring. You may form. Further, as these substituents, a nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (for example, methoxy), an aryloxy group (for example, phenoxy), an acyloxy group (for example, acetoxy), an acylamino group (for example, acetylamino), Sulfonamide group (eg methanesulfonamide), sulfamoyl group (eg methylsulfamoyl), halogen atom (eg fluorine atom, chlorine atom, bromine atom), carboxyl group, carbamoyl group (eg methylcarbamoyl), alkoxycarbonyl group (eg Methoxycarbonyl),
Sulfonyl groups (eg methylsulfonyl) are mentioned. When two or more substituents are present, they may be the same or different. n represents an integer of 2 or more.

The compound represented by the general formula [A] is preferable to the compound represented by the general formula [B].

Preferred formalin scavengers represented by the general formulas [A] and [B] are the general formulas (A-1) to (A-
8), the general formula (B-1) shown in the following chemical formulas 83 and 84.
And a compound represented by (B-2). However,
Also included are keto-enol tautomers.

[0166]

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[0167]

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[0168]

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[0169]

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[0170]

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[0171]

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[0172]

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[0173]

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[0174]

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[0175]

Embedded image Here, R ₁₄ to R ₃₅ and R _{37 to} R ₃₉ are a hydrogen atom, a halogen atom (eg, chlorine atom), an alkyl group (eg, methyl group, ethyl group, n-propyl group, etc.), a substituted alkyl group, It represents an aralkyl group (for example, benzyl), a substituted aralkyl group, an aryl group (for example, phenyl, naphthyl), and a substituted aryl group, and the carbon numbers of R _{14 to} R ₃₅ do not exceed 20, respectively, and R ₂₁ , R ₂₂ , and R ₂₃ Any one of R ₂₄ and R ₂₄ , and any one of R _{29 to} R ₃₃ must be a hydrogen atom. Here, the substituents of the alkyl group, aryl group and aralkyl group include nitro group, hydroxyl group, cyano group, sulfo group, alkoxy group (eg methoxy), aryloxy group (eg phenoxy), acyloxy group (eg acetoxy), acylamino. Group (eg acetylamino), sulfonamide group (eg methanesulfonamide), sulfamoyl group (eg methylsulfamoyl), halogen atom (eg fluorine atom, chlorine atom, bromine atom), carboxyl group, ureido group (eg ureido, 3-methylureido), a carbamoyl group (for example, methylcarbamoyl),
Examples include an alkoxycarbonyl group (for example, methoxycarbonyl) and a sulfonyl group (for example, methylsulfonyl). When two or more substituents are present, they may be the same or different.

R ₃₆ is a halogen atom (eg, chlorine atom,
Bromine atom), alkyl group, substituted alkyl group, aralkyl group, substituted aralkyl group, aryl group, substituted aryl group,
Heterocyclic group, carbonyl group (eg, methylcarbonyl, phenylcarbonyl), sulfonyl group (eg, methylsulfonyl, phenylsulfonyl), carboxyl group, -C
_{S-NH 2, -CS-NHR} ( the R represents an aryl group), - C-represents a (NH) -NH _2.

R ₁₄ and R ₁₅ , R ₁₆ and R ₁₇ , R ₃₄ and R ₃₅ may form a ring, and R _{18 to} R ₂₀ , R _{21 to} R ₂₄ , R _{25 to} R
₂₈ , R _{29 to} R _33, and R _{36 to} R ₃₉ may have any two substituents in each group forming a ring. m is 3 to 6
, And k is an integer of 2 or more.

General formulas [A-1] to [A-8], [B
Among the aldehyde scavengers represented by [-1] and [B-2], more preferred is the general formula [A-3].
To [A-8].

Among them, particularly preferred formalin scavengers are those represented by the general formulas [A-3a] and [A-3b] shown in the following Chemical formulas 85 and 86, and it is more preferable to use these two kinds in combination.

[0180]

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[0181]

Embedded image Specific examples of the aldehyde scavenger of the present invention are shown below.
7 to 101, but not limited to these.

[0182]

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[0183]

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[0184]

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[0185]

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[0186]

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[0187]

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[0188]

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[0189]

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[0190]

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[0191]

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[0192]

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[0193]

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[0194]

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[0195]

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[0196]

Embedded image Here, the compound (S-10) is an oligomer or polymer having one repeating unit.

Formalin Scavenger (S-1) ~
(S-6) and (S-12) to (S-23) are usually commercially available compounds, and (S-7) to (S-1).
1) is the Bulletin of the Chemical Society of Japan
Chemical Society of Japan
n), 39, pp. 1559-1567, 1734-1717.
Page 38 (1966), Hiemiche Berichte (Che
mische Berichte), Volume 54 B, 180
Pages 2-1833, 2441-2479 (1921) Beilstein Handbuch Del Organischen Hiemmy (Beilstein Handbuch)
der Organichen Chemie)
H, p98 (1921) and the like can be easily synthesized. (S-24) and (S-25) are Beilstein Handbuff del Organischen Hiemi (Beilstein)
Handbuch der Organischen
Chemie) First Supplement, Volume 4, Page 354, Volume 3 6
It can be synthesized by the method described on page 3. (S-26)
-(S-28) are the methods described in U.S. Pat. No. 4,411,987, and (S-29) to (S-31) are U.S. Pat. H. RH Wiley, P.M. P. Wile
y), “The Chemistry of Heterocyclic Compounds (The Chemistry of
Heterocyclic Compound
s) ”, Pyrazolones, Pyrazolones and Derivatives
idle Derivatives, Interscience Publishers
It can be easily synthesized from a known compound by the method described in No. Publishers (1964).

The horimarin scavengers used in the present invention may be used in combination of two or more kinds.

The formalin scavenger of the present invention is a silver halide emulsion layer of a silver halide color photographic light-sensitive material.
It is contained in at least one of the undercoat layer, the protective layer, the intermediate layer, the filter layer, the antihalation layer, and other auxiliary layers, but the halogenation containing the uncolored magenta coupler causes deterioration of the photographic performance when contacted with formaldehyde gas. The object of the present invention can be achieved regardless of whether it is added to the silver emulsion layer, the layer closer to the support or the layer farther from the support.

To add the formalin scavenger used in the present invention to these layers, the formalin scavenger in the coating solution for forming the layer is left as it is, or the silver halide color photographic light-sensitive material is adversely affected. It can be added by dissolving it in a suitable solvent such as water or alcohol at an appropriate concentration. Further, the formalin scavenger may be dissolved in a high-boiling organic solvent and / or a low-boiling organic solvent, emulsified and dispersed in an aqueous solution, and then added. The timing of addition of the formalin scavenger may be selected at any time during the production process, but is generally preferably immediately before application. The addition amount is 0.000 per 1 m ² of silver halide color photographic light-sensitive material.
5g-1.5g is suitable, but preferably 0.01g
To 1.0 g, more preferably 0.05 g to 0.5
0 g.

In the present invention, the pH of the photosensitive material film surface is
It is preferably 5.5 or more and less than 7.0,
It is more preferably 6.0 or more and 7.0 or less. Membrane pH
As a method for setting the above range, it is general to add an acid or an alkali to the liquid to be applied. The acid or alkali may be added and mixed in the coating solution in advance, or may be added immediately before coating to adjust the pH.

Here, the film surface pH means a value measured using an electrode for film surface pH measurement. A commercially available composite electrode for measuring the pH on the membrane surface can be used, and for example, a composite electrode # 6210-06T manufactured by Horiba Ltd. can be used. The pH is measured by dropping 20 μl of water with a micropipette onto the sample to be measured under an environment of 25 ° C. and 50 to 60% RH, immediately pressing the electrode, and waiting until the indicated value reaches equilibrium before reading.

The pH value obtained here does not always correspond to the pH value of the coating when the water-soluble coating is applied on the support, and the pH in the film after the coating is dried and hardened. It corresponds to.

In the green-sensitive layer of the silver halide color photographic light-sensitive material of the present invention, it is preferable to use a polymer coupler obtained from a monomer represented by the general formula (PA) shown in the following Chemical Formula 102, depending on the sharpness treatment. Further, it is more preferable in that the image storability after treatment is improved.

[0205]

Embedded image R ₁₂₁ in the general formula (PA) is a hydrogen atom, having 1 to 4 carbon atoms.
-D- represents -COO
-, - CONR ₁₂₂ -, or a substituted or unsubstituted phenyl group, -E- represents a substituted or unsubstituted alkylene group, phenylene group or aralkylene group,
-F- is -CONR ₁₂₂ -, - NR ₁₂₂ CONR
_{122 -, - NR 122 COO -} , - NR 122 CO -, - O
_{CONR 122 -, - NR 122 -} , - COO -, - OCO
-, - CO -, - O -, - S -, - SO 2 -, - NR
_{Represents 122} SO ₂ — or —SO ₂ NR ₁₂₂ —. R
₁₂₂ represents a hydrogen atom or a substituted or unsubstituted aliphatic or aryl group. When two or more _R122s are present in the same molecule, they may be the same or different. p, q, r
Represents 0 or 1. However, p, q, and r are simultaneously 0
It is not.

T in the general formula (PA) is represented by the following formula 103
In the magenta coupler represented by the general formula (PB) (Ar ₅₁ , Z ₅₁ , or R ₁₃₃ , any of the moieties of-(D)-(E)-(of the general formula (PA). F)-
To be attached to).

[0207]

Embedded image Ar ₅₁ in the general formula (PB) is a substituent of a well-known type at the 1-position of the 2-pyrazolin-5-one coupler, for example, an alkyl group, a substituted alkyl group (for example, haloalkyl such as fluoroalkyl, cyanoalkyl, benzylalkyl). A substituted or unsubstituted heterocyclic group (for example, 4-pyridyl, 2-thiazolyl), a substituted or unsubstituted aryl group [as a heterocyclic group or a substituent of an aryl group, an alkyl group (for example, methyl, ethyl), an alkoxy group (Eg methoxy, ethoxy), aryloxy group (eg phenyloxy), alkoxycarbonyl group (eg methoxycarbonyl), acylamino group (eg acetylamino), carbamoyl group, alkylcarbamoyl group (eg methylcarbamoyl, ethylcarbonyl), dialkylcarbamoyl Group ( Example, if dimethylcarbamoyl),
Arylcarbamoyl group (eg phenylcarbamoyl), alkylsulfonyl group (eg methylsulfonyl), arylsulfonyl group (eg phenylsulfonyl), alkylsulfonamide group (eg methanesulfonamide), arylsulfonamide group (eg phenylsulfonamide), sulfamoyl Groups, alkylsulfamoyl groups (eg ethylsulfamoyl), dialkylsulfamoyl groups (eg dimethylsulfamoyl), alkylthio groups (eg methylthio), arylthio groups (eg phenylthio), cyano groups, nitro groups,
Halogen atoms (for example, fluorine, chlorine, bromine) are mentioned, and when there are two or more substituents, they may be the same or different.

Particularly preferred substituents include a halogen atom, an alkyl group, an alkoxy group, an alkoxycarbonyl group and a cyano group. ].

R ₁₂₃ in formula (PB) is an unsubstituted or substituted anilino group, an acylamino group (eg, alkylcarbonamide, phenylcarbonamide, alkoxycarbonamide, phenyloxycarbonamide), a ureido group (eg, alkylureido, Phenylureido), a sulfonamide group, and these substituents include a halogen atom (eg, fluorine, chlorine, bromine), a linear or branched alkyl group (eg, methyl, t-butyl,
Octyl, tetradecyl), alkoxy groups (eg methoxy, atoxy, 2-ethylhexyloxy, tetradecyloxy), acylamino groups (eg acetamide,
Benzamide, butanamide, octanamide, tetradecanamide, α- (2,4-di-tert-amylphenoxy) acetamide, α- (2,4-di-tert.
-Amylphenoxy) butyramide, α- (3-pentadecylphenoxy) hexanamide, α- (4-hydroxy-3-tert-butylphenoxy) tetradecanamide, 2-oxo-pyrrolidin-1-yl, 2-oxo-5 -Tetradecylpyrrolidin-1-yl, N-methyl-tetradecanamide), sulfonamide groups (eg methanesulfonamide, benzenesulfonamide, ethylsulfonamide, p-toluenesulfonamide, octanesulfonamide, p-dodecylbenzenesulfonamide) , N-methyl-tetradecanesulfonamide), a sulfamoyl group (eg, sulfamoyl, N-methylsulfamoyl, N-ethylsulfamoyl, N, N-dimethylsulfamoyl, N, N-dihexylsulfamoyl, N- Hexade Silsulfamoyl, N- [3-
(Dodecyloxy) -propyl] sulfamoyl, N-
[4- (2,4-di-tert-amylphenoxy) butyl] sulfamoyl, N-methyl-N-tetradecylsulfamoyl), carbamoyl group (for example, N-methylcarbamoyl, N-butylcarbamoyl, N-octadecylcarbamoyl) , N- [4- (2,4-di-tert
-Amylphenoxy) butyl] carbamoyl, N-methyl-N-tetradecylcarbamoyl), diacylamino group (for example, N-succinimide, N-phthalimide,
2,5-dioxo-1-oxazolidinyl, 3-dodecyl-2,5-dioxo-1-hydantoinyl, 3- (N
-Acetyl-N-dodecylamino) succinimide),
Alkoxycarbonyl group (eg, methoxycarbonyl, tetradecyloxycarbonyl, benzyloxycarbonyl), alkoxysulfonyl group (eg, methoxysulfonyl, butoxysulfonyl, octyloxysulfonyl, tetradecyloxysulfonyl), aryloxysulfonyl group (eg, phenoxysulfonyl, p −
Methylphenoxysulfonyl, 2,4-di-tert-
Amylphenoxysulfonyl), alkanesulfonyl group (for example, methanesulfonyl, ethanesulfonyl, octanesulfonyl, 2-ethylhexylsulfonyl, hexadecanesulfonyl), arylsulfonyl group (for example, benzenesulfonyl, 4-nonylbenzenesulfonyl),
Alkylthio groups (eg methylthio, ethylthio, hexylthio, benzylthio, tetradecylthio, 2-
(2,4-di-tert-amylphenoxy) ethylthio), arylthio group (eg phenylthio, p-tolylthio), alkyloxycarbonylamino group (eg methoxycarbonylamino, ethyloxycarbonylamino, benzyloxycarbonylamino, hexadecyloxy) Carbonylamino), an alkylureido group (for example, N-methylureido, N, N-dimethylureido, N
-Methyl-N-dodecylureido, N-hexadecylureido, N, N-dioctadecylureido), an acyl group (for example, acetyl, benzoyl, octadecanoyl, p
-Dodecanamide benzoyl), a nitro group, a carboxyl group, a sulfo group, a hydroxy group or a trichloromethyl group.

However, among the above-mentioned substituents, the one defined as an alkyl group has 1 to 36 carbon atoms, and the one defined as an aryl group has 6 to 38 carbon atoms.

Z ₅₁ in the general formula (PB) is a coupling-off group (eg acetoxy, propanoyloxy, benzoyloxy, ethoxyoxaloyl) linked with a hydrogen atom, a halogen atom (eg chlorine, bromine) or an oxygen atom. Oxy, pyruvinyloxy, cinnamoyloxy, phenoxy, 4-cyanophenoxyl, 4-titaniumsulfonamidephenoxy, α-naphthoxy, 4-cyanoxyl,
4-Methanesulfonamide-phenoxy, α-naphthoxy, 3-pentadecylphenoxy, benzyloxycarbonyloxy, ethoxy, 2-cyanoethoxy, benzyloxy, 2-phenethyloxy, 2-phenoxy-ethoxy, 5-phenyltetrazolyl Oxy, 2-benzothiazolyloxy), a coupling-off group linked by a nitrogen atom (for example, those described in JP-A-59-99437, specifically benzenesulfonamide, N-ethyltoluenesulfonamide). , Heptafluorobutanamide, 2,3,4,5,6-pentafluorobenzamide, octanesulfonamide, p-cyanophenylureido, N, N-diethylsulfamoylamino, 1-piperidyl, 5,5-dimethyl- 2,4-dioxo-3-
Oxozolidinyl, 1-benzyl-5-ethoxy-3-
Hydantoinyl, 2-oxo-1,2-dihydro-1-
Pyridinyl, imidazolyl, pyrazolyl, 3,5-diethyl-1,2,4-triazol-1-yl, 5- or 6-bromo-benzotriazol-1-yl, 5-methyl-1,2,3,4- Triazol-1-yl group, benzimidazolyl), coupling-off groups linked by sulfur atom (eg phenylthio, 2-carboxyphenylthio, 2-methoxy-5-octylphenylthio, 4
-Methanesulfonylphenylthio, 4-octanesulfonamidophenylthio, benzylthio, 2-cyanoethylthio, 5-phenyl-2,3,4,5-tetrazolylthio, 2-benzothiazolyl).

A coupling-off group which is preferably linked by a nitrogen atom is preferable, and a pyrazolyl group is particularly preferable.

E in the general formula (PA) is C 1-10.
Represents an unsubstituted or substituted alkylene group, aralkylene group, or phenylene group, and the alkylene group may be linear or branched. Examples of the alkylene group include methylene, methylmethylene, dimethylmethylene, dimethylene,
Trimethylene, tetramethylene, pentamethylene, hexamethylene, decylmethylene, aralkylene groups such as benzylidene, and phenylene groups such as p-
Examples include phenylene, m-phenylene and methylphenylene.

The substituent of the alkylene group, aralkylene group or phenylene group represented by E is, for example, an aryl group (eg phenyl) nitro group, a hydroxyl group, a cyano group, a sulfo group, an alkoxy group (eg methoxy) or an aryloxy group. (Eg phenoxy), acyloxy group (eg acetoxy), acylamino group (eg acetylamino), sulfonamide group (eg methanesulfonamide), sulfamoyl group (eg methylsulfamoyl), halogen atom (eg fluorine, chlorine, bromine) ,
Examples thereof include a carboxy group, a carbamoyl group (eg methylcarbamoyl), an alkoxycarbonyl group (eg methoxycarbonyl), and a sulfonyl group (eg methylsulfonyl). When two or more substituents are present, they may be the same or different.

Next, as the non-color-forming ethylenic monomer which is not coupled with the oxidation product of the aromatic primary amine developing agent which is copolymerizable with the coupler monomer represented by the general formula (PA), for example, acrylic acid can be used. Examples thereof include esters, methacrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, acrylamides, methacrylamides, vinyl ethers and styrenes.

Specific examples of these monomers will be given below. Examples of acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate and hexyl. Examples thereof include acrylate, 2-ethylhexyl acrylate, acetoxyethyl acrylate, phenyl acrylate, 2-methoxy acrylate, 2-ethoxy acrylate, and 2- (2-methoxyethoxy) ethyl acrylate. Examples of the methacrylic acid ester include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, 2-hydroxyethyl methacrylate and 2-ethoxyethyl methacrylate. Examples of the crotonic acid ester include butyl crotonic acid and hexyl crotonic acid. Examples of the vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate and vinyl benzoate. Examples of the maleic acid diester include diethyl maleate, dimethyl maleate, dibutyl maleate and the like. Examples of the fumarate diester include diethyl fumarate, dimethyl fumarate, and dibutyl fumarate. Examples of the itaconic acid diester include diethyl itaconate, dimethyl itaconate, and dibutyl itaconate. Examples of acrylamides include acrylamide, methyl acrylamide, ethyl acrylamide, propyl acrylamide, n-butyl acrylamide, tert-butyl acrylamide, cyclohexyl acrylamide, and 2-.
Examples include methoxyethyl acrylamide, dimethyl acrylamide, diethyl acrylamide, and phenyl acrylamide. Examples of methacrylamides include methyl methacrylamide, ethyl methacrylamide, and n-.
Examples thereof include butyl methacrylamide, tert-butyl methacrylamide, 2-methoxy methacrylamide, dimethyl methacrylamide and diethyl methacrylamide. Examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, and dimethylaminoethyl vinyl ether. Examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, butylstyrene, chloromethylstyrene,
Methoxy styrene, butoxy styrene, acetoxy styrene, chloro styrene, dichloro styrene, bromo styrene, vinyl benzoic acid methyl ester, 2-methyl styrene are mentioned.

Examples of other monomers include, for example, allyl compounds (eg allyl acetate), vinyl ketones (eg methyl vinyl ketone), vinyl heterocyclic compounds (eg vinyl pyridine), glycidyl esters (eg glycidyl acrylate), Unsaturated nitriles (eg acrylonitrile), acrylic acid, methacrylic acid, itaconic acid, maleic acid, monoalkyl itaconate (eg monomethyl itaconate), monoalkyl maleate (eg monomethyl maleate), citraconic acid, vinyl sulfonic acid, Examples thereof include acryloyloxyalkyl sulfonic acid (eg, acryloyloxymethyl sulfonic acid) and acrylamidoalkyl sulfonic acid (eg, 2-acrylamido-2-methylethane sulfone). These acids may be salts of alkali metals (eg, Na, K) or ammonium ions.

Among these monomers, comonomers preferably used include acrylic acid esters, methacrylic acid esters, styrenes, maleic acid esters, acrylamides and methacrylamides.

Two or more kinds of these monomers may be used in combination. Examples of the combination of two or more kinds include n-butyl acrylate and styrene, n-butyl acrylate and butyl styrene, t-butyl methacrylamide and n-butyl acrylate.

The proportion of the color-forming portion corresponding to the general formula (PB) in the magenta polymer coupler is usually 5 to 5.
80% by weight is preferable, but 30 to 70% by weight is preferable in terms of color reproducibility, color developability, processing dependence and stability.
In this case, the equivalent molecular weight (the number of grams of the polymer containing 1 mol of the monomer coupler) is about 250 to 4,000,
It is not limited to this.

The magenta polymer coupler is added in an amount of 0.005 to 0.5 mol, preferably 0.03 to 0.25 mol, per mol of silver when the same layer as silver halide is used based on the coupler monomer. Good to do.

When the magenta polymer coupler is used in the non-photosensitive layer, the coating amount is 0.01 g / m ² to
1.0 g / m ² , preferably 0.1 g / m ^{2 to} 0.5 g
/ M ² .

The polymer coupler used in the present invention is
As described above, the lipophilic polymer coupler obtained by polymerizing the monomer coupler may be dissolved in an organic solvent to emulsify and disperse it in the form of latex in an aqueous gelatin solution, or directly by the emulsion polymerization method. May be.

A method for emulsion-dispersing a lipophilic polymer coupler in the form of a latex in an aqueous gelatin solution is described in US Pat. No. 3,451,820, and an emulsion polymerization is described in US Pat. 370,952
And EP 341 088 A2.

The synthesis of the magenta polymer coupler is
As a polymerization initiator and a polymerization solvent, JP-A-56-5543, JP-A-57-94752, JP-A-57-176038, JP-A-57-204038, JP-A-58-28745, JP-A-58-10738, and JP-A-58-10738 are available. The compounds described in JP-A-58-42044 and JP-A-58-145944 are used.

The polymerization temperature needs to be set in relation to the molecular weight of the polymer to be produced, the kind of the initiator, etc. It can be from 0 ° C. or lower to 100 ° C. or higher, but usually 30 ° C. to 10 °
Polymerizes in the range of 0 ° C.

Next, specific examples of the magenta polymer coupler which can be used in the present invention are shown below.
To Chemical Formula 110, but is not limited thereto. However, the subscript in the structural formula represents the molar ratio.

[0228]

Embedded image

[0229]

Embedded image

[0230]

[Chemical formula 106]

[0231]

Embedded image

[0232]

Embedded image

[0233]

Embedded image

[0234]

Embedded image

[0235]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. Example 1 On a subbed cellulose triacetate film support,
Sample 101, which is a multilayer color photographic material composed of each layer having the following composition, was prepared.

(Composition of photosensitive layer) The coating amount is the amount expressed in g / m ² of silver for silver halide and colloidal silver, and g for couplers, additives and gelatin.
/ M ² units, and for sensitizing dyes, the number is expressed in mol per mol of silver halide in the same layer. The symbols indicating the additives have the following meanings. However, when there are multiple utilities, only one of them is listed as a representative.

UV: UV absorber, Solv: high boiling organic solvent, ExS: sensitizing dye, ExC: cyan coupler,
ExM: Magenta coupler, ExY: Yellow coupler, Cpd: Additive, W: Surfactant, H: Curing agent,
F: Stabilizer.

Further, the above additives are represented by the following chemical formulas 111 to 12
Listed in 3.

[0239]

[Chemical 111]

[0240]

[Chemical 112]

[0241]

[Chemical 113]

[0242]

Embedded image

[0243]

[Chemical 115]

[0244]

Embedded image

[0245]

[Chemical 117]

[0246]

Embedded image

[0247]

[Chemical formula 119]

[0248]

Embedded image

[0249]

[Chemical 121]

[0250]

[Chemical formula 122]

[0251]

Embedded image First layer (antihalation layer) Black colloidal silver 0.15 Gelatin 1.00 ExM-1 5.0 × 10 ^-3 Second layer (intermediate layer) Gelatin 1.00 UV-1 3.0 × 10 ^-2 UV-2 6.0 × 10 ^-2 UV-3 7.0 × 10 ^-2 ExF-1 4.0 × 10 ^-3 Solv-2 7.0 × 10 ^-2 Third Layer (Low Sensitivity Red Sensitive Emulsion Layer) Silver iodobromide emulsion (AgI 2 mol%, internal high AgI type, sphere equivalent) Diameter 0.3 μm, variation coefficient of spherical equivalent diameter 29%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 2.5) 4th layer (medium-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, spherical equivalent diameter 0.55 μm, variation coefficient of spherical equivalent diameter 20%, normal crystal, twin mixed particles, Diameter / thickness ratio 1.0) Fifth layer (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 0.7 μm, variation coefficient of sphere equivalent diameter 30%, twin mixed particles, diameter / thickness Ratio 2.0) Sixth layer (intermediate layer) Gelatin 0.60 P-2 0.17 Cpd-1 0.02 Cpd-4 0.08 Solv-1 5.0 × 10 ^-2 Seventh layer (low sensitivity green emulsion layer) Silver iodobromide emulsion (AgI 2 mol%) , Internal high AgI type, sphere equivalent diameter 0.3 μm, variation coefficient of sphere equivalent diameter 28%, normal crystal, twin crystal mixed particles, diameter / thickness ratio 2.5) Eighth layer (medium-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%, internal high AgI type, equivalent sphere diameter 0.55 μm, variation coefficient of equivalent sphere diameter 20%, normal crystal, twin mixed particles, Diameter / thickness ratio 4.0) 9th layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 0.70 μm, variation coefficient of sphere equivalent diameter 30%, normal crystal, twin crystal mixed grains, Diameter / thickness ratio 2.0) 10th layer (yellow filter layer) Gelatin 0.60 Yellow colloid 5.0 × 10 ^-2 Cpd-1 0.08 Cpd-4 0.12 Solv-1 0.15 11th layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 4 mol%) , Internal high AgI type, sphere equivalent diameter 0.5 μm, variation coefficient of sphere equivalent diameter 15%, octahedral grain) 12th layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion (AgI 10 mol%, internal high AgI type, sphere equivalent diameter 1.3 μm, variation coefficient of sphere equivalent diameter 25%, normal crystal, twin mixed particles, Diameter / thickness ratio 4.5) Thirteenth layer (first protective layer) Fine grain silver iodobromide (average particle size 0.07 μm, AgI 1 mol%) 14th layer (second protective layer) Gelatin 0.40 B-1 (diameter 1.5 μm) 0.10 B-2 (diameter 1.5 μm) 0.10 B-3 2.0 × 10 ^-2 H-1 0.40 Furthermore, storability and processability , Cpd-3, C for improving pressure resistance, antifungal / antibacterial property, antistatic property and coating property.
pd-5, Cpd-6, Cpd-7, Cpd-8, P-
1, W-1, W-2, W-3 were added.

In addition to the above, n-butyl-p-hydroxybenzoate was added. B-4, F-1, F
-4, F-5, F-6, F-7, F-8, F-9, F-
10, F-11, and iron salt, lead salt, gold salt, platinum salt,
Contains iridium and rhodium salts. (Samples 102 to 105) The compound of the present invention (CB-1) added to the fourth and fifth layers of Sample 101 of the present invention.
Samples 102 to 105 were prepared by substituting 3) with other compounds of the present invention in equimolar amounts as shown in Table 1 below. (Samples 106 to 110) Second layer of Samples 101 to 105,
In the sixth layer, the tenth layer and the thirteenth layer, the compound (S
-27) was added in an amount of 0.08 g / m ² to obtain Sample 10
6 to 110 were produced. (Samples 111 to 113) Samples 111 and 112 were prepared by replacing (S-27) in Sample 106 with the compounds (S-5) and (S-6) of the present invention. Sample 10
Sample 113 was prepared by replacing half of (S-27) in 6 with (S-5). (Samples 114 to 117) Fourth Layer and Fifth Sample 106
Sample 11 was prepared by substituting the compound of the present invention (CB-13) added to the layer with a comparative compound as shown in Table 1 below.
4-117 were produced. (Sample 118) P− of the seventh layer and the eighth layer of Sample 111
7 was replaced with 1.5 times molar ExM-2, and
Sample 118 was prepared by multiplying lv-1 and gelatin by 1.3 times.

These samples were prepared by coating 14 layers simultaneously.
After being left under conditions of 50 ° C. and 30% humidity for 7 days, white imagewise exposure was carried out and development processing was carried out. The increase range of cyan density fog is shown in Table 1 below.

[0254] Further, unexposed width 35 mm width 15 cm
Each sample was slowly bent at an angle of 60 ° with the emulsion side facing outward, left for 2 hours, and then subjected to color development described below to measure cyan density with a micro densitometer. It was shown to.

Further, exposure was performed with a pattern for MTF measurement, and the following development was performed to obtain a cyan image of 25 cycles / m.
The MTF value of m was measured, and the results are shown in Table 1 below.

[0256]

[Table 1] However, C-1 to C-4 in Table 1 above are represented by
It is the compound represented by Chemical formula 125.

[0257]

Embedded image

[0258]

Embedded image (Processing method) Process Processing time Processing temperature Color development 3 minutes 15 seconds 38 ℃ Bleaching 6 minutes 30 seconds 38 ℃ Washing with water 2 minutes 10 seconds 24 ℃ Settling 4 minutes 20 seconds 38 ℃ Washing with water (1) 1 minute 05 seconds 24 ℃ Washing with water (2) 1 min 00 sec 24 ℃ Stability 1 min 05 s 38 ℃ Dry 4 min 20 s 55 ℃ Next, write the composition of the treatment liquid. (Color developer) (Unit: g) Diethylenetriaminepentaacetic acid 1.0 1-Hydroxyethylidene-1,1-diphosphonic acid 3.0 Sodium sulfite 4.0 Potassium carbonate 30.0 Potassium bromide 1.4 Potassium iodide 1.5 mg Hydroxylamine sulfate 2.4 4- [N- Ethyl-N-β-hydroxyethylamino] -2-methylaniline sulfate 4.5 Water was added to 1.0 liter pH 10.05 (bleaching solution) (unit g) Ethylenediaminetetraacetic acid ferric sodium trihydrate 100.0 Ethylenediaminetetraacetic acid disodium salt Salt 10.0 Ammonium bromide 140.0 Ammonium sulphate 30.0 Ammonia water (27%) 6.5 ml Add water 1.0 liter pH 6.0 (fixer) (unit g) Ethylenediaminetetraacetic acid disodium salt 0.5 Sodium sulfite 7.0 Sodium bisulfite 5.0 Ammonium thiosulfate Aqueous solution (70%) 170.0 ml Water 1.0 liter pH 6.7 (stabilizing solution) (Unit: g) Formalin (37%) 2.0 ml Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.3 Ethylenediaminetetraacetic acid disodium salt 0.05 Water to add 1.0 liter pH 5.0-8.0 From Table 1 above, the sample of the present invention has less increase in fog during bending, is excellent in pressure property, is less in increase in fog under high temperature and low humidity conditions, and is excellent in sharpness represented by MTF value. It is clear. In the present invention, P
It can be seen that it is more preferable to use the polymer coupler represented by -7 in combination. Example 2 The compound of the present invention (CB-2 was used for the third layer, the fourth layer and the fifth layer of the sample 108 of Example 1 of JP-A-3-157648.
6) ^{0.005g / m 2, 10.015g / m} 2 and 0.025 g / m ² was added, to prepare a sample 201.

S-1 and S-2 in this patent are the compounds (S-27) and (S-5) of the present invention, respectively.

When these samples were evaluated in the same manner as in the examples, the sample 201 of the present invention was excellent in sharpness represented by the MTF value, had little variation in color density during bending, and had little increase in fog during storage. It was confirmed.

Claims (3)

(57) [Claims] 1. A silver halide color photographic light-sensitive material having at least one light-sensitive emulsion layer on a support and containing an aldehyde scavenger, represented by the general formula (I) shown below and / or The general formula (I
A silver halide color photographic light-sensitive material comprising a compound represented by I). Embedded image A in the general formula (I) represents a coupler residue or a redox group, L ₁ and L ₃ represent a divalent timing group, and L ₂ represents a trivalent or higher-valent timing group. And PUG represents a photographically useful group. j
And n each independently represent 0, 1 or 2. m is 1
Or 2 and s is a number obtained by subtracting 1 from the valence of L ₂ and represents an integer of 2 or more, and L ₁ , L ₂ or L
_{When 3} is present in plural in the molecule, they may all be the same or different. There are multiple PUs
All G's may be the same or different. Embedded image A and PUG in the general formula (II) have the same meaning as in the general formula (I). L ₄ represents -OCO- group, -OSO- group, -OSO ₂ -
It represents a group - group, -OCS- group, -SCO- group, -SCS- group or -WCR ₁₁ R _12. Here, W represents an oxygen atom, a sulfur atom or a tertiary amino group (—NR ₁₃ —), and R
₁₁ and R ₁₂ each independently represent a hydrogen atom or a substituent, and R ₁₃ represents a substituent. In addition, the case where each of R ₁₁ , R ₁₂ and R ₁₃ represents a divalent group and is linked to form a cyclic structure is also included. L ₅ represents a group that releases PUG by electron transfer along a conjugated system or a group defined by L ₄ . 2. The formula weight of the residue in the general formula (I) and the general formula (II) excluding the groups represented by A and PUG is 64.
2. The silver halide color photographic light-sensitive material according to claim 1, which is not less than 240 and not more than 240. 3. The silver halide color photographic light-sensitive material according to claim 1, which contains a polymer coupler.