JPH03266836A - Silver halide photographic sensitive material improved in dye image fastness - Google Patents

Abstract

PURPOSE:To reduce discoloration and fading of each dye without causing stains and deteriorating color development performance of each coupler by adding a combination of each specified dye image stabilizer. CONSTITUTION:The photographic constituent layers of this photosensitive material contain at least one of the compounds of formula I and at least one of the compounds of formulae II-V, and in formulae I-V, each of R<1> and R<2> is >=4C alkyl, aryl, or the like; R<11> is an aryl or heterocyclic group; each of Z1 and Z2 is 1-3 C alkylene; (n) in formula II is 1 or 2; R<21> is secondary or tertiary alkyl, such alkenyl, or the like; R<22> is halogen, alkyl, or the like; (n) in formula III is 0-3; X is S, SO, or the like; each of R<31> and R<34> is H, halogen, or the like; R<32> is H, alkyl, or the like; R<33> is H, halogen, or the like; Y<30> is an atomic group necessary to form a chroman or coumaran ring each of R<41>-R<44> is H, halogen, or the like; and Y<40> is an atomic group necessary to form an indan ring.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to the stabilization of organic coloring substances, such as dye images, produced in photographic materials. In particular, the present invention relates to the use of a class of hydroxylamine derivative stabilizers to improve the stability of organic coloring materials, such as dye images, obtained by silver halide photographic materials.

BACKGROUND OF THE INVENTION A typical color photographic material comprises red, green and blue sensitive silver halide emulsion layers containing cyan, magenta and yellow couplers, respectively, in or adjacent to the layers. When developed with a developer containing a P-phinidiamine color developing agent, a dye image is formed.

It is known to include stabilizers in color photographic materials to reduce the deterioration of such dye images due to the effects of light, heat and/or temperature. JP-A-62-262047 describes the use of special bisphenol derivatives to improve the fastness of color images.

However, the drawbacks of the above bisphenol derivatives are that
This is where they cause hue staining in the developed dye image. Furthermore, the effect of preventing fading of coloring pigments is not sufficient.

In addition, as a hydroquinone derivative, JP-A-54-48
No. 538, No. 55-69141, No. 55-89836
Although it has been shown to improve the fastness of color dye images considerably, it is still not sufficient.

[Object of the Invention] An object of the present invention is to provide a photographic material that has an excellent anti-fading effect, and a further object is to prevent fading that does not cause staining or reduce the color development of couplers. An object of the present invention is to provide a silver halide photographic material containing an inhibitor.

Still another object is to provide a silver halide photographic material that is free from precipitation and has improved dispersion stability.

"Structure J of the Invention The above object of the present invention has been achieved by a silver halide photographic material having the following structure.

In a silver halide photographic light-sensitive material having a photographic constituent layer including at least one silver halide emulsion layer on a support, at least one of the compounds represented by the general formula [I] is present in at least one of the photographic constituent layers. and a silver halide photographic material containing at least one compound represented by the general formula [A], CBI, [C] or [D].

General formula [I] group, representing a heterocyclic group, general formula [A] [wherein R represents an aryl group or a heterocyclic group, and zl and Z2 each represent an alkylene group having 1 to 3 carbon atoms ,
However, the total number of carbon atoms in the alkylene groups represented by Zl and Z2 is 3 to 6.

n represents 1 or 2, General formula CB) [In the formula, R1 and R2 are an alkyl group having 4 or more carbon atoms, an aryl group, an alkenyl group, a cycloalkyl group [In the formula, R21
represents a secondary or tertiary alkyl group, a secondary or tertiary alkenyl group, a cycloalkyl group, or an aryl group, R22 is a halogen atom, an alkyl group, an alkenyl group,
The cycloalkyl group represents an aryl group, and n represents an integer of 0 to 3.

X represents S, 5O1S O2 or an alkylene group, general formula [C] [wherein R31 and R34 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a hydroxy group, an aryl group, an aryl group, respectively] Represents an oxy group, an acyl group, an acylamino group, an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group, and R32 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, a cycloalkyl group, or a heterocyclic group. represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group,
Represents an acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group, or alkoxycarbonyl group.

Further, R32 and R33 may be ring-closed with each other to form a 5- or 6-membered ring, or R32 and R33 may be ring-closed with each other to form a methylenedioxy ring.

Y2O represents an atomic group necessary to form a taloman or coumaran ring,] General formula CD) 4 In the U formula, pj4+442, R'3 and R'14 are a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, respectively. ,
Hydroxy group, alkoxy group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group,
Represents a sulfonamide group, cycloalkyl group, or alkoxycarbonyl group, provided that at least one of R'' and R'3 is a hydroxy group or an alkoxy group.

R43 and R44 may be ring-closed with each other to form a 5- or 6-membered hydrocarbon ring.

Y" represents the atomic group necessary to form an indane ring,
] [Specific structure of the invention] Next, the present invention will be specifically explained.

In the formula [I] according to the present invention, examples of the alkyl group represented by RIR2 include a butyl group, a hexyl group, an octyl group, a dodecyl group, an octadecyl group, and the like.

These alkyl groups include those having a substituent, and examples of the substituent include aryl groups such as a phenyl group, p-talolophenyl group, and p-perfluoromethylphenyl group.

Examples of the alkenyl group represented by R1 and R2 include a vinyl group and an allyl group. These alkenyl groups also include those having a substituent, and examples of the substituent include an aryl group.

Examples of the cycloalkyl group represented by R1 and R2 include a cyclopentyl group and a cyclohexyl group,
These cycloalkyl groups also include those having substituents.

Examples of the aryl group represented by R1 and R2 include a phenyl group and a naphthyl group, and these aryl groups include those having an it substituent, and examples of the substituent include an alkyl group (such as a methyl group), Examples include alkoxy groups (such as methoxy groups) and acylamino groups (such as acetylamino groups).

Examples of the heterocyclic group represented by R1 and R2 include a 2-furyl group and a 2-pyridyl group, and these heterocyclic groups include those having a substituent.

If the total number of carbon atoms in the groups represented by R1 and R2 is less than 8, the compound represented by formula [I] will flow out from the photosensitive material into the processing solution during the processing process. The object of the invention cannot be achieved 6 In the present invention, in the above-mentioned formula [I], it is preferable that each RR2 is an alkyl group, and the total number of carbon atoms including the substituents of R1 and R2 is 12
It is particularly preferable that the condition is above.

Specific examples of the dye image stabilizer represented by the general formula [I] of the present invention are shown below, but the present invention is not limited to these examples.

Margin below 3 24 [IO) 12 6 7 8 9 0 Margin below General formula [A) 2.Zl, In general formula [A], R1! Examples of the aryl group represented by include phenyl group and 1-naphthyl group. These aryl groups include those having substituents, and examples of the substituents include alkyl groups, aryl groups, anilino groups, acylamino groups, sulfonamide groups, alkylthio groups, arylthio groups, alkenyl groups, and cycloalkyl groups. It will be done.

Examples of the heterocyclic group represented by R include 2-furyl group and 2-thienyl group. These heterocyclic groups include those having substituents, and examples of the substituents include the substituents mentioned above for the substituents of the aryl group.

Zl and Z2 each represent an alkylene group having 1 to 3 carbon atoms.The alkylene groups represented by Z, , and Z2 include those having a substituent, and the substituent is as described for the substituent of the aryl group above. Examples include substituents.

n represents 1 or 2.

In the present invention, compounds in which R 1 is a phenyl group, Zl and Z2 are each an ethylene group, and n is 2 in formula [A] are particularly preferred.

Specific examples of the dye image stabilizer represented by the general formula [A] of the present invention are shown below, but the present invention is not limited to these examples.

Margin below 1 -2 -3 -4 -6- 7- -9 -10 -11 -12 -21 2 -23 -24 OC2FI.

-28 -29 -13 -17 0 -32 -33 4 C)13 C)I3 -18 H3 Below margin - Formula CB) As the secondary or tertiary alkyl group represented by R'' in the general formula CB), , for example, t-butyl group, S-butyl group, t-amyl group, S-amyl group, t-octyl group,
Examples include i-propyl group.

Examples of the secondary or tertiary alkenyl group represented by R'' include i-propenyl group and 2-hexenyl group.

Examples of the alkyl group represented by R'' include a methyl group,
Examples include ethyl group, t-butyl group, and pentadecyl group. These alkyl groups include those with substituents,
Examples of the substituent include an allyl group, an alkoxy group, and a halogen atom.

Examples of the alkenyl group represented by R22 include a 1-hexenyl group and a butenyl group, and these alkenyl groups may be linear or branched, and include those having a substituent.

As the cycloalkyl group represented by R21 and R22,
Examples include a cyclohexyl group and a cyclopentyl group, and these cycloalkyl groups also include those having one substituent.

Examples of the aryl group represented by R", R" include phenyl group, naphthyl group, etc. These aryl groups include those having one substituent, and examples of the substituent include alkyl group, alkoxy group, Examples include an aryl group, a nitro group, and a halogen atom.

Examples of the alkylene group represented by X include a methylene group, an ethylene group, a propylene group, a butylidene group, a hexamethylene group, and these alkylene groups may have a substituent.

- Among the compounds represented by the formula CB), preferred embodiments are shown in the general formula (B-I:I).

-Formula CB-I] Representative specific examples of the general formula CsE of the present invention are shown below, but the invention is not limited thereto.

Margin below In the formula, R21-R22 and n are the same as in general formula CB)23 represents a group, and Xl represents -S- or -0-.

24 R23 and R24 each represent a hydrogen atom, an alkyl group such as methyl, ethyl, l-propyl, hexyl, benzyl, etc., or an alkenyl group (such as allyl, i-
propenyl, 1-ethyl-1=pentynyl, etc.),
Among these, n is preferably 0 or 1, and when n is 1, R2
2 is preferably a primary or secondary alkyl group, among which,
More preferably in 23, Xl is -C-.

2ml -11 2 -14 -15 CH3 CH3 CH3 CH3 -9 C7H+ s 6 CH3 CH3 7- -19 CH3 CH3 CH3 CH3 C)13 CH3 CH2 C)+3 H H3 28 4 c4Hstt) -25 CH3 -26 CH CH3/ \C)13 -27 CH CH3/\C3H7 -32 M CH3/\C2H6 -33 CH2CH2CH=C(CH3) 2 -34 -35 CHC)13 HCH3 aHs C2H6'' CH C,H7 - Compound represented by formula CB] is U.S. Patent 2,80
No. 7,653, Journal on Chemical Society Park I (J, Chel, Soc, Park
In I), p. 1712 (1979), it can be synthesized according to the method described.

General formula CC) In general formula (C), R'l, R3", R" and R3
The alkyl group represented by ' is preferably one having 1 to 32 carbon atoms, such as a methyl group, an ethyl group, a t-butyl group, a pentadecyl group, and the like.

These alkyl groups also include those having substituents.

Examples of the aryl group represented by R31, R32, R33 and R34 include a phenyl group and a naphthyl group. These aryl groups include those having one substituent, and examples of the substituent include an alkyl group, an alkoxy group, an aryl group, a nitro group, and a halogen atom.

The alknyl groups represented by R31, R32, R33 and R34 preferably have, for example, 2 to 32 carbon atoms, and these alknyl groups may be straight or branched. Moreover, these alknyl groups include those having a substituent.

Examples of the alkoxy group represented by R3' and R'' include a methoxy group and an ethoxy group, and these alkoxy groups include those having one substituent.

Examples of the acyl group represented by R'', R32, R33, and R3' include an alkylcarbonyl group and an arylcarbonyl group, and these acyl groups include those having a substituent.

Examples of the acylamino group represented by R31, R'' and R34 include an alkylcarbonylamino group and an arylcarbonylamino group, and these acylamino groups also include those having a substituent.

Examples of the acyloxy group represented by R31, R33 and R3' include an alkylcarbonyloxy group and an arylcarbonyloxy group, and these acyloxy groups include those having substituents.

Examples of the sulfonamide group represented by R'', R33 and R34 include an alkylsulfonylamino group and an arylsulfonylamino group, and these sulfonamide groups also include those having a substituent.

The cycloalkyl group represented by R31, R32, R33 and R34 preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, etc., and these cycloalkyl groups are substituted with Also includes those with groups.

The heterocyclic group represented by R32 is preferably a 5- to 7-membered ring, such as a 2-furyl group, a 2-thienyl group, or a 2-membered ring.
-pyrimidinyl group, 2-benzothiazolyl group, etc. These heterocyclic groups include those having substituents.

R'' and R33 may be ring-closed with each other to form a 5- or 6-membered ring, or R32 and R33 may be ring-closed with each other to form a methylenedioxy ring.

Y" represents an atomic group necessary to form a taloman or coumaran ring.

This Taloman or Claman ring may be monosubstituted with a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alknyl group, an aryloxy group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, etc. It may form a ring.

Among the compounds represented by the general formula [C], the compounds particularly useful in the present invention are - formula [C-■], (C-II), (
C-I), ((, I'V) and [CV].

- Mathematical formula [:C-I) 3 General formula (C-n) 3 - Mathematical formula [C-I [[] General formula [C-IV] General formula [:C-V] 3 34 General formula CC-I), [C-I[], [C-In), [C
-IV) and CC-V]: bRs+, R32!
R33 and R34 have the same meaning as in the above-mentioned formula [C], R'' represents a substituent, and m is 0 or ζ 1 to 4
1 represents an integer of 0 or 1 to 6.

When m represents an integer of 2 to 4, and when 1 represents an integer of 2 to 6, multiple R35s may be the same or include specific examples of substituents represented by R35. Examples include halogen atoms, alkyl groups, cycloalkyl groups, alkenyl groups, cycloalkenyl groups, alkynyl groups, aryl groups, heterocyclic groups, acyl groups, sulfonyl groups, sulfinyl groups, phosphonyl groups, carbamoyl groups, sulfamoyl groups, cyano group, spiro compound residue, bridged hydrocarbon compound residue, alkoxy group, aryloxy group, heterocyclic oxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, acylamino group, sulfonamide group,
Examples include imide group, ureido group, sulfamoylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, alkoxycarbonyl group, aryloxycarbonyl group, alkylthio group, arylthio group, and heterocyclic thio group.

Examples of the halogen atom include a chlorine atom and a bromine atom, with a chlorine atom being particularly preferred.

Alkyl groups have 1 to 32 carbon atoms, alkenyl groups, alkynyl groups have 2 to 32 carbon atoms, cycloalkyl groups, and cycloalkenyl groups have 3 carbon atoms.
-12, particularly preferably 5-7, and the alkyl group, alkenyl group, and alkynyl group may be monovalent or branched.

In addition, these alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, and cycloalkenyl groups are substituents [e.g., aryl, cyano, halogen atoms, heterocycles, cycloalkyl, cycloalkenyl, spiro compound residues, bridged hydrocarbon compounds] In addition to residues, those substituted via a carbonyl group such as acyl, carboxy, carbamoyl, alkoxycarbonyl, and aryloxycarbonyl, and those substituted via a heteroatom, specifically hydroxy, alkoxy, and aryloxy. , heterocyclic oxy,
Those substituted through an oxygen atom such as siloxy, acyloxy, carbamoyloxy, nitro, amine (including dialkylamine, etc.), sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, acylamino, sulfonamide, imide, ureido Substituents via the nitrogen atom such as alkylthio, arylthio, heterocyclic thio, sulfonyl, sulfinyl,
(such as those substituted via a sulfur atom such as sulfamoyl, and those substituted via a phosphorus atom such as phosphonyl).

Specifically, for example, methyl group, ethyl group, isopropyl group, t-butyl group, pentadecyl group, heptadecyl group, 1
〜hexylnonyl group, 1,1′ dibenthylnonyl group, 2
-chloro-t-butyl group, trifluoromethyl group, 1-
Ethoxytridecyl group, 1-methoxyisopropyl group,
methanesulfonylethyl group, 2.4-di-t-amylphenoxymethyl group, anilino group, 1-phenylisopropyl group, 3-m-butanesulfonaminophenoxypropyl group, 3-4'-+α-[4'' (p -hydroxybenzenesulfonyl)phenoxy]dodecanoylamino)
Funinylprobyl group, 3-+4'-Cα-(2″, 4″
-di-t-amylphenoxy)butanamido]phenyl)-propyl group, 4-[α-(0-chlorophenoxy)
Examples include a tetradecaneamide phenoxyfupropyl group, an allyl group, a cyclopentyl group, a cyclohexyl group, and the like.

As the aryl group, a phenyl group is preferable, and a substituent (
For example, it may have an alkyl group, an alkoxy group, an acylamino group, etc.).

Specifically, phenyl group, 4-t-butylphenyl group,
2.4-di-t-amylphenyl group, 4-tetradecanamidophenyl group, hexadecyloxyphenyl group, 4
'-[α-(4″-t-butylphenoxy)tetradecanamidophenyl group and the like.

The heterocyclic group is preferably 5 to 7@, and may be substituted or fused, specifically 2-furyl group, 2-thienyl group, 2-pyrimidinyl group,
Examples include 2-benzothiazolyl group.

Examples of the acyl group include acetyl group, phenylacetyl group, dodecanoyl group, alkylcarbonyl group such as α-2,4-di-1-amylphenoxybutanoyl group, benzoyl group, 3-bentatecyloxybenzoyl group, p-
Examples include arylcarbonyl groups such as chlorobenzoyl group.

Examples of the sulfonyl group include a methylsulfonyl group, an alkylsulfonyl group such as a dodecylsulfonyl group, an arylsulfonyl group such as a benzenesulfonyl group, and a p-)luenesulfonyl group.

Examples of the sulfinyl group include alkylsulfinyl groups such as ethylsulfinyl group, octylsulfinyl group, and 3-phenoxybutylsulfinyl group, and arylsulfinyl groups such as phenylsulfinyl group and m-pentadecylphenylsulfinyl group.

The phosphonyl group includes an alkylphosphonyl group such as a butyloctylphosphonyl group, an alkoxyphosphonyl group such as an octyloxyphosphonyl group, an aryloxyphosphonyl group such as a phenoxyphosphonyl group, and an arylphosphonyl group such as a phenylphosphonyl group. Examples include groups.

The carbamoyl group may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as N-methylcarbamoyl group, N,N-dibutylcarbamoyl group, N-(2-pentadecyl)octyl-N- Ethylcarbamoyl group, N-ethyl-N-dodecylcarbamoyl group,
Examples include N-+3-(2,4-di-t-amylphenoxy)propyl)carbamoyl group.

The sulfamoyl group may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., for example, N-
Propylsulfamoyl group, N.

N-diethylsulfamoyl group, N-(2-pentadecyloxyethyl)sulfamoyl group, N-ethyl-N-
Examples include dodecylsulfamoyl group and N-phenylsulfamoyl group.

Examples of spiro compound residues include spiro[3°3]hebutan-1-yl and the like.

Examples of the bridged carbonized compound residue include hiscyclo(2,2
,1]hebutan-1-yl, tricycloC3,3,1,
1":l decane-1-yl, 7fudimethyl-bidiclo[2,2,1)heptane-1-yl, and the like.

The alkoxy group may be further substituted with the substituents listed above for the alkyl group, such as a methoxy group,
Examples include propoxy group, 2-ethoxyethoxy group, pentadecyloxy group, 2-dodecyloxyethoxy group, phenethyloxyethoxy group, and the like.

The aryloxy group is preferably phenoxy, and the aryl nucleus may be further substituted with any of the substituents or atoms listed above for the aryl group, such as phenoxy group, pt-butylphenoxy group, m-pentaphenoxy group, etc. Examples include decylphenoxy group.

The heterocyclic oxy group preferably has a 5 to 7-heterocycle, and the heterocycle may further have a 1f substituent, for example, 3,4,5,6-tetrahydrobilanyl -2-oxy group, 1-phenyltetrazole-5-
An example is an oxy group.

Examples of the siloxy group include trimethylsiloxy group,
Examples include triethylsiloxy group and dimethylbutylsiloxy group.

Examples of the acyloxy group include an alkylcarbonyloxy group, an arylcarbonyloxy group, etc., and may further have a substituent, specifically an acetyloxy group, an α-taloloacetyloxy group, a benzoyloxy group, etc. etc.

The carbamoyloxy group may be substituted with an alkyl group, an aryl group, etc., such as N-ethylcarbamoyloxy group, N,N-diethylcarbamoyloxy group, N-
Examples include phenylcarbamoyloxy group.

The amino group may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., such as ethylamino group, anilino group, m-chloroanilino group, 3-pentadecyloxysulfonylanilino group, 2- Chloro-5-
Examples include hexadecaneamide anilino group.

Examples of the acylamino group include an alkylcarbonylamino group, an arylcarbonylamino group (preferably a phenylcarbonylamino group), and may further have one substituent, specifically an acetamido group, an α-ethylpropanamide group, etc. , N-phenylacetamide group, dodecanamide group, 2,4-di-7-amylphenoxyacetamide group, α-3-t-butyl-4-hydroxyphenoxybutanamide group, and the like.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group, which may further have a substituent, specifically a methylsulfonylamino group, a pentadecylsulfonylamino group, a benzenesulfonylamino group, Examples include p-toluenesulfonamide group and 2-methoxy-5-t-amylbenzenesulfonamide group.

The imide group may be open-chain or cyclic.
It may have a substituent, for example, a succinimide group,
3-hegetadecylsuccinimide group, phthalimide group,
Examples include glutarimide group.

The ureido group may be substituted with an alkyl group, an aryl group (preferably a phenyl group), etc., for example, N-
Examples include ethylureido group, N-methyl-N-decylureido group, N-phenylureido group, N-p-)silureido group, and the like.

The sulfamoylamino group is an alkyl group, an aryl group (
It may be monosubstituted, preferably with a phenyl group), such as N,N-dibutylsulfamoylamino group, N-methylsulfamoylamino group, N-phenylsulfamoylamino group, etc.

The alkoxycarbonylamino group may further have a substituent, such as a methoxycarbonylamino group, a methoxyethoxycarbonylamino group, an octadecyloxycarbonylamino group, and the like.

The aryloxycarbonylamino group may have a substituent, for example, a phenoxycarbonylamino group, 4
-methylphenoxycarbonylamino group.

The alkoxycarbonyl group may further have a substituent, such as a methoxycarbonyl group, a butyloxysulfonyl group, a dotecyloxycarbonyl group, an octadecyloxysulfonyl group, an ethoxymethoxycarbonyloxy group, a pencyloxycarbonyl group, and a butyloxycarbonyl group. Examples include nyl group.

The aryloxycarbonyl group may further have a substituent, such as phenoxycarbonyl group, p-chlorophenoxycarbonyl group, m-pentadecyloxyphenoxycarbonyl group, and the like.

The alkylthio group may further have a substituent, and examples thereof include an ethylthio group, a dodecylthio group, an octadecylthio group, a phenethylthio group, and a 3-phenoxypropylthio group.

The arylthio group is preferably a phenylthio group, and may further have a substituent, such as a phenylthio group, a p-methoxyphenylthio group, a 2-t-octylphenylthio group,
Examples include 3-octadecylphenylthio group, 2-carboxyphenylthio group, and p-acetaminophenylthio group.

The heterocyclic thio group is preferably a 5- to 7-membered heterocyclic thio group, which may further have a fused ring or a substituent. For example, a 2-pyridylthio group, a 2-benzo Thiazolylthio group, 2,4-diphetoxy 1,3.5
-1 lyazole-6-thio group is mentioned.

Further, in the present invention, - formula (C-I), [C-I
t), [C-V], the case where the carbon atom forming the coumaran ring or the taloman ring is a spiro atom is also included.

Furthermore, in formulas [C-1 [[] and (C-IVI), a taloman ring is formed and a carbon atom other than the carbon atom that is already present as a spiro atom becomes a spiro atom.

In addition, in formulas (c-I), cc-m], [C-■], and CC-V), a coumaran or chroman ring is formed, and two adjacent carbon atoms and two R35 cooperate The present invention also includes cases where a 5- to 7-membered cycloalkyl ring is formed.

Typical specific examples of these compounds are shown below, but the compounds used in the present invention are not limited thereto.

Margin below -1 -2 -9 -3 -4 -10 H -5 -6- -7- -8 [I(3 CH co H3 H3 13 H3 C.T.

-21 -22 H3 -24 H3 -17 -18 -19 -20 Shit13 113 -25 -26 -27 -29 I General formula CD] R4 Additionally, a spiro ring may be formed.

Among the compounds represented by the general formula [D], compounds particularly useful in the present invention are included in the compounds represented by the formula (D-I:l~[)-I[).

- R'', R'2, R43 and R'' in formula CD)
As for R3R3' in -formula CC), the groups detailed above can be mentioned.

Further, R'3 and R4' may be ring-closed with each other to form a 5- or 6-membered hydrocarbon ring. This 5- or 6-membered hydrocarbon ring is a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkenyl group, a hydroxy group, an aryl group, an aryloxy group, an acyl group, an acylamino group, an acyloxy group, or a heterocycle. It may be substituted with a group or the like.

Y2O represents an atomic group necessary to form an indane ring. This indane ring may be substituted with a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, a cycloalkyl group, a hydroxy group, an aryl group, an aryloxy group, a heterocyclic group, etc. (44 R41R4 in the general formula [D-I[] and the following margin general formula [D-I], CD-, I[])
2, R543 and R544 have the same meaning as in general formula [D], R4'5 represents a substituent, and m is 0 or 1
represents an integer of ~6, and j represents O or an integer of 1-4.

When m represents an integer of 2 to 6, or when 1 represents an integer of 2 to 4, a plurality of R45s may be the same or different. Specific examples of the substituent represented by R4'5 include the same groups as those listed for the general formulas (C-I] to (C-V'l)R35 above.

Further, in the present invention, in -formula CD-I),
This also includes cases where the carbon atoms forming the indane ring are spiro atoms.

Furthermore, the case where a carbon atom other than the carbon atom that forms an indane ring and already exists as a spiro atom in formula [D-II') becomes a spiro atom is also included.

Also, in formulas CD-I) and CD-I[), an indane ring is formed, and two adjacent carbon atoms and two R
A case where 45 cooperates to form a 5-7-cycloalkyl ring is also included in the present invention.

Typical specific examples of these compounds are shown below, but the compounds used in the present invention are not limited by these.

Below margin 1 -3 -5 -7 QC) +3 -15 6- -4 -8 -10 1 -12 -13 4 CH3 CH3 -19 0 -21 CH3 -22 CH3 CH3 D-23 D-24 -25 -26 -27 Below margin In the present invention, - one of the compounds represented by the formula [I] and at least one of the compounds represented by the general formula [A] or [B] or [C] or [D] At the same time, it is used as an anti-fading agent, and the proportion of the compound represented by formula [A] is preferably 5 to 95%, more preferably 10%.
~90%.

The amount of the anti-fading agent used in the present invention is preferably 5 to 400 mol%, more preferably 10 to 300 mol%, based on the organic coloring substance.

The organic coloring substance whose fading is prevented according to the present invention is an organic substance having at least one absorption maximum between 300 nm and 800 nm, preferably between 400 nm and 700 nm in a methanol solution, and includes basic dyes, acid dyes,
Due to the dyeing properties of water-soluble dyes such as direct dyes, soluble vat dyes, mordant dyes, insoluble dyes such as sulfur dyes, vat dyes, oil-soluble dyes, disperse dyes, azoic dyes, oxidation dyes, or reactive dyes. It includes all dyes that fall under the category of .

Among these dyes, preferred dyes whose fading is prevented by the present invention include quinone imine dyes (azine dyes, ogissacin dyes, thiazine dyes, etc.), methine and polymethine dyes (cyanine dyes, azomethine dyes, etc.), azo dyes, and anthraquinone dyes. , indoamine and indophenol dyes, indigoid dyes, carbonium dyes, formazan dyes, and other dyes belonging to chemical elliptical classes.

Organic coloring substances whose fading is prevented according to the present invention include image-forming dyes used in the field of photography, such as couplers,
Dyes formed from colored couplers, DRR compounds, DDR couplers, amitracine compound dye developers, etc.
Includes all dyes used in silver dye bleaching methods.

Particularly preferred dyes whose fading is prevented according to the invention are:
The dyes most preferably used in the present invention are methine and polymethine dyes and indoamine and indophenol dyes, such as anthraquinone, quinoneimine, azo, methine, polymethine, indoamine, indophenol and formazan dyes.

The foregoing couplers include those of the yellow, magenta and cyan dye-forming types. This coupler is described, for example, in U.S. Pat.
The so-called 4-equivalent type as described in No.
Alternatively, it may be a two-equivalent type in which the carbon atom at the coupling position is substituted with a substituent (split-off group) that can be separated during the Kablink reaction.

Furthermore, by coupling with a coupler having a color correction effect, a competitive coupler, and an oxidized product of a color developing agent, a development accelerator, a bleach accelerator, a developer, a silver halide solvent, a toning agent, a hardening agent, Fogging agent, antifogging agent, chemical sensitizer,
Compounds that release photographically useful fragments such as spectral enhancers and desensitizers can also be used.

It is also possible to use colorless couplers that do not form dyes to carry out the coupling reaction with the oxidized form of the aromatic primary amine developer.

Preferred yellow couplers that can be used include benzoylacetanilide type couplers and pivaloylacetanilide type couplers; macenta couplers include 5-pyrazolone type, pyrazolotriazole type and intazolone type couplers; and cyan dye-forming couplers include: There are phenol-based, naphthol-based, pyrazoloquinazolone-based, pyrazolopyrimidine-based, pyrazolotriazole-based, and intazolone-based couplers.

Next, typical examples of yellow couplers will be given.

-1 -2 Below margin -3 -4 j -5 CNOH3 -6 10 CH3 1 ¥-14 -12 1 -15 In addition to these, yellow couplers that can be used in combination include, for example, 0L32.163,812, Kaisho 47-261
No. 33, No. 48-29432, No. 50-65321, No. 51-3631, No. 51-50734, No. 51
-102636, 4866835, 48-94
432, No. 49-1229, No. 49-10736, Japanese Patent Publication No. 51-33410, No. 52-25733, etc., and can be synthesized according to the methods described therein. be able to.

Next, typical examples of magenta couplers will be given.

-2 Below margin -3 NHS02C+ 6To3 4 1 -5 2H5 -6 -7- j I -15 j -8 0 -16 C" j -17 -18 -19 CsH+7ft) 4Hs C9HI7[tl M-20 M-21 - 22 0OCJs -23 j -24 1 -25 In addition to these, macentor couplers that can be used in combination include, for example, U.S. Patent No. 3,684,514 and British Patent No. 1183.
．． No. 515, Special Publication No. 40-6031, No. 40-603
No. 5, No. 44-15754, No. 45-40757,
No. 46-19032, No. 50-13041, No. 53-129035, No. 51-37646, No. 55
-62454, U.S. Patent No. 3,725,067, British Patent No. 1,252,418, British Patent No. 1,334,515,
JP 59-171956, JP 59-162548, JP 60-43659, JP 60-33552, Research, Disclosure No. 24626 (1984
), Patent Application No. 59-243007, No. 59-2430
No. 08, No. 59-243009, No. 59-24301
2, No. 60-70197, No. 60-70198, etc., and can be synthesized according to the methods described therein.

Next, typical examples of cyan couplers will be given.

Below margin 1 C-4 H -9 4H9 C3H7(il CH3 -5 -6- 7- H -13 H 4 H 5 CsH+7(t) -16 OCH2CH2SCHCOOH [Il?H2S C-17 C-21 H N -18 H f1lc4HsOcONH0CH2CH2SCHCOO
Hl2H25 -22 -19 -23 OCH2CONHCH2CH20CH3-24 N 4H9 In addition to these, cyan couplers include, for example, U.S. Pat. No. 134644, No. 51109630, No. 54-55380, No. 56-
No. 65134, No. 56-80045, No. 57-155
No. 538, No. 57-204545, No. 58-9873
No. 1, No. 59-31953, etc., and can be synthesized according to the methods described therein.

When such couplers are used in the present invention, dyes are formed from these couplers by reaction with an oxidized aromatic primary amine silver halide developer.

The developer mentioned above includes aminophenol and phenylenediamine, and these developers can be used in combination.

The above-mentioned anti-fading agent of the present invention is preferably present in the photographic material, particularly in the organic coloring substance or the layer in which it is formed, or in a layer adjacent thereto.

The methods effective for dispersing these compounds of this invention are the same as those used for dispersing couplers.

The compounds used in the present invention are generally oil-soluble and are commonly found in U.S. Pat. Nos. 2,322,027 and 2,801.
No. 170, No. 2,801,171, No. 2,272,1
91 and No. 2304.940, it is preferable to dissolve it in a high-boiling 7-point solvent, if necessary in combination with a low-boiling point solvent, disperse it, and add it to the hydrophilic colloid solution. There is no problem in using a coupler, a hydroquinone derivative, an ultraviolet absorber, or a known pigment surface @ anti-fading agent, etc., depending on the situation.

For example, as a known pigment image fading preventive agent, JP-A-61
Compounds described in JP-143754 and the like can be mentioned.

The silver halide emulsion used in the photographic light-sensitive material of the present invention is generally one in which silver halide grains are dispersed in a hydrophilic colloid, and the silver halide includes silver chloride, silver bromide, silver bromide,
Silver iodide, silver chlorobromide, silver iodobromide, silver chloroiodobromide, and mixtures thereof.

[Example] Next, the present invention will be explained in detail with reference to Examples, but the present invention is not limited thereto.

Example 1 On a paper support double-sided laminated with polyethylene, the following layers were sequentially coated from the support # side to produce a multicolor photographic silver halide photonic material, which was designated as Sample 1.

1st layer: blue-sensitive silver halide emulsion layer yellow coupler (Y-11) 6.8■/100
cd, blue-sensitive silver chlorobromide emulsion (containing 85 mol% silver bromide) converted to silver is 3.2 ■/100aJ, dibutyl phthalate is 3.5ffill' 1ooi and hgelatin is 1
The coating was applied so that the thickness was 3.5■/100d.

2nd layer: Intermediate layer 2.5-di-t-octylhydroquinone 0.5μ/
100a&, dibutyl phthalate 0.5■/100
d and gelatin were coated at a rate of 9.0 cm/100 cd.

3rd layer: green-sensitive silver halide emulsion layer magenta coupler (M-17) 35μ/100 cd
, green-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) in terms of silver is 25 µ/100 cH, dibutyl phthalate is 30 µ/100 c+J, and seratin is 12 µ/100 cH. O■/
It was coated so that it became 400-.

4th layer: Intermediate layer UV absorber 2-(2-hydroxy-35-di-t-butylphenyl)benzitriazole at 0.7/10
0cd, dibutyl phthalate 6.0■/100a
d, 0.5 of 2,5-di-t-octylhydroquinone
■/100cd and gelatin 12.0■/10
It was coated so that it was 0 cd.

5th layer: red-sensitive silver halide emulsion layer cyan coupler (C-5) 4.2■/IQOcd,
Red-sensitive silver chlorobromide emulsion (containing 80 mol% silver bromide) is 3.0 ■/100 cd in terms of silver, tricresyl phosphate is 3.5 ■/100-, and seratin is 11.5 ■.
/10Qaa.

6th layer: Protective layer Ceratin was coated at a thickness of 8.0 cm/100 cd.

Comparative Compound 1 Comparative Compound 2 In the above sample 1, the dye image stabilizer was added to the third layer in a proportion as shown in Table 1 (equal moles for those using two types) such that the total amount was 100 mol% relative to the coupler. was added to prepare multilayer samples 2 to 10.

After exposing the sample obtained above through an optical wedge according to a conventional method,
The treatment was carried out in the following steps.

[Processing process] Processing temperature Processing time Color development @
Bleach fixing at 33°C for 3 minutes and 30 seconds Washing with water at 33°C for 3 minutes Drying at 50°C to 80°C for 2 minutes The composition of the processing solution used in each processing step is as follows.

[Color developer] Benzyl alcohol 12rr+J diethylene glycol 10m layer Potassium carbonate 25 g Sodium bromide
0.6g anhydrous sodium sulfite
2. Of hydroxylamine sulfate
2.5 g Ki'-ethyl-N-β-methanesulfonamidoethyl-3-methyl-4 aminoaniline sulfate 4.5 f Water was added to make 1 fJ, and the pH was adjusted to 10.2 with sodium hydroxide.

[Bleach-fix solution Ammonium cothiosulfate 120 g Sodium metabisulfite 15 M Anhydrous sodium sulfite 3 g Eethynediaminetetra#acid 29P.

65 g of ammonium salt was added with water to bring the mixture to 11, and the pH was adjusted to 6.7 to 6.8.

The concentrations of the samples 1 to 1o treated above were measured using a densitometer (model KD-7R manufactured by Koniriki Co., Ltd.) at the following stripes.

The processed sample was exposed to a xenon fade meter for 16 days to examine the light resistance of the dye image.

Table 1 From the results in Table 1, the use of the compound of the present invention was effective in stabilizing magenta dye images formed from magenta couplers, and Y-stin in unexposed areas was also improved. Further, during dissolution, there was no precipitation and the dispersion stability was good.

Example 2 A silver chlorobromide emulsion containing 99.5 mol % of silver chloride was used in place of each silver halide ashing agent used in Example 1, and the couplers and dye image stabilizers in each layer were as shown in Table 2. Samples 11 to 26 were prepared in the same manner as Sample 1 of Example 1, except that
was created.

Samples 11 to 26 were subjected to light wedge exposure according to a conventional method, and then subjected to the following treatments.

[Processing process] coloring phenomenon bleach fixing Stabilization drying drying [Color developer] Processing temperature 35.0 standing 0.3℃ 35.0±0.5°C 30-34℃ Room temperature (25℃) processing time 45 seconds 45 seconds 90 seconds Dry naturally with Pure water triethanolamine N,N-diethylhydroxylamine potassium bromide potassium chloride potassium sulfite 1-hydroxyethylidene-1,1 diphosphonic acid Ethylenediaminetetraacetic acid Catechol-3,5-disulfonic acid disodium salt N-ethyl-N-β-methanesulfone Amidoethyl-3-methyl-4- Aminoaniline sulfate Optical brightener (4,4°-diamino stilbenedisulfonic acid derivatives) potassium carbonate Add water to bring the total volume to 11, pH 10 do.

E Bleach-fix solution J 800 ml 10゜g 0.02g g o, 3g 1, Og 1.0g 1.0g g 1, Of 7g Adjust to 10 Ethylenediaminetetra# acid ferric ammonium dihydrate eog Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% water soluble i) 100ml
Sub-Km ammonium (40% water soluble i) 27.5on
Add 1 liter of water to bring the total volume to 11, and add potassium carbonate or ice #
Adjust the pH to 6.2 with acid.

[Stabilizing liquid co-5-chloro-2-methyl-4=isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1 1-diphosphonic acid 2.01 r ethylenediaminetetra #B 1, Og ammonium hydroxide <20% aqueous solution) 3.0°
Ammonium acid 3.0g Fluorescent brightener (44°-diaminostilbendisulfonic acid derivative) 1.5g Add water to bring the total volume to 11, and adjust the pH with sulfuric acid or potassium hydroxide.
8M to 7.0.

The light resistance of each sample after treatment was tested and evaluated in the same manner as in Example 1. The results are shown in Table 2.

Margin Example 3 Samples 27 to 36 were prepared in the same manner as Sample 1 of Example 1, except that the magenta coupler and dye image stabilizer in the third layer were changed as shown in Table 3.

This was subjected to the same treatment as in Example 1, and the light resistance of each sample after treatment was tested and evaluated in the same manner as in Example 1. The results are shown in Table 3.

Margin Table 2 Table 3 As is clear from Table 2.3, the samples using the exemplified compounds according to the present invention showed good light fastness of dye images and good dispersion stability.

E Effects of the present invention Silver halide photographic materials prepared using the dye image stabilizer according to the present invention exhibit extremely little discoloration or fading of the formed yellow, magenta, and cyan dyes, and have good color balance after light fastness tests. It is possible to maintain extremely good color reproducibility.

Claims (1)

[Scope of Claims] A silver halide photographic material having a photographic constituent layer including at least one silver halide emulsion layer on a support, in which at least one of the photographic constituent layers is represented by the general formula [I]. A silver halide photographic light-sensitive material characterized by containing at least one compound and at least one compound represented by the general formula [A] or [B] or [C] or [D]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^1 and R^2 are alkyl groups with 4 or more carbon atoms,
Represents an aryl group, alkenyl group, cycloalkyl group, or heterocyclic group. ] General formula [A] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the formula, R^1^1 represents an aryl group or a heterocyclic group,
Z_1 and Z_2 each represent an alkylene group having 1 to 3 carbon atoms. However, the total number of carbon atoms in the alkylene groups represented by Z_1 and Z_2 is 3 to 6. n represents 1 or 2. ] General formula [B] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^2^1 is a secondary or tertiary alkyl group,
Represents a secondary or tertiary alkenyl group, cycloalkyl group, or aryl group, R^2^2 represents a halogen atom, alkyl group, alkenyl group, cycloalkyl group, or aryl group, and n is an integer of 0 to 3. represent. X represents S, SO, SO_2 or an alkylene group. ] General formula [C] ▲Mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^3^1 and R^3^4 are hydrogen atoms, halogen atoms, alkyl groups, alkenyl groups, alkoxy groups, hydroxyl groups, respectively. group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group, R^3^2 is a hydrogen atom, an alkyl group,
Represents an alkenyl group, aryl group, acyl group, cycloalkyl group or heterocyclic group, R^3^3 is a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an aryl group, an aryloxy group, an acyl group, an acylamino group, Represents an acyloxy group, a sulfonamide group, a cycloalkyl group, or an alkoxycarbonyl group. Further, R^3^2 and R^3^3 may be ring-closed with each other to form a 5- or 6-membered ring. Also R^3^2 and R^3^3
may be ring-closed to form a methylenedioxy ring. Y^3^0 represents an atomic group necessary to form a chroman or coumaran ring. ] General formula [D] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R^4^1, R^4^2, R^4^3 and R^4
^4 is a hydrogen atom, a halogen atom, an alkyl group,
Represents an alkenyl group, hydroxy group, alkoxy group, aryl group, aryloxy group, acyl group, acylamino group, acyloxy group, sulfonamide group, cycloalkyl group or alkoxycarbonyl group. However, R^4^
At least one of 2 and R^4^3 is a hydroxy group or an alkoxy group. Further, R^4^3 and R^4^4 may be ring-closed with each other to form a 5- or 6-membered hydrocarbon ring. Y^4^0 represents an atomic group necessary to form an indane ring. ]