JPH05127329A - Silver halide photographic sensitive material with improved color reproducibility - Google Patents

Abstract

PURPOSE:To make sufficiently show color reproducibility improving effect due to fluorescent material and to prevent the durability of an image dyestuff from lowering. CONSTITUTION:In a silver halide photographic sensitive material having a photography constituting layer containing a halogenated silver emulsion layer and a ultraviolet rays absorbent containing layer on a support body, a compound capable of discharging a mercapto compound as a function of exposed silver halide is included in at least one layer of the ultraviolet rays absorbent containing layer and the photography constituting layer on the nearer side of the support body than the former layer, and at least one of fluorescent compound precursors capable of forming fluorescent material by reacting with a mercapto compound discharged from a compound capable of discharging the above mercapto compound on color development or fluorescent compound precursors capable of forming fluorescent material by reacting with a mercapto compound discharged from a compound capable of discharging the above mercapto compound on color development and a color developer component are included in at least one layer of the ultraviolet rays absorbent containing layer and the photography constituting layer on the farther side of the support body than the former layer.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material having improved color reproducibility.

[0002]

BACKGROUND OF THE INVENTION In a silver halide photographic light-sensitive material, a so-called dye-forming coupler is generally used which reacts with a light-sensitive silver halide emulsion and an oxidized aromatic primary amine developing agent to form a dye. In the case of color photographic paper used for use, a combination of a yellow coupler, a magenta coupler and a cyan coupler is usually used.

The dyes produced from these couplers ideally absorb only blue light in the case of a yellow coupler, green light in the case of a magenta coupler, and red light in the case of a cyan coupler. However, in reality, each of them has unwanted unwanted absorption. Therefore, it cannot be said that the current silver halide photographic light-sensitive materials have sufficient performance in terms of color reproducibility.
Amid the increasing demand for higher quality and higher image quality in the market,
The improvement is desired.

As a technique for correcting the spectral absorption of dye images produced from couplers, US Pat. No. 4,774,181 describes imaging elements containing couplers that release fluorescent dyes. This is to optically correct the unnecessary absorption of the image dye produced by releasing the fluorescent dye imagewise from the coupler by color development.

However, when the coupler which releases the fluorescent dye is used, most of the released fluorescent dye is washed out to the outside of the photographic constituent layers during the development process, and a sufficient effect cannot be obtained. Further, it is described that a mordant is used for the purpose of preventing the washout of the fluorescent dye, but in this case, there is a problem that the stain, which is considered to be due to the sensitizing dye or the water-soluble dye, increases and cannot be put to practical use. is doing. In addition, the fluorescent compound precursor must be used as the leaving group of the coupler, which limits the range of structural choices of the fluorescent substance that can be used and limits the characteristics of the emitted fluorescent dye. In addition, there is a problem that the stability of fluorescence with time is not sufficient.

On the other hand, Japanese Patent Application No. 3-53714 discloses that a compound capable of releasing a mercapto compound as a function of the silver halide exposed to a silver halide photographic light-sensitive material, and a reaction with the released mercapto compound. It is described that a fluorescent compound precursor capable of forming a fluorescent substance is contained, and the color reproduction is improved by the fluorescent substance which is imagewise generated.

However, when a layer containing an ultraviolet absorber is provided in an attempt to enhance the fastness of the image dye in a color photographic paper or the like which is directly used for viewing, the unnecessary absorption of the image dye by the above-mentioned fluorescent substance is optically absorbed. There is a problem that the correction effect is significantly reduced, and the fastness of the image dye is deteriorated unless an ultraviolet absorber is used, which causes a dilemma.

[0008]

SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a color reproducibility by a fluorescent substance in a silver halide photographic light-sensitive material for forming a fluorescent substance imagewise. Another object of the present invention is to provide a silver halide photographic light-sensitive material capable of sufficiently exhibiting the improving effect and preventing the fastness of the image dye from being lowered.

[0009]

The object of the present invention is: (1) In a silver halide photographic light-sensitive material having a photographic constituent layer comprising a silver halide emulsion layer and a UV absorber containing layer on a support, a UV absorber containing layer and At least one layer selected from the photographic constitutional layers on the support side of the layer contains at least one compound capable of releasing a mercapto compound as a function of exposed silver halide, and contains the ultraviolet absorber. A fluorescent substance by reacting with a mercapto compound released from a compound capable of releasing the mercapto compound during color development in at least one layer selected from a layer and a photographic constitutional layer on the side farther from the support than the layer. A silver halide photographic light-sensitive material comprising at least one fluorescent compound precursor capable of forming a. (2) In a silver halide photographic light-sensitive material having a photographic constituent layer including a silver halide emulsion layer and a UV absorber-containing layer on a support, the UV absorber-containing layer and the photographic constituent layer on the support side of the layer At least one selected layer contains at least one layer of a compound capable of releasing a mercapto compound as a function of exposed silver halide, and is separated from the ultraviolet absorber-containing layer and the layer from the support. Fluorescence capable of forming a fluorescent substance by reacting with a mercapto compound released from the compound capable of releasing the mercapto compound during color development and a color developer component in at least one layer selected from the photographic constituent layers on the side. A silver halide photographic light-sensitive material containing at least one compound precursor. (3) The silver halide photographic light-sensitive material as described in (1) above, wherein the fluorescent compound precursor capable of forming a fluorescent substance is a compound represented by the general formula [I].

[0010]

[Chemical 11] [In the formula, FL represents an n-valent fluorescent compound residue having a bond in the nucleus. (4) The silver halide photographic light-sensitive material as described in (1) or (3) above, wherein the fluorescent compound precursor capable of forming a fluorescent substance is a compound represented by the general formula [I-1]. ..

[0011]

[Chemical 12][In the formula, R ₁Represents a substituent capable of substituting on the benzene ring,
m represents an integer of 0 to 5, and when m is 2 or more, a plurality of R
₁May be the same or different, and adjacent R₁
May be condensed with each other to form a ring. (5) A fluorescent compound precursor capable of forming a fluorescent substance is generally used.
A compound represented by the formula [I-2]
The silver halide photographic light-sensitive material described in (1) or (3) above.
Fee.

[0012]

[Chemical 13] [In the formula, R ₂ represents a substituent capable of substituting on the benzene ring,
m ′ represents an integer of 0 to 4, and when m ′ is 2 or more, a plurality of R ₂ may be the same or different, and adjacent R ₂ are condensed with each other to form a ring. It may be one. R ₃ represents a hydrogen atom or a substituent. (6) The silver halide photographic light-sensitive material as described in (1) above, wherein the fluorescent compound precursor capable of forming a fluorescent substance is a compound represented by the general formula [II].

[0013]

[Chemical 14] [In the formula, R ₄ , R ₅ and R ₆ represent a hydrogen atom or a substituent, and Z represents a halogen atom. However, R ₄ , R ₅ and R
₆ does not represent a hydrogen atom at the same time. (7) The silver halide photographic light-sensitive material as described in (2) above, wherein the fluorescent compound precursor capable of forming a fluorescent substance is a compound represented by the general formula [III].

[0014]

[Chemical 15] [In the formula, R ₇ , R ₈ , R ₉ and R ₁₀ represent a hydrogen atom and a substituent capable of substituting for a benzene ring, and R ₇ , R ₈ and R ₈ which are adjacent to each other.
₈ and R ₉ , and R ₉ and R ₁₀ may be condensed with each other to form a hydrocarbon ring or a heterocycle. X and Y represent O or N—R ₁₁ , and R ₁₁ represents a substituent. (8) The silver halide photographic light-sensitive material as described in (1) to (7) above, wherein the compound releasing the mercapto compound is a compound represented by the general formula [IV-1].

[0015]

[Chemical 16] [In the formula, Cp represents a coupler residue, SR ₂₁ represents a group which is released upon coupling with an oxidation product of a color developing agent during development processing, and R ₂₁ represents alkyl, aryl, heterocycle, substituted alkyl or substituted aryl. , Represents each group of the substituted heterocycle. (9) The silver halide photographic light-sensitive material as described in (1) to (7) above, wherein the compound releasing the mercapto compound is a compound represented by the general formula [IV-2].

[0016]

[Chemical 17] [In the formula, Cp represents a coupler residue, Time represents a timing group bonded at the coupling position of Cp, and R ₂₂ represents an alkyl, aryl, heterocycle, substituted alkyl, substituted aryl, or substituted heterocycle group. Represent (10) The silver halide photographic light-sensitive material as described in (1) to (7) above, wherein the compound releasing the mercapto compound is a compound represented by the general formula [IV-3].

[0017]

[Chemical 18] [In the formula, R ₂₃ represents each group of alkyl, aryl, heterocycle, substituted alkyl, substituted aryl, and substituted heterocycle;
₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , and R ₂₈ represent a hydrogen atom or a substituent, and at least two of them are —OH or —NH.
SO ₂ R ₂₉ , wherein R ₂₉ represents each group of alkyl, aryl, heterocycle, substituted alkyl, substituted aryl, and substituted heterocycle. (11) The silver halide photographic light-sensitive material as described in (1) to (7) above, wherein the compound releasing the mercapto compound is a compound represented by the general formula [IV-4].

[0018]

[Chemical 19] [In the formula, R ₃₁ represents a substituent, l represents an integer of 0 to 4, R ₃₀ represents an alkyl, aryl, heterocycle, substituted alkyl, substituted aryl, or substituted heterocycle group, and A represents hydrogen. Represents an atom or halogen. (12) The silver halide photographic light-sensitive material as described in (1) to (7) above, wherein the compound releasing the mercapto compound is a compound represented by the general formula [IV-5].

[0019]

[Chemical 20] [In the formula, R ₃₃ represents an organic group having at least one group selected from carboxy, sulfo, and hydroxy and having 16 or less carbon atoms, and R ₃₄ represents a hydrogen atom or a water-soluble acidic group,
Time represents a timing group, R ₃₂ represents an alkyl, aryl, heterocycle, substituted alkyl, substituted aryl, or substituted heterocycle group, and G represents a hydrogen atom or, upon development, is eliminated by hydrolysis or intramolecular nucleophilic substitution. Represents a possible blocking group. ] It is achieved by.

The present invention will be described in detail below.

In the present invention, a mercapto compound released from a compound capable of releasing a mercapto compound as a function of exposed silver halide (hereinafter referred to as a mercapto compound releasing compound) is a mercapto compound described above during development processing. A fluorescent compound precursor capable of forming a fluorescent substance by reacting with a mercapto compound released from the releasing compound (hereinafter referred to as fluorescent compound precursor A), or a mercapto compound released from the mercapto compound releasing compound and a color developer. It reacts with a fluorescent compound precursor capable of forming a fluorescent substance by reacting with the component (hereinafter referred to as fluorescent compound precursor B) to form a fluorescent substance having high quantum efficiency.

The reaction is shown below.

[0023]

[Chemical 21]

[0024]

[Chemical formula 22] Examples of the mercapto compound-releasing compound are represented by the general formula [IV-1], the general formula [IV-2], the general formula [IV-3], the general formula [IV-4], and the general formula [IV-5]. Compounds.

Examples of the fluorescent compound precursor A include, for example, general formula [I], general formula [I-1], and general formula [I-2].
And a compound represented by the general formula [II]. The fluorescent compound precursor B includes, for example, a compound represented by the general formula [III].

The compound represented by the general formula [I] will be described.

[0027]

[Chemical formula 23] [In the formula, FL represents an n-valent fluorescent compound residue having a bond in the nucleus. Examples of the fluorescent compound represented by FL in the general formula [I] include diaminostilbene compounds, distyrylbenzene compounds, benzidine compounds, diaminocarbazole compounds,
Triazole, imidazole, thiazole, oxazole, imidazolone, dihydropyridine, coumarin, carbostyryl, diaminodibenzothiophene dioxide, diaminofluorene, oxacyanine, aminonaphthalimide, pyrazoline, oxadi Commonly known fluorescent compounds such as azole compounds are mentioned.

The fluorescent substance formed in the present invention means
A compound that emits fluorescence in the visible region.

Next, the compound represented by the general formula [I-1] will be described.

[0030]

[Chemical formula 24][In the formula, R ₁Represents a substituent capable of substituting on the benzene ring,
m represents an integer of 0 to 5, and when m is 2 or more, a plurality of R
₁May be the same or different, and adjacent R₁
May be condensed with each other to form a ring. ]
In the above general formula [I-1], R₁As a substituent represented by
Are not particularly limited, and are typically alkyl and aryl.
Le, anilino, acylamino, sulfonamide, alk
Ruthio, arylthio, alkenyl, cycloalkyl, etc.
Each of the groups of
Ralkenyl, alkynyl, heterocycle, sulfonyl, sulphone
Finyl, phosphonyl, acyl, carbamoyl, sulf
Amoyl, cyano, alkoxy, aryloxy, complex
Ring oxy, siloxy, acyloxy, sulfonyloxy
Ci, carbamoyloxy, amino, alkylamino, a
Mid, ureido, sulfamoylamino, alkoxyca
Rubonylamino, aryloxycarbonylamino, a
Lucoxycarbonyl, aryloxycarbonyl, hetero
Ring thio, thioureido, carboxy, hydroxy, mel
Capto, nitro, sulfo, etc. groups and spiro compounds
And residue of bridged hydrocarbon compounds.

These substituents may further have a substituent.

The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group is preferably a phenyl group.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include the above-mentioned alkyl group and aryl group.

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5 carbon atoms.
The alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred.

The sulfonyl group is an alkylsulfonyl group, an arylsulfonyl group or the like; the sulfinyl group is an alkylsulfinyl group, an arylsulfinyl group or the like;
The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; The acyl group is an alkylcarbonyl group, an arylcarbonyl group, etc .; The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group. Etc .; as sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc .; as acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .; as sulfonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, etc .; Examples of the carbamoyloxy group include an alkylcarbamoyloxy group and an arylcarbamoyloxy group, and the like; examples of the ureido group include an alkylureido group and an arylureido group; a sulfamoylamino group. Was alkylsulfamoyl amino group is, and aryl sulfamoylamino group; preferably has 5 to 7 membered the heterocyclic group, specifically 2-benzimidazole group, 1-benzotriazole group, 2-
Benzotriazole group, 2-pyridyl group, 3-pyridyl group, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc .; as a heterocyclic oxy group Is preferably one having a 5- to 7-membered heterocycle, for example 3,4,5,6-
A tetrahydropyranyl-2-oxy group, a 1-phenyltetrazole-5-oxy group, etc .; a heterocyclic thio group is 5
To 7-membered heterocyclic thio groups are preferable, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group is trimethyl. Siloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; succinimide group, 3-heptadecyl succinimide group, phthalimide group, glutarimide group, etc. as imide group; spiro compound residue as spiro compound (3.3) ] Heptan-1-yl, etc .; as the bridged hydrocarbon compound residue, bicyclo [2.
2.1] heptan-1-yl, tricyclo [3.3.
1.1 ^3,7 ] Decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

Examples of the alkyl group having a substituent include a halogenated alkyl group, a hydroxyalkyl group, an aminoalkyl group (including a quaternary ammonium salt), a sulfonylalkyl group and an alkoxyalkyl group.

The above groups may further have a substituent such as a long chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

Of the substituents represented by R ₁ , preferred are aryl, alkenyl, anilino, acylamino, sulfonamide, heterocycle, sulfonyl, sulfinyl, acyl, carbamoyl, sulfamoyl, cyano,
Each group of nitro can be mentioned.

When m is 2 or more and a plurality of R _1's are adjacent to each other, the adjacent R _1's may be condensed with each other to form a ring. Preferred examples thereof are as follows.

[0044]

[Chemical 25] [In the formula, * and ** represent a position condensed with the benzene ring, and R ′ ₁ and R have the same meanings as the above R ₁ . Further, a substitutable position in these condensed rings may be substituted with a substituent represented by R ₁ . Examples of the compound represented by the general formula [I-1] are shown below, but the invention is not limited thereto.

[0045]

[Chemical formula 26]

[0046]

[Chemical 27]

[0047]

[Chemical 28]

[0048]

[Chemical 29]

[0049]

[Chemical 30]

[0050]

[Chemical 31]

[0051]

[Chemical 32] Next, a method for synthesizing the compound represented by the general formula [I-1] will be described by taking the compound I-1-7 as an example. Other compounds can also be synthesized according to this. Synthesis Example 1 (Synthesis Method of Exemplified Compound I-1-7) Synthetic Route

[0052]

[Chemical 33] Synthesis of Intermediate 3 1 21.6 g and 2 67.8 g were dissolved in 400 ml ethyl acetate,
The mixture was heated under reflux for 3 hours. The ethyl acetate solution was neutralized with a 5% aqueous sodium hydrogen carbonate solution, further washed with water and then dried over anhydrous magnesium sulfate, and ethyl acetate as a solvent was distilled off under reduced pressure. The obtained product was recrystallized from acetonitrile to obtain 69.0 g of Intermediate 3 .

( ¹ HNMR, FD mass spectrum, IR
It was confirmed to be Intermediate 3 by spectrum. ) Synthesis of I-1-7 61.6 g of Intermediate 3 was dissolved in 500 ml of pyridine, 14.7 g of maleic anhydride was further added, and the mixture was stirred at room temperature for 3 hours. Neutralize the reaction solution by adding 4N hydrochloric acid, and then add ethyl acetate 300m.
Extract with l, wash the organic phase with water and dry, then add concentrated sulfuric acid 7.2
87 g was added and the mixture was heated under reflux for 2 hours. This solution was washed with water and dried, the solvent ethyl acetate was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography to prepare Exemplified Compound I-1-7.
26.4 g was obtained. (It was confirmed to be I-1-7 by ¹ HNMR, FD mass spectrum and IR spectrum.) Next, the compound represented by the general formula [I-2] will be described.

[0054]

[Chemical 34] [In the formula, R ₂ represents a substituent capable of substituting on the benzene ring,
m ′ represents an integer of 0 to 4, and when m ′ is 2 or more, a plurality of R ₂ may be the same or different, and adjacent R ₂ are condensed with each other to form a ring. It may be one. R ₃ represents a hydrogen atom or a substituent. In the general formula [I-2], the substituent represented by R ₂ and R ₃ is not particularly limited, and is typically alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, Examples of each group such as cycloalkyl are halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, and the like. Acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thi Each group such as aureido, carboxy, hydroxy, mercapto, nitro and sulfo, as well as a spiro compound residue, a bridged hydrocarbon compound residue and the like can be mentioned.

These substituents may further have a substituent.

The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group is preferably a phenyl group.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include the above-mentioned alkyl group and aryl group.

The alkenyl group preferably has 2 to 32 carbon atoms, and the cycloalkyl group preferably has 3 to 12 carbon atoms, particularly 5 to 7 carbon atoms, and the alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred.

Examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group;
The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; The acyl group is an alkylcarbonyl group, an arylcarbonyl group, etc .; The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group. Etc .; as sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc .; as acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .; as sulfonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, etc .; Examples of the carbamoyloxy group include an alkylcarbamoyloxy group and an arylcarbamoyloxy group, and the like; examples of the ureido group include an alkylureido group and an arylureido group; a sulfamoylamino group. Was alkylsulfamoyl amino group is, and aryl sulfamoylamino group; preferably has 5 to 7 membered the heterocyclic group, specifically 2-benzimidazole group, 1-benzotriazole group, 2-
Benzotriazole group, 2-pyridyl group, 3-pyridyl group, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc .; as a heterocyclic oxy group Is preferably one having a 5- to 7-membered heterocycle, for example 3,4,5,6-
A tetrahydropyranyl-2-oxy group, a 1-phenyltetrazole-5-oxy group, etc .; a heterocyclic thio group is 5
To 7-membered heterocyclic thio groups are preferable, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group is trimethyl. Siloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; succinimide group, 3-heptadecyl succinimide group, phthalimide group, glutarimide group, etc. as imide group; spiro compound residue as spiro compound (3.3) ] Heptan-1-yl, etc .; as the bridged hydrocarbon compound residue, bicyclo [2.
2.1] heptan-1-yl, tricyclo [3.3.
1.1 ^3,7 ] Decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

Examples of the alkyl group having a substituent include a halogenated alkyl group, a hydroxyalkyl group, an aminoalkyl group (including a quaternary ammonium salt), a sulfonylalkyl group and an alkoxyalkyl group.

The above groups may further have a substituent such as a long chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

Of the substituents represented by R ₂ , preferred are amino, hydroxy, acylamino, sulfonamide, alkylamino, anilino, alkoxy, aryloxy, alkylthio, arylthio, sulfonyl,
Sulfinyl groups are mentioned, and more preferable examples are amino, alkylamino, acylamino, hydroxy, and alkoxy groups.

When m ′ is 2 or more and a plurality of R _2's are adjacent to each other, the adjacent R _2's may be condensed with each other to form a ring. Preferred examples thereof are as follows.

[0068]

[Chemical 35] [In the formula, * and ** represent a position condensed with a benzene ring, and R ′ ₂ has the same meaning as R ₂ described above. Further, the substitutable position in these condensed rings may be substituted with a substituent represented by R ₂ . Of the substituents represented by R ₃ , preferred are alkyl, aryl, alkyl halide, halogen atom, carboxyl, cyano and alkoxycarbonyl groups, and more preferred are alkyl, halogen atom and halogenated group. Each group of alkyl may be mentioned.

Examples of the compound represented by the general formula [I-2] are shown below, but the invention is not limited thereto.

[0070]

[Chemical 36]

[0071]

[Chemical 37]

[0072]

[Chemical 38] The compound represented by the general formula [I-2] is represented by Chemical and Pharmaceutical Burtin (Chem.Pharm.B).
ull.) Volume 23 (6) 1385-1386 (1975) and Chemical and Pharmaceutical Bulletin (Che.
m.Pharm.Bull.) Vol. 16, p. 1747 (1968), Biochimika et biophysica Actor (Biochim.Biophys.
Acta,) 207, p. 269 (1970).

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

[0074]

[Chemical Formula 39] [In the formula, R ₄ , R ₅ and R ₆ represent a hydrogen atom or a substituent, and Z represents a halogen atom. However, R ₄ , R ₅ and R
₆ does not represent a hydrogen atom at the same time. ] The above general formula [I
In the above [I], the substituent represented by R ₄ , R ₅ and R ₆ is not particularly limited, and typically each of alkyl, aryl, anilino, acylamino, sulfonamide, alkylthio, arylthio, alkenyl, cycloalkyl and the like. Examples thereof include a halogen atom and cycloalkenyl, alkynyl, heterocycle, sulfonyl, sulfinyl,
Phosphonyl, acyl, carbamoyl, sulfamoyl,
Cyano, alkoxy, aryloxy, heterocyclic oxy,
Siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido, sulfamoylamino, alkoxycarbonylamino, aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclethio, thioureido, carboxy, hydroxy, hydroxy, Each group such as mercapto, nitro, sulfo, etc., as well as a spiro compound residue, a bridged hydrocarbon compound residue and the like can be mentioned. These substituents are
Further, it may have a substituent.

The alkyl group preferably has 1 to 32 carbon atoms and may be linear or branched.

The aryl group is preferably a phenyl group.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include the above alkyl groups and aryl groups.

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5 carbon atoms.
The alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred.

Examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group;
The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; The acyl group is an alkylcarbonyl group, an arylcarbonyl group, etc .; The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group. Etc .; as sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc .; as acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .; as sulfonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, etc .; Examples of the carbamoyloxy group include an alkylcarbamoyloxy group and an arylcarbamoyloxy group, and the like; examples of the ureido group include an alkylureido group and an arylureido group; a sulfamoylamino group. Was alkylsulfamoyl amino group is, and aryl sulfamoylamino group; preferably has 5 to 7 membered the heterocyclic group, specifically 2-benzimidazole group, 1-benzotriazole group, 2-
Benzotriazole group, 2-pyridyl group, 3-pyridyl group, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc .; as a heterocyclic oxy group Is preferably one having a 5- to 7-membered heterocycle, for example 3,4,5,6-
A tetrahydropyranyl-2-oxy group, a 1-phenyltetrazole-5-oxy group, etc .; a heterocyclic thio group is 5
To 7-membered heterocyclic thio groups are preferable, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group is trimethyl. Siloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; succinimide group, 3-heptadecyl succinimide group, phthalimide group, glutarimide group, etc. as imide group; spiro compound residue as spiro compound (3.3) ] Heptan-1-yl, etc .; as the bridged hydrocarbon compound residue, bicyclo [2.
2.1] heptan-1-yl, tricyclo [3.3.
1.1 ^3,7 ] Decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

Examples of the alkyl group having a substituent include a halogenated alkyl group, a hydroxyalkyl group, an aminoalkyl group (including a quaternary ammonium salt), a sulfonylalkyl group and an alkoxyalkyl group.

The above groups may further have a substituent such as a long chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

In the general formula [II], preferred examples of the substituents represented by R ₄ and R ₅ include alkyl and aryl groups, and preferred examples of the substituents represented by R ₆ are: , Alkyl, and substituted aryl groups.

In the general formula [II], the halogen atom represented by Z includes fluorine, chlorine, bromine and iodine, with chlorine and bromine being preferred.

Examples of the compound represented by the general formula [II] used in the present invention are shown below, but the invention is not limited thereto.

[0088]

[Chemical 40]

[0089]

[Chemical 41] Compounds represented by these general formulas [II] are Anal.Biochem.
It can be easily synthesized by referring to Vol. 107, page 1 (1980) and Vol. 111, page 357 (1981).

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

[0091]

[Chemical 42] [In the formula, R ₇ , R ₈ , R ₉ and R ₁₀ represent a hydrogen atom and a substituent capable of substituting for a benzene ring, and R ₇ , R ₈ and R ₈ which are adjacent to each other.
₈ and R ₉ , and R ₉ and R ₁₀ may be condensed with each other to form a hydrocarbon ring or a heterocycle. X and Y represent O or N—R ₁₁ , and R ₁₁ represents a substituent. In the general formula [I], the substituents represented by R ₇ , R ₈ , R ₉ and R ₁₀ are not particularly limited, and typically include alkyl, aryl, anilino,
Examples include groups such as acylamino, sulfonamide, alkylthio, arylthio, alkenyl, and cycloalkyl. In addition to these, a halogen atom and cycloalkenyl,
Alkynyl, heterocycle, sulfonyl, sulfinyl, phosphonyl, acyl, carbamoyl, sulfamoyl, cyano, alkoxy, aryloxy, heterocycleoxy, siloxy, acyloxy, sulfonyloxy, carbamoyloxy, amino, alkylamino, imide, ureido,
Sulfamoylamino, alkoxycarbonylamino,
Aryloxycarbonylamino, alkoxycarbonyl, aryloxycarbonyl, heterocyclic thio, thioureido, carboxy, hydroxy, mercapto, nitro,
Each group such as sulfo, etc., as well as a spiro compound residue, a bridged hydrocarbon compound residue and the like can be mentioned.

These substituents may further have a substituent.

The above alkyl group has 1 to 32 carbon atoms.
Those which are straight chain or branched may be preferable.

The aryl group is preferably a phenyl group.

Examples of the acylamino group include an alkylcarbonylamino group and an arylcarbonylamino group.

Examples of the sulfonamide group include an alkylsulfonylamino group and an arylsulfonylamino group.

Examples of the alkyl component and the aryl component in the alkylthio group and the arylthio group include the above alkyl groups and aryl groups.

The alkenyl group has 2 to 32 carbon atoms, and the cycloalkyl group has 3 to 12 carbon atoms, especially 5
The alkenyl group may be linear or branched.

The cycloalkenyl group has 3 to 10 carbon atoms.
12, especially 5 to 7, are preferred.

Examples of the sulfonyl group include an alkylsulfonyl group and an arylsulfonyl group; examples of the sulfinyl group include an alkylsulfinyl group and an arylsulfinyl group;
The phosphonyl group is an alkylphosphonyl group, an alkoxyphosphonyl group, an aryloxyphosphonyl group, an arylphosphonyl group, etc .; The acyl group is an alkylcarbonyl group, an arylcarbonyl group, etc .; The carbamoyl group is an alkylcarbamoyl group, an arylcarbamoyl group. Etc .; as sulfamoyl group, alkylsulfamoyl group, arylsulfamoyl group, etc .; as acyloxy group, alkylcarbonyloxy group, arylcarbonyloxy group, etc .; as sulfonyloxy group, alkylsulfonyloxy group, arylsulfonyloxy group, etc .; Examples of the carbamoyloxy group include an alkylcarbamoyloxy group and an arylcarbamoyloxy group, and the like; examples of the ureido group include an alkylureido group and an arylureido group; a sulfamoylamino group. Was alkylsulfamoyl amino group is, and aryl sulfamoylamino group; preferably has 5 to 7 membered the heterocyclic group, specifically 2-benzimidazole group, 1-benzotriazole group, 2-
Benzotriazole group, 2-pyridyl group, 3-pyridyl group, 2-furyl group, 2-thienyl group, 2-pyrimidinyl group, 2-benzothiazolyl group, 1-pyrrolyl group, 1-tetrazolyl group, etc .; as a heterocyclic oxy group Is preferably one having a 5- to 7-membered heterocycle, for example 3,4,5,6-
A tetrahydropyranyl-2-oxy group, a 1-phenyltetrazole-5-oxy group, etc .; a heterocyclic thio group is 5
To 7-membered heterocyclic thio groups are preferable, for example, 2-pyridylthio group, 2-benzothiazolylthio group, 2,4-diphenoxy-1,3,5-triazole-6-thio group, etc .; siloxy group is trimethyl. Siloxy group, triethylsiloxy group, dimethylbutylsiloxy group and the like; imide group as succinimide group, 3-heptadecyl succinimide group, phthalimido group, glutarimide group, etc .; spiro compound residue as spiro [3.3 ] Heptan-1-yl, etc .; as the bridged hydrocarbon compound residue, bicyclo [2.
2.1] heptan-1-yl, tricyclo [3.3.
1.1 ^3,7 ] Decan-1-yl, 7,7-dimethyl-bicyclo [2.2.1] heptan-1-yl and the like can be mentioned.

Examples of the alkyl group having a substituent include a halogenated alkyl group, a hydroxyalkyl group, an aminoalkyl group (including a quaternary ammonium salt), a sulfonylalkyl group, an alkoxyalkyl group and the like.

The above groups may further have a substituent such as a long chain hydrocarbon group or a diffusion resistant group such as a polymer residue.

In the general formula [III], the substituent represented by R ₁₁ has the same meaning as R ₇ , R ₈ , R ₉ and R ₁₀ described above.

Adjacent R ₇ and R ₈ , R ₈ and R ₉ , R ₉ and R ₁₀
Preferred examples in the case where the above groups are condensed with each other to form a ring are as follows.

[0105]

[Chemical 43] Wherein * and ** indicates the position at which the condensed with a benzene ring, R _'7 has the same meaning as R ₇ above. Further, the substitutable position in these condensed rings may be substituted with a substituent represented by R ₇ . Examples of the compound represented by the general formula [III] used in the present invention are shown below, but the invention is not limited thereto.

[0106]

[Chemical 44]

[0107]

[Chemical 45] Next, a method for synthesizing the compound represented by the general formula [III] will be described by taking Exemplified Compound III-3 as an example. Other compounds can also be synthesized according to this. Synthesis Example 2 (Synthesis Method of Exemplified Compound III-3) 500 ml of chloroform and 120.3 g of dodecanoyl chloride were added to 67.1 g of o-phthalaldehyde, and 73.3 g of aluminum chloride was gradually added under ice cooling for about 1 hour. After the reaction was carried out at 5 ° C. for 4 hours, 500 ml of water was added to wash the chloroform phase. After the solvent chloroform was distilled off under reduced pressure, the residue was purified by column chromatography to obtain 62.0 g of white crystals III-3. ( ¹ HNMR, FD mass spectrum, IR spectrum confirmed that the compound was Exemplified Compound III-3.)
The fluorescent compound precursor A or the fluorescent compound precursor B is preferably 1 × 10 ⁻⁵ to 1 m ^{2 of the} silver halide photographic light-sensitive material.
1 × 10 ⁻² mol, more preferably 5 × 10 ⁻⁵ mol to 5
X10 ^-3 mol is contained.

Next, the compound represented by the general formula [IV-1] will be described.

[0109]

[Chemical 46] [In the formula, Cp represents a coupler residue, SR ₂₁ represents a group which is released upon coupling with an oxidation product of a color developing agent during development processing, and R ₂₁ represents alkyl, aryl, heterocycle, substituted alkyl or substituted aryl. , Represents each group of the substituted heterocycle. In the general formula [IV-1], as the coupler residue represented by Cp, generally known yellow couplers, magenta couplers and cyan couplers can be used. [Cp-1]
To [Cp-9].

[0110]

[Chemical 47] Wherein, - △ represents the position which binds to SR _21. ] In addition,
The coupler mother nucleus shown here may have a substituent, and examples of the substituent include those shown by R ₁ in the above general formula [I-1]. Preferred is when at least one substituent is a diffusion resistant group.

Examples of the substituent represented by R ₂₁ include those represented by R ₁ of the general formula [I-1], preferably a hydroxyl group, a carboxyl group, an amino group, a ureido group, an acylamino group, Carbamoyl group, alkoxycarbonyl group, aryloxycarbonyl group, acyloxy group, aryloxy group, urethane group, alkoxy group, mercapto group, alkylthio group, arylthio group,
An alkyl group and an aryl group substituted with a halogen atom or the like.

The general formula [IV-
Examples of the compound represented by 1] are shown below, but the invention is not limited thereto.

[0113]

[Chemical 48]

[0114]

[Chemical 49]

[0115]

[Chemical 50]

[0116]

[Chemical 51]

[0117]

[Chemical 52]

[0118]

[Chemical 53]

[0119]

[Chemical 54] Next, a method for synthesizing the compound represented by the general formula [IV-1] will be described by taking the exemplified compounds IV-1-4 and IV-1-8 as examples. Other compounds can also be synthesized according to this. Synthesis Example 3 (Synthesis Method of Exemplified Compound IV-1-4) Synthesis Route

[0120]

[Chemical 55] 71.5 g of intermediate (B) was added to dimethylformamide (DMF)
After dissolving in 400 ml at room temperature, bromine 51.1 g under nitrogen atmosphere
Was dripped. After the completion of dropping, the mixture was stirred for 5 minutes, 118.2 g of the intermediate (A) was added, and the mixture was further reacted at room temperature for 6 hours. Water (600 ml) and ethyl acetate (800 ml) were added to the reaction solution to extract organic substances, and ethyl acetate was distilled off under reduced pressure to obtain 186 g of a yellow solid. The solid was recrystallized from 300 ml of acetonitrile to obtain 141 g of white crystals.

( ¹ H NMR, IR, FD mass spectrum confirmed that Exemplified Compound IV-1-4.) Synthesis Example 4 (Synthesis Method of Exemplified Compound IV-1-8) Synthetic Route

[0122]

[Chemical 56] To 25.4 g of the intermediate (C), 300 ml of ethanol (EtOH) was added and dissolved under a nitrogen gas stream. 7.6g in this solution
Anhydrous potassium carbonate and 7.0 g of bromoacetic acid were added,
The solution was heated and stirred at a solution temperature of 65 to 70 ° C. for 4 hours.

After distilling off the solvent ethanol under reduced pressure, 200 ml of water was added.
And 400 ml of ethyl acetate were added, and the product was extracted by further neutralizing with 5N hydrochloric acid. The organic phase was washed with water and dried over anhydrous sodium sulfate, and then the solvent ethyl acetate was distilled off under reduced pressure. The obtained solid was recrystallized from ethanol to obtain 20.8 g of Exemplified compound IV-8. ( ¹ H NMR, FD mass spectrum, IR spectrum confirmed that the compound was Exemplified Compound IV-1-8.)
Next, the compound represented by the general formula [IV-2] will be described.

[0124]

[Chemical 57] [In the formula, Cp represents a coupler residue, Time represents a timing group bonded at the coupling position of Cp, and R ₂₂ represents an alkyl, aryl, heterocycle, substituted alkyl, substituted aryl, or substituted heterocycle group. Represent ] General formula [IV-
In 2], Cp has the same meaning as Cp in formula [IV-1], and R ₂₂ has the same meaning as R ₂₁ in formula [IV-1].

Examples of the group represented by Time include (1) a group which causes a cleavage reaction by utilizing an electron transfer reaction along a conjugated system, and (2) a cleavage reaction which utilizes an intramolecular nucleophilic substitution reaction. And (3) a group that utilizes a hemiacetal cleavage reaction, (4) a group that uses an iminoketal cleavage reaction, and (5) a group that uses a hydrolytic cleavage reaction of an ester.

Regarding the group (1), for example, JP-A-56-1 is used.
14946, 57-154234, 57-188035, and
58-98728, 58-160954, 58-209736, 58-209
737, 58-209738, 58-209739, 58-209740
Nos. 62-86361 and 62-87958, the group (2) is described in, for example, JP-A-57-56837 and U.S. Pat. No. 4,248,96.
Regarding the group (3) in JP-A-2, for example, JP-A-60-249148
No. 60-249149, US Pat. No. 4,146,396, and the group (4) is described in, for example, US Pat. No. 4,546,073, (5)
Regarding the group of, for example, in West German Published Patent No. 2,626,315,
It is described in detail.

Further, Time may be such that after the bond between Cp and Time is cleaved, the bond between Time and -SR ₂₂ is further cleaved by the reaction with the oxidized product of the developing agent. Examples thereof include a coupler component which undergoes a coupling reaction with an oxidized product of a developing agent and a redox component which undergoes a redox reaction with an oxidized product of a developing agent.

When Time is a coupler component, examples thereof include each coupler residue listed for Cp.

When Time is a redox component, examples thereof include hydroquinones, catechols, pyrogallols and aminophenols (eg p-
Aminophenols, o-aminophenols), naphthalenediols (for example, 1,2-naphthalenediols, 1,4-naphthalenediols, 2,6-naphthalenediols), or aminonaphthols (for example, 1,
2-aminonaphthols, 1,4-aminonaphthols, 2,6-aminonaphthols) and the like.

Of the groups represented by Time, those represented by the following structural formulas are preferred. In the structural formula, * 1 is Cp,
* 2 indicates a site that binds to SR ₂₂ .

[0131]

[Chemical 58] R ¹ represents a substituent, R ² and R ³ represent a hydrogen atom or a substituent, l ′ represents 0, 1 or 2, and when R ′ is 2, each R
^1's may be the same or different from each other, and R ^1's may form a condensed ring. p represents 0, 1 or 2.

Examples of the substituent represented by R ¹ include halogen atom, alkyl group, alkenyl group, alkoxy group, alkoxycarbonyl group, anilino group, acylamino group, ureido group, cyano group, nitro group, sulfonamide group, Examples thereof include a sulfamoyl group, a carbamoyl group, an aryl group, a carboxyl group, a sulfo group, a cycloalkyl group, an alkanesulfonyl group, an arylsulfonyl group and an acyl group, and these further include those having a substituent.

As the substituents represented by R ² and R ³ ,
Examples thereof include an alkyl group, an alkenyl group, a cycloalkyl group and an aryl group, and these include those having a substituent.

The general formula [IV-
Examples of the compound represented by 2] are shown below, but the invention is not limited thereto.

[0135]

[Chemical 59]

[0136]

[Chemical 60]

[0137]

[Chemical formula 61]

[0138]

[Chemical formula 62]

[0139]

[Chemical 63]

[0140]

[Chemical 64] These compounds are disclosed in JP-A-54-145135 and JP-A-56-114946.
No. 56-137353, No. 57-154234 and the like. Synthesis Example 5 (Synthesis of Exemplified Compound IV-2-15) <Synthesis Route>

[0141]

[Chemical 65] (Synthesis of Intermediate 2) 5.0 g of Intermediate 1 and 16.5 g of benzenethiol sodium salt were added to dimethylformamide (DM
It was dissolved in F) and stirred at room temperature for 1 hour. The reaction solution was poured into dilute hydrochloric acid, and the precipitated solid was collected by filtration. This solid was dissolved in ethyl acetate, washed with aqueous potassium carbonate solution, and the ethyl acetate phase was concentrated. 20 ml of the obtained oily substance is ethanol.
The resulting product was dissolved in, and 1 ml of hydrochloric acid was added, and the mixture was cooled to obtain 25.0 g of a white crystalline intermediate 2. (The structure was confirmed by ¹ HNMR, IR, and FD mass spectra.) (Synthesis of Exemplified Compound IV-2-15) 5.0 g of Intermediate 2 and 3.0 g of Intermediate 3 were dissolved in 30 ml of dioxane, and 2.5 g of dicyclohexylcarbodiimide was added. The reaction was carried out at room temperature for 8 hours. The precipitated crystals were separated by filtration, the filtrate was concentrated, and the obtained oily substance was recrystallized with a mixed solvent of benzene-hexane to obtain 3.7 g of Exemplified compound IV-2-15. (The structure was confirmed by ¹ HNMR, IR, and FD mass spectra.) Next, the compound represented by the general formula [IV-3] will be described.

[0142]

[Chemical 66] [In the formula, R ₂₃ represents each group of alkyl, aryl, heterocycle, substituted alkyl, substituted aryl, and substituted heterocycle;
₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , and R ₂₈ represent a hydrogen atom or a substituent, and at least two of them are —OH or —NH.
SO ₂ R ₂₉ , wherein R ₂₉ represents each group of alkyl, aryl, heterocycle, substituted aralkyl, substituted aryl, and substituted heterocycle. In the general formula [IV-3], R ₂₃ has the same meaning as R _{21 in the} general formula [VI-1], and R ₂₄ , R ₂₅ , R ₂₆ , R
_The substituents represented by ₂₇ and R _{28 have} the same meanings as those represented by R _{1 in} the general formula [I-1].

[0143]

[Chemical 67] The compound represented by Chemical formula 67 is generally called a redox compound, and is a cross-oxidation type DIR compound (for example, US Pat. No. 3,379,529, JP-A-48-56129, and JP-A-49-1295).
No. 36, No. 52-57828, No. 56-153336, No. 60-233648,
No. 61-156043, No. 61-213847, No. 63-24239, Research Disclosure Nos. 10,038, 18,104, etc.) from which the development inhibiting group is removed. The compound represented by the general formula [IV-3] of the present invention also includes a compound having a group derived from the compound represented by the above Chemical Formula 67.

The general formula [IV-
Examples of the compound represented by 3] are shown below, but the invention is not limited thereto.

[0145]

[Chemical 68]

[0146]

[Chemical 69] These compounds are disclosed in U.S. Pat.
No. 9536, No. 52-57828, No. 56-153336, No. 60-233648
No. 61-156043, No. 61-213847, No. 63-24239, Research Disclosure No. 10,038, No. 18,104
It can be easily synthesized according to the method described in No.

Next, the compound represented by the general formula [IV-4] will be described.

[0148]

[Chemical 70] [In the formula, R ₃₁ represents a substituent, l represents an integer of 0 to 4, R ₃₀ represents an alkyl, aryl, heterocycle, substituted aralkyl, substituted aryl, or substituted heterocycle group, and A represents hydrogen. Represents an atom and halogen. In the general formula [IV-4], R ₃₀ has the same meaning as R _{21 in the} general formula [IV-1], and R ₃₁
The substituent represented by is the same as that represented by R _{1 in} formula [I-1].

[0149]

[Chemical 71] The compound represented by Chemical formula 71 is a DIR compound which forms a colorless compound when reacted with an oxidized product of a color developing agent (for example, US Pat. No. 3,958,993, JP-A-51-64927, JP-A-53-135333,
Nos. 53-143223 and 54-73033) except for the development inhibiting group. The compound represented by the general formula [IV-4] of the present invention also includes a compound having a group derived from the compound represented by the above chemical formula 71.

The general formula [IV-
Examples of the compound represented by 4] are shown below, but the invention is not limited thereto.

[0151]

[Chemical 72]

[0152]

[Chemical formula 73] These compounds are disclosed in U.S. Pat. No. 3,958,993 and JP-A-51-64.
It can be easily synthesized according to the method described in Nos. 927, 53-135333, and 53-143223.

Next, the compound represented by the general formula [IV-5] will be described.

[0154]

[Chemical 74] [In the formula, R ₃₃ represents an organic group having at least one group selected from carboxy, sulfo, and hydroxy and having 16 or less carbon atoms, and R ₃₄ represents a hydrogen atom or a water-soluble acidic group,
Time represents a timing group, R ₃₂ represents an alkyl, aryl, heterocycle, substituted alkyl, substituted aryl, or substituted heterocycle group, and G represents a hydrogen atom or, upon development, is eliminated by hydrolysis or intramolecular nucleophilic substitution. Represents a possible blocking group. ] In the general formula [IV-5], as the organic group having 16 or less carbon atoms, which has at least one group selected from carboxy, sulfo and hydroxy represented by R ₃₃ ,
A carbamoyl group having at least one carboxy, sulfo, and hydroxy group and having 16 or less carbon atoms (eg, an alkylcarbamoyl group, an arylcarbamoyl group, a heterocyclic carbamoyl group), a sulfamoyl group, (eg, an alkylsulfamoyl group, an arylsulfamoyl group). Moyl group, heterocyclic sulfamoyl group, etc.), acyl group (eg, alkylcarbonyl group, arylcarbonyl group, arylsulfonyl group, etc.), aryl group, or heterocyclic group.

Examples of the water-soluble acidic group represented by R ₃₄ include carboxy, sulfo, carboxyalkyl, sulfoalkyl, carboxyalkylamino and sulfoalkylamino groups.

The blocking group represented by G is, for example, a group which can be released by hydrolysis, for example, the aliphatic carbonyls described in US Pat. Nos. 2,575,182, 2,706,685, 2,865,748 and 4,123,281. A group, an aromatic carbonyl group, an aliphatic sulfonyl group, an aromatic sulfonyl group, and the like, which can be removed by intramolecular nucleophilic substitution, such as those described in JP-A-55-53330.

Such a group can be represented by the following general formula.

-E ¹ -X ¹ -Nu ¹ P In the formula, E ¹ represents an electrophilic group, Nu ¹ P represents a nucleophilic group precursor which is converted to a nucleophilic group under alkaline conditions, and X 1
¹ is an E intramolecular nucleophilic substitution reaction that cleaves the bond between E ¹ and the oxygen atom of the 1-naphthol coupler to which it is bonded after Nu ¹ P is converted to a nucleophilic group. ¹
Represents a bonding group that sterically relates Nu ¹ P to Nu.

Time is Ti in the general formula [IV-2].
has the same meaning as me, and R ₃₂ is R in the general formula [IV-1].
Synonymous with ₂₁ .

Among the compounds represented by the general formula [IV-5], particularly preferable compounds for achieving the object of the present invention include the compounds represented by the following general formula [IV-5 ']. ..

[0161]

[Chemical 75] In the formula, G and Time are G and Ti of the general formula [IV-5].
Synonymous with me. R ₃₅ represents hydrogen or an alkyl group having 4 or less carbon atoms (for example, methyl, ethyl, butyl, etc.), and R ₃₆ represents 12 or less carbon atoms, more preferably 8 or less carboxyalkyl group, sulfoalkyl group or hydroxyalkyl group. (As these, for example, carboxymethyl, sulfomethyl, carboxyethyl, sulfoethyl, hydroxyethyl, sulfo-2-methylpropyl,
Examples thereof include sulfo-2,2-dimethylpropyl, sulfobutyl, carboxybutyl, sulfo-4-ethylbutyl, sulfopentyl and 4-carboxymethoxybenzyl. ), And at least one or more of carboxy, sulfo, or hydroxy directly or having 1 to 4 carbon atoms.
Alkylene group (e.g. -CO -, - CONH -, - SO 2 NH
-, - NHCO -, - NHSO 2 -, or may methylene be via -O-, ethylene, phenyl group having through-butylene, etc.), or a phenylene group, a naphthyl group or a 5- or 6-membered heterocyclic group, (For example, a furyl group, a pyridyl group, a thiazolyl group, etc.) is represented. This phenyl group,
The naphthyl group, or the 5- or 6-membered heterocyclic group is further a halogen atom (eg chlorine, bromine, iodine, etc.), nitro, cyano, an alkyl group having 1 to 4 carbon atoms (eg methyl, ethyl, propyl, inpropyl, Butyl),
It may be substituted with an alkoxy group having 1 to 4 carbon atoms (eg, methoxy, ethoxy, butoxy, etc.), an alkylamino group having 1 to 4 carbon atoms (eg, methylamino, dimethylamino, ethylamino, etc.).

R ₃₅ and R ₃₆ are carboxy, sulfo,
Alternatively, a nitrogen-containing 5- or 6-membered ring having hydroxy may be formed.

As is clear from the above description, the compound represented by the general formula [IV-5] enhances the reactivity with the oxidant of the color developing agent and, at the same time, the reaction product thereof (that is, the cyan dye). ) Is made alkali-soluble, and the flowability from the photographic element is imparted.

[0164]

[Chemical 76] In the compound represented by Chemical formula 76, a development-inhibiting group of a bleaching outflow type DIR coupler (for example, JP-A-58-162949) is used.
It also includes the one changed to e-SR ₃₂ .

The general formula [IV-
Examples of the compound represented by 5] are shown below, but the invention is not limited thereto.

[0166]

[Chemical 77]

[0167]

[Chemical 78]

[0168]

[Chemical 79]

[0169]

[Chemical 80] These compounds can be easily synthesized according to the method described in JP-A-58-162949. Synthesis Method 6 (Exemplified Compound IV-5-4) <Synthesis Route>

[0170]

[Chemical 81] Intermediate 1 20.0 g and p-toluenethiol sodium salt
After dissolving 4.0 g in 100 ml of DMF and refluxing for 1 hour, the reaction solution was poured into 500 ml of ice water. The obtained solid was collected by filtration, washed with water and then dried. This was recrystallized using a mixed solvent of ethyl acetate-hexane to obtain 21.1 g of Exemplified compound IV-5-4. (The structure was confirmed by ¹ HNMR, IR, and FD mass spectra.) The mercapto compound releasing compound is preferably 1 × 10 ⁻⁵ to 1 × per 1 m ^{2 of} silver halide photographic light-sensitive material.
10 ⁻² mol, more preferably 5 × 10 ^{−5 to} 5 × 10 ⁻³
Molar content.

Examples of the color developing solution component that reacts with the fluorescent compound precursor B include aromatic primary amine color developing agents contained in commonly used color developing solutions. As the color developing agent preferably used in the present invention, the compounds (I-
1) to (I-16) and the like.

Next, the ultraviolet absorbent contained in the ultraviolet absorbent-containing layer of the present invention will be described. The ultraviolet absorber in the present invention is 300 nm to 400 nm in ethyl acetate.
Has the maximum value of the spectral absorption spectrum in the wavelength region of, and the molar absorption coefficient εmax at the maximum absorption wavelength is 1.0 ×
It is preferable that the compound is 10 ⁴ or more and has substantially no absorption in the visible region (400 to 700 nm). Furthermore, the maximum value of the molar extinction coefficient at 400 to 700 nm is 1.
It is preferably 0 × 10 ³ or less. Further, the ultraviolet absorbent of the present invention is preferably a lipophilic compound having a diffusion resistant group.

The UV absorber of the present invention is preferably a benzotriazole UV absorber or a benzophenone UV absorber, more preferably a compound represented by the following general formula [UV-I].

[0174]

[Chemical formula 82] [In the formula, R ₅₁ and R ₅₂ represent a substituent capable of substituting on the benzene ring, and a and b represent an integer of 0 to 4. When a or b is 2 or more, plural R ₅₁ or R ₅₂ may be the same or different. ] The above general formula [UV-I]
In the above, examples of the substituent represented by R ₅₁ or R ₅₂ include the groups exemplified as the substituent represented by R _{1 in} the general formula [II].

The substituent represented by R ₅₁ or R ₅₂ is preferably a halogen atom, a nitro group, a hydroxy group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an acylamino group or an alkenyl group, and more preferably,
It is a halogen atom, an alkyl group, or an alkoxy group. The substituent represented by R ₅₁ or R ₅₂ may further have a substituent.

The examples of the ultraviolet absorber used in the present invention are shown below, but the invention is not limited thereto.

[0177]

[Chemical 83] Further, in addition to the above compounds, the exemplified compounds UV-1 to UV- described in JP-A-63-264748, page 4 to page 5
29, JP-A No. 63-143540, exemplary compounds UV-1L to UV-23L described on page 4, JP-A No. 1-156748.
Exemplified compounds IIc-1 to IIc-17 described on page 39, and exemplified compounds UV-1 to UV-20 described on pages 125 to 127 of JP-A No. 62-215272 can be mentioned. , In addition, Research Disclosure 17643, Section VIIIc.
Mention may be made of the compounds listed in the section.

In the present invention, the ultraviolet absorber is preferably 0.01 to 10 g per 1 m ^{2 of} silver halide photographic light-sensitive material,
More preferably, 0.1 g to 5 g is added.

The mercapto compound-releasing compound, the fluorescent compound precursor A, the fluorescent compound precursor B and the ultraviolet absorber of the present invention are usually used in a high boiling point organic solvent having a boiling point of about 150 ° C. or higher or a water-insoluble polymer compound. Accordingly, a low boiling point and / or a water-soluble organic solvent is used in combination to dissolve it, and a surfactant is used in a hydrophilic binder such as an aqueous gelatin solution, which may be used in a stirrer, a homogenizer, a colloid mill, a flow jet mixer, an ultrasonic device, etc. After emulsifying and dispersing using a dispersing means,
It may be added to the desired hydrophilic colloid layer.

The fluorescent compound precursor A or the fluorescent compound precursor B of the present invention is contained in at least one ultraviolet absorber-containing layer or in the photographic constituent layer on the side farther from the support. In the photographic constituent layer on the side farther from the support than the photographic constituent layer containing the fluorescent compound precursor A or the fluorescent compound precursor B,
It is preferable that no ultraviolet absorber is contained. The mercapto compound-releasing compound of the present invention is contained in the ultraviolet absorber-containing layer having the above-mentioned positional relationship with the photographic constituent layer containing the fluorescent compound precursor A or the fluorescent compound precursor B, or in the photographic constituent layer on the support side thereof. It is necessary to be contained in.

When a plurality of ultraviolet absorbent layers are present,
Preferably, the fluorescent compound precursor A or the fluorescent compound precursor B is contained in the ultraviolet absorber layer located farthest from the support, or in the photographic constituent layer on the side farther from the support, The mercapto compound-releasing compound is contained in the ultraviolet absorber layer located farthest from the support or in the photographic constituent layer on the support side of the UV absorber layer.

As the silver halide used in the silver halide emulsion layer of the present invention, any halogen such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide and silver chloroiodide can be used. There is silver oxide. The silver halide grains preferably used in the present invention have a silver chloride content of 90 mol% or more, a silver bromide content of 10 mol% or less, and a silver iodide content of 0.5 mol%.
The following is preferable. More preferably, it is a silver chlorobromide having a silver bromide content of 0.1 to 2 mol%. The silver halide grains may be used alone or in combination with other silver halide grains having different compositions. Further, it may be used as a mixture with silver halide grains having a silver chloride content of 90% or less. Further, in a silver halide emulsion agent layer containing silver halide grains having a silver chloride content of 90 mol% or more, the silver chloride content in the total silver halide grains contained in the emulsion layer is 90 mol%. % Of silver halide grains above
It is at least 60% by weight, preferably at least 80% by weight. The composition of the silver halide grain may be uniform from the inside to the outside of the grain, or the composition inside and outside the grain may be different. When the composition inside and outside the particle is different, the composition may be continuously changed or may be discontinuous.

The grain size of the silver halide grain is not particularly limited, but considering other photographic performance such as rapid processing property and sensitivity, it is preferably 0.2 to 1.6 μm, more preferably 0.25 to 1.2.
It is in the range of μm. The particle size can be measured by various methods generally used in the art. A typical method is Lapland's “Particle size analysis method” (ASMTM Symposium on Right Microscopy, 1955, pp. 94-122).
Alternatively, it is described in "Theory of Photographic Process" (Mith and James, 3rd edition, Chapter 2 published by Macmillan, Inc. (1966)). This particle diameter can be obtained by using the projected area of the particle or an approximate diameter value. If the particles are substantially uniform in shape, the particle distribution can be fairly accurately represented using diameter or projected area. The particle size distribution of silver halide grains may be polydisperse or monodisperse. In the grain distribution of silver halide grains, the coefficient of variation is preferably 0.22 or less, more preferably 0.
It is a monodisperse silver halide grain of 15 or less. Here, the coefficient of variation and the coefficient indicating the breadth of the particle size distribution are defined by the following mathematical expression 1.

[0184]

[Equation 1] Here, ri represents the particle size of each particle, and ni represents the number. The particle size refers to the diameter of spherical silver halide grains, or the diameter of a cubic image or a grain of a shape other than spherical when the projected image is converted into a circular image of the same area.

The silver halide grains used in the present invention may be those obtained by any of the acidic method, the neutral method and the ammonia method. The particles may be grown at one time, or may be grown after forming seed particles. The method of making seed particles and the method of growing seed particles may be the same or different.
The method of reacting the soluble silver salt and the soluble halogenated salt may be any of a forward mixing method, a back mixing method, a simultaneous mixing method and a combination thereof, but a method obtained by the simultaneous mixing method is preferable. Furthermore, as one type of simultaneous mixing method, Japanese Patent Laid-Open No.
It is also possible to use the pAg-controlled double jet method described in US Pat.

If necessary, a silver halide solvent such as thioether may be used. Further, a compound such as a mercapto group-containing compound, a nitrogen-containing heterocyclic compound or a sensitizing dye may be added during the formation of silver halide grains or after the completion of grain formation.

The silver halide grains used in the present invention may have any shape. One preferable example is a cube having a {100} plane as a crystal surface. Also, U.S. Patents 4,183,756 and 4,225,666, JP
55-26589, Japanese Patent Publication No. 55-42737, etc., The Journal
Of Photographic Science (J.Photgr.Sc
i.), 21 , 39 (1973), and the like, particles having an octahedron, a tetradecahedral shape, a dodecahedron shape, and the like can be prepared and used. Further, grains having twin planes may be used. The silver halide grain used in the present invention may be a grain having a single shape or a mixture of grains having various shapes.

The silver halide grains used in the present invention are:
In the process of forming and / or growing silver halide grains, a metal ion is used by using a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or a complex salt thereof. Can be added to the inside of the grain and / or included in the surface of the grain, and reduction sensitized nuclei can be imparted to the inside of the grain and / or the surface of the grain by placing it in a suitable reducing atmosphere.

In the emulsion containing silver halide grains, unnecessary soluble salts may be removed after the completion of growth of silver halide grains, or may be kept contained. When removing the salts, research disclosure
It can be performed based on the method described in 17643.

In the present invention, the silver halide grain used in the emulsion may be a grain in which a latent image is mainly formed on the surface, or may be a grain mainly formed inside the grain. Grains whose latent image is mainly formed on the surface are preferable.

In the present invention, the emulsion is chemically sensitized by a conventional method. That is, a sulfur-containing compound capable of reacting with silver ions, a sulfur sensitization method using active gelatin, a selenium sensitization method using a selenium compound, a reduction sensitization method using a reducing substance, a noble metal sensitization method using gold or another noble metal compound. Sensing methods and the like can be used alone or in combination.

The emulsion can be optically sensitized to a desired wavelength region by using a sensitizing dye. As the sensitizing dye, a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye, and a hemioxanol dye can be used.

The dye-forming coupler used in the silver halide photographic light-sensitive material of the present invention is usually selected so that a dye which absorbs light in the light-sensitive spectrum of the emulsion layer is formed for each emulsion layer. A yellow coupler is used for the blue-sensitive emulsion layer, a magenta coupler is used for the green-sensitive emulsion layer, and a cyan coupler is used for the red-sensitive emulsion layer. However, the silver halide color photographic light-sensitive material may be prepared by a method different from the above combination depending on the purpose.

In the present invention, an acylacetanilide type coupler can be preferably used as the yellow dye-forming coupler. Among these, benzoylacetanilide compounds and pivaloylacetanilide compounds are advantageous.

Specific examples of the yellow couplers preferably used in the present invention will be given below, but the present invention is not limited thereto.

[0196]

[Chemical 84]

[0197]

[Chemical 85]

[0198]

[Chemical formula 86] Furthermore, in addition to the above compounds, JP-A-63-85631, No. 7
Exemplified compounds Y-1 to Y-146 described on pages 6 to 16, Exemplified compounds Y-1 to Y-98 described on pages 6 to 10 of JP-A-63-97951, Exemplified compounds Y-1 to Y-24 described in JP-A No. 156748, pages 18 to 20, JP-A-2-2989.
Exemplified Compounds I-1 to 1 described in JP-A-43-43, pages 4 to 7
I-50 and the exemplified compounds Y-1 to Y-48 described on pages 114 to 120 of JP-A-62-215272 can be mentioned.

In the present invention, as the magenta dye forming coupler, known couplers such as 5-pyrazolone type couplers, pyrazoloazole type couplers and pyrazolobenzimidazole type couplers can be used.

Specific examples of the magenta coupler preferably used in the present invention will be given below, but the present invention is not limited thereto.

[0201]

[Chemical 87]

[0202]

[Chemical 88]

[0203]

[Chemical 89] Further, in addition to the above compounds, JP-A-62-166339, No. 1
Exemplified compounds 1-223 described on pages 8 to 32, JP-A 2-10
Exemplified compound M-1 described on pages 5 to 6 of the publication
-M-29, exemplary compounds M-1 to M-30 described in JP-A-3-214155, pages 9 to 12, and JP-A-62-215272, pages 104 to 114. Exemplified compounds M-1 to M
-47 etc. can be mentioned.

In the present invention, a naphthol type coupler and a phenol type coupler can be preferably used as the cyan dye forming coupler.

In particular, when the present invention is used as a light-sensitive material for direct appreciation such as color paper, the fastness and color reproducibility of the dye image are improved, for example, US Pat. No. 2,859,826,
JP-A-50-112038, JP-A-53-109630, JP-A-55-163537,
2,5-diacylaminophenol cyan couplers disclosed in JP-A-63-96656 and U.S. Pat.
No. 4,443,536, etc., a phenolic cyan coupler having an alkyl group having 2 or more carbon atoms at the 5-position is advantageously used. In addition to naphthol-based and phenol-based cyan couplers, JP-A 1-156748 and 3-174153
No. 3-196039 imidazole cyan couplers disclosed in such as JP-A-2-136854, 3-196039 etc. pyrazoloazole cyan couplers, pyrazoloazine cyan couplers, Japanese Patent Laid-Open No. 3-103848
Nos. 3-103849 and the like, hydroxypyridine cyan couplers, hydroxydiazine cyan couplers, and aminopyridine cyan couplers disclosed in JP-A-3-206450 are color reproducibility and image storability. It is excellent in terms of color recovery and is advantageously used.

Specific examples of cyan couplers preferably used in the present invention are shown below, but the present invention is not limited to these.

[0207]

[Chemical 90]

[0208]

[Chemical Formula 91]

[0209]

[Chemical Formula 92] Further, in addition to the above compounds, exemplified compounds C-1 to C-31 described on pages 4 to 6 of JP-A-63-96656 as phenol cyan couplers and JP-A-1-196048.
Exemplified compounds III-1 to III-31 described on pages 10 to 13,
IV-1 to IV-20, exemplified compounds C-1 to C-22 described in JP-A-3-109549, pages 9 to 11 and JP-A-62-215.
Exemplified Compound C-1 described on pages 99 to 103 of Japanese Patent No. 272
To C-42, and the like. Exemplified compounds A-1 to A-13 and B-1 to B described on pages 5 to 7 of JP-A-2-136854 as cyan couplers other than phenols. −
16, C-1 to C-8, D-1 to D-8, JP-A-3-03848
Exemplified compounds (1) described on pages 7 to 13 of the publication
(69), Exemplified compounds C-1 to C-103 and D- described in JP-A-3-96039, pages 10 to 16 and pages 18 to 20.
1 to D-31 and the like. The above-mentioned hydrophobic compound such as a dye-forming coupler is usually dissolved in a high-boiling point organic solvent having a boiling point of about 150 ° C. or higher or a water-insoluble polymer compound in combination with a low-boiling point and / or water-soluble organic solvent as necessary. ,
In a hydrophilic colloid layer of interest, after emulsifying and dispersing by using a dispersing agent such as a stirrer, homogenizer, colloid mill, flow jet mixer, ultrasonic device, etc., using a surfactant in a hydrophilic binder such as gelatin aqueous solution. Can be added to.

Examples of the high boiling point organic solvent used in the present invention include esters such as phthalic acid ester and phosphoric acid ester,
Examples thereof include organic acid amides, ketones, hydrocarbon compounds and the like. Specific examples thereof include compounds represented by Exemplified Compounds A-1 to A-120 described on pages 4 to 7 of JP-A 1-196048, and Exemplified compounds described on pages 8 to 9
Compounds represented by II-1 to II-29, exemplified compounds H-1 to H22 described on pages 14 to 15, described in JP-A 1-209446, pages 3 to 7 Compounds represented by Exemplified Compounds S-1 to S-69, Exemplified Compounds I-1 to I- described in JP-A-63-253943, pages 10 to 12
Examples thereof include compounds represented by 95.

The water-insoluble and organic solvent-soluble polymers used for dispersing couplers and the like include (1) vinyl polymers and copolymers, (2) polycondensates of polyhydric alcohols and polybasic acids, and (3 ) Polyester obtained by the ring-opening polymerization method, (4) In addition, polycarbonate resin, polyurethane resin, polyamide resin and the like can be mentioned.

The number average molecular weight of these polymers is not particularly limited, but is preferably 200,000 or less, more preferably
It is 5,000 to 100,000.

Specific examples of polymers that are preferably used are shown below, but the invention is not limited thereto. However, the copolymer represents the weight ratio of the monomers. [PO-1] poly (Nt-butyl acrylamide) [PO-2] Nt-butyl acrylamide-methyl methacrylate copolymer (60:40) [PO-3] polybutyl methacrylate [PO-4] methyl Methacrylate-styrene copolymer (90:10) [PO-5] Nt-butylacrylamide-2-methoxyethyl acrylate copolymer (55:45) [PO-6] ω-methoxy polyethylene glycol acrylate (additional mole Number n = 9) -Nt-butyl acrylamide copolymer (25:75) Further, in addition to the above compounds, No. 10 of JP-A-64-537 can be used.
Exemplified compounds P-1 to P-200 described on pages 15 to 16 may be mentioned.

The light-sensitive material of the present invention contains a color antifoggant,
Image stabilizer, hardener, plasticizer, anti-irradiation dye, polymer latex, ultraviolet absorber, formalin scavenger, development accelerator, development retarder, optical brightener, matting agent, lubricant, antistatic agent, A surfactant or the like can be optionally used. These are described, for example, in JP-A Nos. 62-215272 and 63-46436. The light-sensitive material of the present invention can form an image by performing color development processing known in the art.

[0215]

EXAMPLES Next, the present invention will be explained based on examples.
Embodiments of the present invention are not limited to these. Example 1 A polyethylene support was laminated on one side of a paper support and polyethylene containing titanium oxide was laminated on the other side, and each layer having the constitution shown in Tables 1 and 2 below was used. By coating on the layer side, a multilayer silver halide color photographic material sample 101 was prepared. The coating liquid was prepared as follows. First layer coating liquid 26.7 g of yellow coupler (YC-8), 10.0 g of dye image stabilizer (ST-1), dye image stabilizer (ST-2)
To 6.67 g, an anti-stain agent (HQ-1) 0.67 g and a high boiling point organic solvent (DNP) 6.67 g, 60 ml of ethyl acetate was added and dissolved, and this solution was mixed with 20% of a surfactant (SU-2) of 7 ml 10 % Gelatin aqueous solution 220 ml was emulsified and dispersed using an ultrasonic homogenizer to prepare a yellow coupler dispersion. This dispersion was mixed with a blue-sensitive silver halide emulsion (containing 8.67 g of silver) shown below, and an anti-irradiation dye (AIY-1) was further added to prepare a coating solution for the first layer.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. Also, as a hardener, the second layer and the fourth layer
(HH-1) was added to the layer and (HH-2) was added to the seventh layer. As the coating aid, surfactants (SU-1), (S
U-3) was added to adjust the surface tension.

[0217]

[Table 1]

[0218]

[Table 2]

[0219]

[Chemical formula 93]

[0220]

[Chemical 94]

[0221]

[Chemical 95] Blue-sensitive silver halide emulsion (Em-B) Average grain size 0.85 μm, coefficient of variation = 0.07, silver chloride content 99.5
Mol% monodisperse cubic emulsion sodium thiosulfate 0.8 mg / mol AgX chloroauric acid 0.5 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye BS-1 4 × 10 ⁻⁴ Mol / mol AgX sensitizing dye BS-2 1 × 10 ⁻⁴ mol / mol AgX green-sensitive silver halide emulsion (Em-G) average grain size 0.43 μm, coefficient of variation = 0.08, silver chloride content 99.5
Mol% monodisperse cube emulsion sodium thiosulfate 1.5 mg / mol AgX chloroauric acid 1.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye GS-1 4 × 10 ⁻⁴ Mol / mol AgX red-sensitive silver halide emulsion (Em-R) average particle size 0.50 μm, coefficient of variation = 0.08, silver chloride content 99.5
Mol% monodisperse cubic emulsion sodium thiosulfate 1.8 mg / mol AgX chloroauric acid 2.0 mg / mol AgX stabilizer STAB-1 6 × 10 ⁻⁴ mol / mol AgX sensitizing dye RS-1 1 × 10 ⁻⁴ Mol / mol AgX

[0222]

[Chemical 96] Next, the coupler CC-2 of the fifth layer of Sample 101 was replaced with an equimolar amount of the compound shown in Table 3 below, whether or not the ultraviolet absorber of the 6th layer was added, and the addition layer was changed as shown in Table 3. Furthermore, the fluorescent compound precursor of the present invention was emulsified and dispersed in the fifth layer to the seventh layer together with other hydrophobic compounds and added as shown in Table 3 to prepare samples 102 to 115.

The thus-prepared sample was wedge-exposed with red light according to a conventional method, and then processed according to the following processing steps. The composition of each treatment liquid is shown below.

The replenishment amount of each processing solution is silver halide photographic light-sensitive.
Material 1m² It is 80 ml per unit. Color developer Tank solution Replenisher Pure water 800ml 800ml Triethanolamine 10g 18g N, N-diethylhydroxylamine 5g 9g Potassium chloride 2.4g 1-Hydroxyethylidene-1,1-diphosphonic acid 1.0g 1.8g N-ethyl -N-β-methanesulfonamidoethyl-3-methyl-4-aminoaniline sulfate 5.4g 8.2g Optical brightener (4,4'-diaminostilbenesulfonic acid derivative) 1.0g 1.8g Potassium carbonate 27g 27g Add water to make the total volume 1 liter.
Adjust the pH to 10.10 and the replenisher to 10.60. Bleach-fixing solution (tank solution and replenisher are the same) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 60g Ethylenediaminetetraacetic acid 3g Ammonium thiosulfate (70% aqueous solution) 100ml Ammonium sulfite (40% aqueous solution) 27.5ml Water and the total amount 1 liter, potassium carbonate or ice
Adjust the pH to 5.7 with acetic acid. Stabilizer (tank solution and replenisher are the same) 5-chloro-2-methyl-4-isothiazolin-3-one 1.0 g ethylene glycol 1.0 g 1-hydroxyethylidene-1,1-diphosphonic acid 2.0 g ethylenediamine Tetraacetic acid 1.0 g Ammonium hydroxide (20% aqueous solution) 3.0 g Optical brightener (4,4'-diaminostilbenedisulphonic acid derivative) 1.5 g Water is added to bring the total volume to 1 liter, and sulfuric acid or potassium hydroxide is added.
Adjust pH to 7.0 with um.

The following evaluations were performed using the obtained samples. <Light resistance> The obtained sample was stored in sunlight for 2 months, and the residual rate (%) of the cyan dye image at an initial density of 1.0 was determined. The results are shown in Table 3. The reflection absorption spectrum of the <reflection absorption spectrum> The resulting samples were measured using a color analyzer with a xenon light source, the blue portion of the time of the concentration of maximum absorption of the cyan dye image 1.0 density D _B of (440 nm) I asked. The results are shown in Table 3.

[0226]

[Table 3]In Samples 102 to 115, the UV of the fifth layer and the sixth layer
The amount of the line absorber added was the same as that of the sample 101,
~ The amount of the fluorescent compound precursor added to the seventh layer is 0.6 mmol.
/ M² Is. Addition to the 7th layer is DNP 0.2g / m²With
It was emulsified and dispersed.

As is clear from Table 3, the cyan coupler in the fifth layer of Sample 101 was replaced with the fluorescent compound precursor of the present invention as compared with the conventional Sample 101 containing no fluorescent compound precursor or mercapto compound releasing compound of the present invention. Samples 103 and 1 only changed to body and mercapto compound releasing compounds
No. 13 has a small decrease in D _{B and} a small effect of reducing asymmetric absorption. On the other hand contains a fluorescent compound precursor and a mercapto compound releasing compounds of the present invention, the fifth layer to the seventh layer samples 102 and 104 UV absorber except of a small D _B, the effect of reducing the large asymmetric absorption Although obtained, the light resistance is poor. On the other hand, the sample 105 of the present invention having the constitution of the present invention
It can be seen that 112, 114 and 115 all have a small D _B , a large effect of reducing asymmetric absorption is obtained, and they are also excellent in light resistance. Example 2 The cyan coupler of the fifth layer of the sample 101 of Example 1 was replaced with an equimolar cyan coupler shown in Table 4 below, and
Change the UV absorber of the layer, the sixth layer as shown in Table 4,
Further, Sample 1 was prepared except that the mercapto compound releasing compound and the fluorescent compound precursor of the present invention were added as shown in Table 4.
Samples 201 to 208 were manufactured in the same manner as 01. The same evaluation as in Example 1 was performed using the obtained sample. The results are shown in Table 4.

[0228]

[Table 4] The effects of the present invention were also obtained in this example. Also,
Sample 208 mercapto compound releasing compound IV-5-16
The effects of the present invention were obtained even in the samples in which IV-3-3 and IV-4-8 were used, and the fluorescent compound precursor I-1-30 was changed to I-1-17 and III-14, respectively. Example 3 Magenta coupler MC of the third layer of Sample 101 of Example 1
-10 was replaced with an equimolar compound shown in Table 5 below, the ultraviolet absorbers in the fourth to sixth layers were changed as shown in Table 5, and the fluorescent compound precursor of the present invention was shown in Table 5. Sample 301-
307 was produced. The obtained sample was subjected to wedge exposure with green light, the same treatment as in Example 1 was performed, and then the obtained magenta dye image was evaluated in the same manner as in Example 1. The results are shown in Table 5.

[0229]

[Table 5] The effect of the present invention was obtained also in this example.

[0230]

According to the present invention, the color reproducibility is excellent, and
It was possible to provide a silver halide photographic light-sensitive material excellent in image storability.

Claims (12)

[Claims] 1. A silver halide photographic light-sensitive material having a photographic constituent layer including a silver halide emulsion layer and a UV absorber-containing layer on a support, and the photographic constituent on the support side of the UV absorber-containing layer and the layer. At least one layer selected from the layers contains at least one compound capable of releasing a mercapto compound as a function of exposed silver halide, and is separated from the ultraviolet absorber-containing layer and the support from the support. At least one selected from the photographic constituent layers on the opposite side
The layer contains at least one fluorescent compound precursor capable of forming a fluorescent substance by reacting with a mercapto compound released from a compound capable of releasing the mercapto compound during color development, which is characterized in that it contains silver halide. Photographic material. 2. A silver halide photographic light-sensitive material having a photographic constituent layer comprising a silver halide emulsion layer and a UV absorber-containing layer on a support, wherein the UV absorber-containing layer and the photographic constituent on the support side of the layer. From at least one layer selected from the layers, containing at least one compound capable of releasing a mercapto compound as a function of exposed silver halide, and from the support containing the ultraviolet absorber-containing layer and the layer. At least one selected from the photographic constituent layers on the remote side
The layer contains at least one of a fluorescent compound precursor capable of forming a fluorescent substance by reacting with a mercapto compound released from a compound capable of releasing the mercapto compound during color development and a color developer component. And a silver halide photographic light-sensitive material. 3. The silver halide photographic light-sensitive material according to claim 1, wherein the fluorescent compound precursor capable of forming a fluorescent substance is a compound represented by the general formula [I]. [Chemical 1] [In the formula, FL represents an n-valent fluorescent compound residue having a bond in the nucleus. ] 4. A fluorescent compound precursor capable of forming a fluorescent substance.
Is a compound represented by the general formula [I-1]
The silver halide photographic light-sensitive material according to claim 1 or 3,
Fee. [Chemical 2][In the formula, R ₁Represents a substituent capable of substituting on the benzene ring,
m represents an integer of 0 to 5, and when m is 2 or more, a plurality of R
₁May be the same or different, and adjacent R₁
May be condensed with each other to form a ring. ] 5. The silver halide photographic light-sensitive material according to claim 1, wherein the fluorescent compound precursor capable of forming a fluorescent substance is a compound represented by the formula [I-2]. [Chemical 3] [In the formula, R ₂ represents a substituent capable of substituting on the benzene ring,
m ′ represents an integer of 0 to 4, and when m ′ is 2 or more, a plurality of R ₂ may be the same or different, and adjacent R ₂ are condensed with each other to form a ring. It may be one. R ₃ represents a hydrogen atom or a substituent. ] 6. The silver halide photographic light-sensitive material according to claim 1, wherein the fluorescent compound precursor capable of forming a fluorescent substance is a compound represented by the general formula [II]. [Chemical 4] [In the formula, R ₄ , R ₅ and R ₆ represent a hydrogen atom or a substituent, and Z represents a halogen atom. However, R ₄ , R ₅ and R
₆ does not represent a hydrogen atom at the same time. ] 7. The silver halide photographic light-sensitive material according to claim 2, wherein the fluorescent compound precursor capable of forming a fluorescent substance is a compound represented by the general formula [III]. [Chemical 5] [In the formula, R ₇ , R ₈ , R ₉ and R ₁₀ represent a hydrogen atom and a substituent capable of substituting for a benzene ring, and R ₇ , R ₈ and R ₈ which are adjacent to each other.
₈ and R ₉ , and R ₉ and R ₁₀ may be condensed with each other to form a hydrocarbon ring or a heterocycle. X and Y represent O or N—R ₁₁ , and R ₁₁ represents a substituent. ] 8. The silver halide photographic light-sensitive material according to claim 1, wherein the compound releasing the mercapto compound is a compound represented by the general formula [IV-1]. [Chemical 6] [In the formula, Cp represents a coupler residue, SR ₂₁ represents a group which is released upon coupling with an oxidation product of a color developing agent during development processing, and R ₂₁ represents alkyl, aryl, heterocycle, substituted alkyl or substituted aryl. , Represents each group of the substituted heterocycle. ] 9. The silver halide photographic light-sensitive material according to claim 1, wherein the compound releasing the mercapto compound is a compound represented by the general formula [IV-2]. [Chemical 7] [In the formula, Cp represents a coupler residue, Time represents a timing group bonded at the coupling position of Cp, and R ₂₂ represents an alkyl, aryl, heterocycle, substituted alkyl, substituted aryl, or substituted heterocycle group. Represent ] 10. The silver halide photographic light-sensitive material according to claim 1, wherein the compound releasing the mercapto compound is a compound represented by the general formula [IV-3]. [Chemical 8] [In the formula, R ₂₃ represents each group of alkyl, aryl, heterocycle, substituted alkyl, substituted aryl, and substituted heterocycle;
₂₄ , R ₂₅ , R ₂₆ , R ₂₇ , and R ₂₈ represent a hydrogen atom or a substituent, and at least two of them are —OH or —NH.
SO ₂ R ₂₉ , wherein R ₂₉ represents each group of alkyl, aryl, heterocycle, substituted alkyl, substituted aryl, and substituted heterocycle. ] 11. The silver halide photographic light-sensitive material according to claim 1, wherein the compound releasing the mercapto compound is a compound represented by the general formula [IV-4]. [Chemical 9] [In the formula, R ₃₁ represents a substituent, l represents an integer of 0 to 4, R ₃₀ represents an alkyl, aryl, heterocycle, substituted alkyl, substituted aryl, or substituted heterocycle group, and A represents hydrogen. Represents an atom or halogen. ] 12. The silver halide photographic light-sensitive material according to claim 1, wherein the compound releasing the mercapto compound is a compound represented by the general formula [IV-5]. [Chemical 10] [In the formula, R ₃₃ represents an organic group having at least one group selected from carboxy, sulfo, and hydroxy and having 16 or less carbon atoms, R ₃₄ represents a hydrogen atom or a water-soluble acidic group, and Time represents a timing group. R ₃₂ is alkyl,
Each represents an aryl group, a heterocycle group, a substituted alkyl group, a substituted aryl group, or a substituted heterocycle group, and G represents a hydrogen atom or a blocking group which can be split off during development by hydrolysis or intramolecular nucleophilic substitution. ]