JP2003149760A - Processing method for silver halide photographic sensitive material and processing composition for silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a processing method which diminishes stains due to the residual sensitizing dye of a silver halide photographic sensitive material. SOLUTION: In the processing method, a silver halide photographic sensitive material is irradiated with light or brought into contact with an oxidizing agent in the presence of at least one compound of the formula (X)k -(L)m -(A-B)n wherein X is a silver halide attracting group or a light absorbing group; L is a divalent linking group; A is an electron donative group; B is a releasable group or H and is released or deprotonated after oxidation to generate a radical A.; k and m are each an integer of 0-3; and n is 1 or 2.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, preferably a silver halide photographic light-sensitive material, and more particularly to a method for reducing stains resulting from residual sensitizing dye in the light-sensitive material after processing. is there. Moreover,
The present invention relates to a silver halide photographic light-sensitive material processing composition used for this purpose.

[0002]

2. Description of the Related Art With the remarkable progress of digital cameras and color printers, in the processing of silver halide color photographic light-sensitive materials, it is desired to promptly provide customers with high quality images. However, if the conventional processing method is simply shortened, the processing is completed before the sensitizing dye in the light-sensitive material is sufficiently washed out, so the image is colored by the large amount of the sensitizing dye remaining on the white background of the color print. It became hard to appreciate it. Also in the color negative film, the density in the minimum density portion is increased, so that the color balance is disturbed and proper printing cannot be provided.

Further, in recent years, the use of tabular silver halide grains, which is an important basic technique in high-sensitivity photographic light-sensitive materials, improves the sensitivity and the sensitivity-granular ratio because the amount of sensitizing dye used per unit volume can be increased. On the other hand, the amount of sensitizing dye remaining in the processed light-sensitive material is increased. Depending on the processing conditions, an increase in the amount of residual sensitizing dye cannot be ignored, and a phenomenon such as an increase in the density of the minimum density portion of the color negative film or a coloring of the highlight portion of the color reversal film occurs.

Research Disclosure Magazine 20733
The publication discloses a method using a bistriazinylaminostilbenedisulfonic acid compound as an example of a method for removing stains caused by a sensitizing dye, and this method has been widely used in the processing of color photographic light-sensitive materials.
Japanese Unexamined Patent Publication No. 6-329936 discloses a bistriazinylaminostilbenedisulfonic acid compound which has excellent solubility and can reduce stain even by a treatment that shortens the time. Also, in US Pat. No. 6,153,364, 2,
A stain reduction method using a 6-diarylaminotriazine compound has been proposed.

The compound contained in the photographic processing solution in order to reduce the stain caused by the sensitizing dye is called a stain reducing agent and promotes the outflow of the sensitizing dye from the silver halide light-sensitive material. The effect of the stain-reducing agent decreases as the rinse liquid becomes fatigued after continuous processing of the silver halide photographic light-sensitive material, as compared with the case where the rinse liquid is new. This is because the sensitizing dye flowing out from the silver halide photographic light-sensitive material is accumulated in the processing solution, and a part of the sensitizing dye that is stable in a normal processing bath is incorporated into the silver halide light-sensitive material, resulting in sensitization. This is to prevent the washout of the dye. This inhibitory effect is remarkable in recent photographic processing liquids in which the amount of waste liquid has been reduced.

Further, as the amount of the coating sensitizing dye of the silver halide photographic light-sensitive material increases, the stain reducing agent in the photographic processing solution also needs to have a high concentration, which causes a problem of solubility in the kit and reduces the stain. In the high concentration range of the agent, the stain reducing effect depending on the concentration added may not always be exhibited. Therefore, in order to reduce the stain caused by the sensitizing dye, the fundamental solution is to decompose the sensitizing dye itself remaining in the silver halide photographic light-sensitive material to make it colorless.

US Pat. No. 6,207,359 B1 contains N-
It has been proposed to irradiate a light-sensitive material with light in the presence of an oxyazinium compound to reduce stain. However, since this compound produces pyridines by the reaction, the silver halide light-sensitive material is in a basic atmosphere, which is not preferable for image storability.

The compound of the present invention produces an active radical species by photoirradiation or oxidation treatment, which attacks the sensitizing dye to make it colorless, so that the processing of the silver halide light-sensitive material in which the amount of the coating sensitizing dye is increased. The stain caused by the sensitizing dye can be suppressed to a low level even if the continuous treatment is performed. Further, even if the reaction product of the compound of the present invention remains in the light-sensitive material, the influence on the image stability is small. This is a preferable feature in performing development processing with a shortened processing time.

[0009]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a processing method and a processing composition which provide a silver halide photographic light-sensitive material having a reduced stain resulting from residual sensitizing dye after processing. is there.

[0010]

The above-mentioned problems have been solved by the following means. That is,

(1) A silver halide photograph characterized in that an imagewise exposed silver halide photographic light-sensitive material is irradiated with light in the presence of at least one compound represented by the following general formula (I). Method of processing photosensitive material. In formula (I) (X) _k- (L) _m- (AB) _n , X represents a silver halide adsorbing group or a light absorbing group.
L represents a divalent linking group. A represents an electron-donating group, B represents a leaving group or a hydrogen atom, and after oxidation, it is eliminated or deprotonated to generate a radical A. k and m each represent an integer of 0 to 3, and n represents 1 or 2. (2) A silver halide photographic light-sensitive material, characterized in that an oxidant is brought into contact with the silver halide photographic light-sensitive material in the presence of at least one compound represented by the general formula (I) described in (1). Processing method. (3) The method for processing a silver halide photographic light-sensitive material as described in (1) or (2), wherein the compound represented by the general formula (I) is used as an aqueous solution. (4) A silver halide photographic light-sensitive material processing composition containing a compound represented by the general formula (I).

The present invention provides a processing method for the above-described silver halide photographic light-sensitive material, preferably a processing method for reducing the stain of the sensitizing dye. The compound represented by the general formula (I) in the present invention is preferably a radical generator that generates a radical (also referred to as a free radical) upon irradiation with light or contact with an oxidizing agent, and more preferably a radical generator upon irradiation with light. This is the case of a photo-radical generator that is generated.

Next, the compound represented by formula (I) of the present invention will be described in detail. The compound of the present invention represented by the general formula (I) may be used at any time during preparation of an emulsion, during the process of producing a light-sensitive material, during processing such as development of a light-sensitive material. For example, during grain formation, desalting step, during chemical sensitization, before coating, between development and fixing, and the like. It is also possible to add them in multiple times during these steps.

Next, the case of adding the compound of the general formula (I) other than the treatment step will be described. The compound of the present invention is preferably added by dissolving it in water, a water-soluble solvent such as methanol or ethanol, or a mixed solvent thereof. When the compound is dissolved in water, the compound whose solubility is increased by increasing or decreasing the pH may be adjusted by adjusting the pH and then added. The compound of the present invention represented by the general formula (I) is preferably used in the emulsion layer,
It may be added to the protective layer or the intermediate layer together with the emulsion layer and diffused during coating. Timing of addition of the compounds of the present invention may be before or after the sensitizing dyes, the amount is preferably per mole of silver ^{halide, 1 × 10 -9 ~5 × 10} -2 mol, more preferably 1 × 10 ^{- It} is contained in the silver halide emulsion layer in a proportion of ^{8 to} 2 × 10 ^-3 mol. The compound of the present invention will be described in detail. In formula (I), X represents a silver halide adsorbing group or a light absorbing group, and k represents an integer of 0 to 3. When k is 2 or more, a plurality of X may be the same or different. X
The silver halide adsorbing group represented by is preferably one having at least one selected from the group consisting of N, S, P, Se and Te, and more preferably a silver ion ligand structure of It is a thing. Examples of the silver ion ligand structure include the following. In the general formula _{(X-1) -G 1 -Z} 1 -R 1 ( wherein, G ₁ represents a divalent linking group, a substituted or unsubstituted alkylene group, alkenylene group, alkynylene group, arylene group, SO _A divalent group consisting of a divalent group, a divalent heterocyclic group, or a combination thereof, Z ₁ is S,
Represents a Se or Te atom. R ₁ represents a hydrogen atom or a counter ion necessary when it becomes a dissociation product of Z ₁ , and represents a sodium ion, a potassium ion, a lithium ion and an ammonium ion. )

[0015]

[Chemical 1]

(General formulas (X-2a), (X-2b) and (X-2c) form a ring, and the form thereof is a hetero saturated ring, a hetero unsaturated ring or an unsaturated carbocycle. _a is O,
It is a residue having at least one N, S, Se or Te atom and preferably completing a 5- to 7-membered ring, and may be benzo-condensed or naphtho-condensed if necessary. Z _b is
It may have an O, N, S, Se or Te atom, and is preferably a residue that completes a 5- to 7-membered ring, and may be benzo-condensed or naphtho-condensed if necessary. R ₂ represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group or an aryl group. ) General formula _{(X-3) -R 3 -} (Z 2) n 2 -R 4 ( wherein, Z ₂ is S, Se or Te atom, n ₂ is 1
Represents an integer of 3; R ₃ is a divalent linking group, and is an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, or a divalent heterocyclic group and an alkylene group, an alkenylene group, an alkynylene group, an arylene group, It represents a divalent group bonded to any of the SO ₂ groups.
R ₄ represents an alkyl group, an aryl group or a heterocyclic group.
When n ₂ is 2 or more, a plurality of Z ₂ may be the same or different. ) General formula (X-4)

[0017]

[Chemical 2]

(In the formula, R ₅ and R ₆ each independently represent an alkyl group, an alkenyl group, an aryl group or a heterocyclic group.)

[0019]

[Chemical 3]

(In the formula, Z ₃ represents an S, Se or Te atom, E ₁ represents a hydrogen atom, NH ₂ , NHR ₁₀ , N (R ₁₀ ).
₂ , NHN (R ₁₀ ) ₂ , OR ₁₀ or SR ₁₀ . E ₂
Is a divalent linking group, NH, NR ₁₀ , NHNR ₁₀ , O
Or represents S. R ₇ , R ₈ and R ₉ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group, and R ₈ and R ₉ may be bonded to each other to form a ring. R ₁₀ represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group or a heterocyclic group. )

[0021]

[Chemical 4]

(In the formula, R ₁₁ is a divalent linking group and represents a group consisting of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group or a combination thereof. G ₂ and J Are independently COOR ₁₂ , S
O ₂ R ₁₂ , COR ₁₂ , SOR ₁₂ , CN, CHO or N
Represents O ₂ . R ₁₂ represents an alkyl group, an alkenyl group or an aryl group. The general formula (X-1) will be described in detail. In the formula, G ₁
The connecting group represented by is a substituted or unsubstituted linear or branched alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, trimethylene, propylene, tetramethylene, hexamethylene, 3-oxapentylene). , 2-hydroxytrimethylene), carbon number 3-18
, A substituted or unsubstituted cyclic alkylene group (eg, cyclopropylene, cyclopentylene, cyclohexylene), a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms (eg, ethene, 2-butenylene), 2 carbon atoms.
An alkynylene group having 10 to 10 carbon atoms (for example, ethyne)
And 20 substituted or unsubstituted arylene groups (eg, unsubstituted p-phenylene, unsubstituted 2,5-naphthylene). In the formula, the SO ₂ group represented by G ₁ is —S
O ₂ - in other groups, having 1 to 10 carbon atoms, a substituted or unsubstituted, linear or branched alkylene group having 3-6 carbon atoms
A substituted or unsubstituted cyclic alkylene group or an —SO ₂ — group bonded to an alkenylene group having 2 to 10 carbon atoms. Further, as the divalent linking group represented by G ₁ , a divalent heterocyclic group or a divalent heterocyclic group and any one of an alkylene group, an alkenylene group, an alkynylene group, an arylene group, and an SO ₂ group. A divalent group bonded thereto or a heterocyclic moiety of these groups benzo- or naphtho-condensed (for example, 2,3-tetrazolediyl, 1,
3-triazolediyl, 1,2-imidazolediyl, 3,5-oxadiazoludiyl, 2,4-thiazoldiyl, 1,5-benzimidazolediyl, 2,5
-Benzothiazol-diyl, 2,5-benzoxazo-
Ludiyl, 2,5-pyrimidinediyl, 3-phenyl-
2,5-tetrazolediyl, 2,5-pyridinediyl, 2,4-furandiyl, 1,3-piperidinediyl, 2,4-morpholinediyl). In the above formula, G ₁ may have a substituent as much as possible. The substituents are shown below, and these substituents are referred to as the substituent Y here.
Called. Examples of the substituent include a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, etc.), an alkyl group (eg, methyl, ethyl, isopropyl, n-propyl, t
-Butyl), alkenyl group (eg allyl, 2-butenyl), alkynyl group (eg propargyl), aralkyl group (eg benzyl), aryl group (eg phenyl, naphthyl, 4-methylphenyl), heterocyclic group (eg pyridyl, Furyl, imidazolyl, piperidinyl, morpholyl), alkoxy group (eg methoxy, ethoxy, butoxy, 2-ethylhexyloxy, ethoxyethoxy, methoxyethoxy), aryloxy group (eg phenoxy, 2-naphthyloxy), amino group (eg unsubstituted) Amino, dimethylamino, diethylamino, dipropylamino, dibutylamino, ethylamino, anilino), acylamino group (eg acetylamino, benzoylamino), ureido group (eg unsubstituted ureido,
N-methylureido), urethane group (eg methoxycarbonylamino, phenoxycarbonylamino), sulfonylamino group (eg methylsulfonylamino,
Phenylsulfonylamino), sulfamoyl group (eg unsubstituted sulfamoyl, N, N-dimethylsulfamoyl, N-phenylsulfamoyl), carbamoyl group (eg unsubstituted carbamoyl, N, N-diethylcarbamoyl, N-phenylcarbamoyl) , A sulfonyl group (eg, mesyl, tosyl), a sulfinyl group (eg, methylsulfinyl, phenylsulfinyl), an alkyloxycarbonyl group (eg, methoxycarbonyl, ethoxycarbonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl), an acyl group (eg, acetyl, Benzoyl, formyl, pivaloyl), acyloxy group (eg acetoxy, benzoyloxy), phosphoric acid amide group (eg N, N-diethylphosphoric acid amide), cyano group, sulfo group, Osuruhon acid group, a sulfinic acid group, a carboxy group, hydroxy group, a phosphono group, a nitro group, an ammonio group, phosphonio group, a hydrazino group, and a Chiazorino group. When there are two or more substituents, they may be the same or different, and the substituent may further have a substituent. As preferred general formula (X-1), G ₁ is an arylene group, an alkylene group, a heterocyclic group bonded to an arylene group, or a benzo-condensed or naphtho-condensed heterocyclic group, and Z ₁ is S. Or Se, and R ₁ is a hydrogen atom, sodium ion or potassium ion. More preferably, G ₁ is a heterocyclic group bonded to an arylene group or a benzo-fused heterocyclic group, Z ₁ is S, and R ₁ is a hydrogen atom or a sodium ion. Particularly preferred heterocyclic groups have the following structures.

[0023]

[Chemical 5]

(In the formula, Z_cIs O, N, S, Se or T
may have an e atom, preferably completing a 5 to 7 membered ring
Is a residue that is optionally a benzo-condensed or naphtho-condensed
You may ring. ) General formula (X-2a), (X-2b) and (X-2c)
Will be described in detail. Where R₂Represented by
1 carbon atom as a alkenyl group, alkenyl group, or alkynyl group
10 substituted or unsubstituted, straight chain or branched chain
Alkyl group (eg methyl, ethyl, isopropyl, n-
Propyl, n-butyl, t-butyl, 2-pentyl, n
-Hexyl, n-octyl, t-octyl, 2-ethyl
Hexyl, 2-hydroxyethyl, 1-hydroxyethyl
, Diethylaminoethyl, n-butoxypropyl,
Toxylmethyl), substituted or unsubstituted, having 3 to 6 carbon atoms
Cyclic alkyl groups (eg cyclopropyl, cyclopen
(Cyl, cyclohexyl), alkenyl having 2 to 10 carbon atoms
A group (eg, allyl, 2-butenyl, 3-pentenyl),
Alkynyl groups having 2 to 10 carbon atoms (for example, propargyl,
3-pentynyl), an aralkyl group having 6 to 12 carbon atoms (eg,
For example, benzyl) and the like. As an aryl group,
A substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg,
Examples include unsubstituted phenyl and 4-methylphenyl)
Be done. R above₂May further have a substituent Y or the like. one
With general formulas (X-2a), (X-2b) and (X-2c)
And preferably R ₂Is a hydrogen atom, and has 1 to 6 carbon atoms
Alternatively, an unsubstituted alkyl group or a substituent having 6 to 10 carbon atoms
Or an unsubstituted aryl group, Z_aOr Z_bBut
When having at least one O, N or S atom
It More preferably, R₂Is hydrogen atom or carbon number
1 to 4 alkyl groups, Z_aOr Z_bIs N or
This is the case of having at least one S atom.

Next, the general formula (X-3) will be described in detail. In the formula, the linking group represented by R ₃ has 1 carbon atom.
To 20 substituted or unsubstituted, linear or branched alkylene groups (for example, methylene, ethylene, trimethylene, isopropylene, tetramethylene, hexamethylene, 3-oxapentylene, 2-hydroxytrimethylene), and 3 carbon atoms. ~ 18, a substituted or unsubstituted cyclic alkylene group (for example, cyclopropylene, cyclopentynylene, cyclohexylene), a substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms (for example, ethene, 2-butenylene), carbon An alkynylene group having 2 to 10 carbon atoms (eg ethyne), a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (eg unsubstituted p-phenylene, unsubstituted 2,5
-Naphthylene), and examples of the heterocyclic group include a substituted or unsubstituted heterocyclic group, and an alkylene group, an alkenylene group, an arylene group, or a heterocyclic group bonded to the heterocyclic group (for example, 2,5-pyridinediyl). , 3-phenyl-2,5-pyridinediyl, 1,3-piperidinediyl, 2,4-morpholinediyl). In the formula,
The alkyl group represented by R ₄ has 1 to 10 carbon atoms.
A substituted or unsubstituted, linear or branched alkyl group (eg, methyl, ethyl, isopropyl, n-propyl, n-butyl, t-butyl, 2-pentyl, n-hexyl, n-octyl, t-octyl). , 2-ethylhexyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, methoxymethyl), a substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms (for example, cyclopropyl). , Cyclopentyl, cyclohexyl), and the aryl group includes a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (eg, unsubstituted phenyl, 2-methylphenyl). The heterocyclic group is an unsubstituted or alkyl group, an alkenyl group, an aryl group, or
Further substituted with a heterocyclic group (eg pyridyl, 3
-Phenylpyridyl, piperidyl, morpholyl). The above R ₄ may further have a substituent Y or the like.

As the general formula (X-3), R is preferable.₃But
A substituted or unsubstituted alkylene group having 1 to 6 carbon atoms,
Or a substituted or unsubstituted aryl having 6 to 10 carbon atoms.
Rene group, R_FourIs a substituted or non-substituted one having 1 to 6 carbon atoms.
Substituted alkyl group or C6-10 substituted
Is an unsubstituted aryl group, Z₂Is S or Se
Yes, n₂Is 1 to 2. More preferably,
R₃Is an alkylene group having 1 to 4 carbon atoms, and R_FourIs the carbon number
1 to 4 alkyl groups, Z₂Is S and n ₂Is 1
This is the case. Next, the general formula (X-4) will be described in detail.
To do. Where R_FiveAnd R₆An alkyl group represented by
The alkenyl group has 1 to 10 carbon atoms and is substituted or non-substituted.
A substituted, linear or branched alkyl group (eg methyl,
Ethyl, isopropyl, n-propyl, n-butyl, t
-Butyl, 2-pentyl, n-hexyl, n-octyl
L, t-octyl, 2-ethylhexyl, hydroxyme
Chill, 2-hydroxyethyl, 1-hydroxyethyl,
Diethylaminoethyl, dibutylaminoethyl, n-bu
Toxymethyl, n-butoxypropyl, methoxymethy
), A substituted or unsubstituted cyclic alkyl group having 3 to 6 carbon atoms
Kill groups (eg cyclopropyl, cyclopentyl, cyclyl)
Lohexyl), an alkenyl group having 2 to 10 carbon atoms (for example,
Allyl, 2-butenyl, 3-pentenyl).
It If the aryl group has 6 to 12 carbon atoms and is substituted,
Or an unsubstituted aryl group (eg, unsubstituted phenyl, 4-
Methylphenyl), and the heterocyclic group is unsubstituted
Or alkylene group, alkenylene group, arylene
A group, or one in which a heterocyclic group is further substituted (eg pyridin)
Dil, 3-phenylpyridyl, furyl, piperidyl, molybdenum
Lefolil).

In the above formula, R ₅ and R ₆ may further have a substituent Y or the like. As the general formula (X-4), R ₅ and R ₆ are preferably a substituted or unsubstituted alkyl group having 1 to ₆ carbon atoms, or a substituted or unsubstituted aryl group having 6 to 10 carbon atoms. . More preferably, R ₅ and R ₆ are aryl groups having 6 to 8 carbon atoms. Next, general formulas (X-5a) and (X-5b) will be described in detail. In the formula, examples of the group represented by E ₁ include NH ₂ , NHCH ₃ , NHC ₂ H ₅ , NHPh, and N.
(CH ₃ ) ₂ , N (Ph) ₂ , NHNHC ₃ H ₇ , NHNH
Ph, OC ₄ H ₉ , OPh and SCH ₃ can be mentioned, and E ₂ is, for example, NH, NCH ₃ , NC ₂ H ₅ , NPh or NH.
NC ₃ H ₇ and NHNPh can be mentioned (wherein Ph = phenyl group; the same applies hereinafter).

General formulas (X-5a) and (X-5b)
In the above, as the alkyl group and alkenyl group represented by R ₇ , R ₈ and R ₉ , a substituted or unsubstituted linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl,
Ethyl, isopropyl, n-propyl, n-butyl, t-
Butyl, 2-pentyl, n-hexyl, n-octyl,
t-octyl, 2-ethylhexyl, hydroxymethyl, 2-hydroxyethyl, 1-hydroxyethyl, diethylaminoethyl, dibutylaminoethyl, n-butoxymethyl, n-butoxypropyl, methoxymethyl), substituted with 3 to 6 carbon atoms Alternatively, an unsubstituted cyclic alkyl group (eg, cyclopropyl, cyclopentyl, cyclohexyl) and an alkenyl group having 2 to 10 carbon atoms (eg, allyl, 2-butenyl, 3-pentenyl) can be mentioned. As the aryl group, a substituted or unsubstituted aryl group having 6 to 12 carbon atoms (for example, unsubstituted phenyl,
4-methylphenyl), the heterocyclic group is unsubstituted or has an alkylene group, an alkenylene group, an arylene group, or a heterocyclic group further substituted (for example, pyridyl, 3-phenylpyridyl, furyl, piperidyl, morpholyl). ) Is mentioned. R ₇ , R ₈ and R ₉ may further have a substituent Y or the like. In formulas (X-5a) and (X-5b), preferably E ₁ is an alkyl-substituted or unsubstituted amino group or alkoxy group,
E ₂ is an alkyl-substituted or unsubstituted amino linking group, R ₇ , R ₈ and R ₉ are substituted or unsubstituted alkyl groups having 1 to 6 carbon atoms, or substituted or unsubstituted groups having 6 to 10 carbon atoms. Is a substituted aryl group, Z ₃ is S or S
This is the case of e. More preferably, E ₁ is an alkyl-substituted or unsubstituted amino group, E ₂ is an alkyl-substituted or unsubstituted amino linking group, and R ₇ , R ₈ and R ₉ are substituted or unsubstituted C 1-4 or It is an unsubstituted alkyl group and Z ₃ is S.

Next, formulas (X-6a) and (X-6)
The b) will be described in detail. In the formula, G₂And represented by J
The group that can be used is COOR₁₅(COOH, COOC
H₃. R₁₅Is a hydrogen atom, substituted or unsubstituted alkyl
Represents a group or an aryl group. same as below. ), COR₁₅
(Eg COC₂H_Five, COPh), CHO, CN, SO
₂R₁₅(Eg SO₂CH₃), SOR₁₅(Eg SOC
H₃, SOPh), NO ₂Etc. Where R₁₁so
The linking group represented by each has 1 to 20 carbon atoms,
Substituted or unsubstituted, linear or branched alkylene group
(For example, methylene, ethylene, trimethylene, propylene
Amine, tetramethylene, hexamethylene, 3-oxapene
Ethylene, 2-hydroxytrimethylene), carbon number 3 to 1
8 is a substituted or unsubstituted cyclic alkylene group (for example,
Cyclopropylene, cyclopentylene, cyclohexyl
), A substituted or unsubstituted alkene having 2 to 20 carbon atoms
Nylene group (eg ethene, 2-butenylene), carbon number 2
An alkynylene group having 10 to 10 carbon atoms (for example, ethyne)
20 substituted or unsubstituted arylene groups (eg,
Substituted p-phenylene and unsubstituted 2,5-naphthylene) are listed.
You can

Further, the divalent linking group represented by R ₁₁ includes a divalent heterocyclic group or a divalent heterocyclic group and an alkylene group, an alkenylene group, an alkynylene group, an arylene group or an SO ₂ group. A divalent group bonded to any of them (eg 2,5-pyridinediyl, 3-phenyl-2,5-pyridinediyl, 2,4-furandiyl, 1,3-piperidinediyl, 2,4-morpholinediyl) Is mentioned.
In the formula, R ₁₁ may further have a substituent Y or the like. As the general formulas (X-6a) and (X-6b), G ₂ and J are preferably carboxylic acid esters or carbonyls having 2 to 6 carbon atoms, and R ₁₁ is substituted or unsubstituted. A substituted alkylene group or C6-10,
This is the case of a substituted or unsubstituted arylene group. More preferably, G ₂ and J are carboxylic acid esters having 2 to 4 carbon atoms, and R ₁₁ is a substituted or unsubstituted alkylene group having 1 to 4 carbon atoms or a substituted or unsubstituted alkylene group having 6 to 8 carbon atoms. This is the case of a substituted arylene group. A preferred general formula of the silver halide adsorbing group represented by X is (X
-1)>(X-2a)>(X-2b)>(X-3)>
(X-5a)>(X-5b)>(X-4)> (X-6
a)> (X-6b). Next, in the general formula (I), X
The light absorbing group represented by will be described in detail. In the general formula (I), the light absorbing group represented by X includes the following. General formula (X-7)

[0031]

[Chemical 6]

(In the formula, Z ₄ represents an atomic group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and L ₂ , L ₃ , and L
₄ and L ₅ represent a methine group. p ₁ represents 0 or 1, and n ₃ represents an integer of 0-3. M ₁ represents a charge-balancing counterion, and m ₂ is 0 to necessary for neutralizing the charge of the molecule.
Represents an integer of 10. The nitrogen-containing heterocycle formed by Z ₄ includes
An unsaturated carbocycle such as a benzene ring may be condensed. In the formula, the 5- or 6-membered nitrogen-containing heterocycle represented by Z ₄ includes a thiazolidine nucleus, a thiazole nucleus, a benzothiazole nucleus, an oxazoline nucleus, an oxazole nucleus, a benzoxazole nucleus, a selenazoline nucleus, a selenazole nucleus, and benzoselena. Zole nucleus, 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline nucleus, 4- Examples thereof include a quinoline nucleus, a 1-isoquinoline nucleus, a 3-isoquinoline nucleus, an imidazo [4,5-b] quinoxaline nucleus, an oxadiazole nucleus, a thiadiazole nucleus, a tetrazole nucleus and a pyrimidine nucleus. The 5- or 6-membered nitrogen-containing heterocycle represented by Z ₄ may have the aforementioned substituent Y.

Where L₂, L₃, L_FourAnd L_FiveAre each
Represents an independent methine group. L₂ , L ₃, L_FourAnd L_Fiveso
The methine group represented may have a substituent,
As, for example, substituted or unsubstituted carbon number 1 to 15
Alkyl groups (eg methyl, ethyl, 2-carboxy)
Ethyl), a substituted or unsubstituted ant having 6 to 20 carbon atoms
Group (eg phenyl, o-carboxyphenyl),
A substituted or unsubstituted heterocyclic group having 3 to 20 carbon atoms (eg,
For example, one hydrogen atom from N, N-diethylbarbituric acid
Except for monovalent groups), halogen atoms (eg salts)
(Elemental, bromine, fluorine, iodine), carbon dioxide having 1 to 15 carbon atoms
Si group (eg methoxy, ethoxy), having 1 to 15 carbon atoms
Alkylthio group (eg methylthio, ethylthio), charcoal
An arylthio group having a prime number of 6 to 20 (eg, phenylthio group)
E), an amino group having 0 to 15 carbon atoms (for example, N, N-diff
Phenylamino, N-methyl-N-phenylamino, N-
Methyl piperazino) and the like. Also other methines
You may form a ring with a group. Or other parts and rings
Can also be formed.

Wherein M ₁ is included in the formula to indicate the presence of a cation or anion when required to neutralize the ionic charge of the light absorbing group. Typical cations are inorganic cations such as hydrogen ion (H ⁺ ) and alkali metal ions (eg sodium ion, potassium ion, lithium ion), ammonium ion (eg ammonium ion, tetraalkylammonium ion, pyridinium ion, ethyl). Organic cations such as pyridinium ion). The anion may be either an inorganic anion or an organic anion,
Halogen anion (eg, fluorine ion, chlorine ion,
Iodide ion), substituted aryl sulfonate ion (for example, p-toluene sulfonate ion, p-chlorobenzene sulfonate ion), aryl disulfonate ion (for example, 1,3-benzene disulfonate ion, 1,5-naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkylsulfate ion (eg methylsulfate ion), sulfate ion, thiocyanate ion, perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, trifluoromethanesulfonate ion. Is mentioned. Further, an ionic polymer or a light absorbing group having an opposite charge may be used. In the present invention, for example, a sulfo group is described as SO ₃ ⁻ and a carboxy group is described as CO ₂ ⁻ , but when the counter ion is a hydrogen ion, each is SO _{3 −.}
It can be expressed as H or CO ₂ H. In the formula, m ₂ represents the number necessary for balancing the charges, and is 0 when forming a salt in the molecule.

As the general formula (X-7), preferably Z ₄
Is a benzoxazole nucleus, a benzothiazole nucleus, a benzimidazole nucleus or a quinoline nucleus, and L ₂ , L ₃ , L
₄ and L ₅ are unsubstituted methine groups, p ₁ is 0, and n ₃ is 1 or 2. More preferably, Z ₄ is a benzoxazole nucleus or a benzothiazole nucleus, n ₃ is 1, and particularly preferably Z ₄ is a benzothiazole nucleus. In general formula (I), k is preferably 0 or 1, and more preferably 1. However, when k is 2 or more, X may be coupled not only in series but also to L at a plurality of locations (k locations). Specific examples of the X group used in the present invention are shown below, but the compound used in the present invention is not limited thereto.

[0036]

[Chemical 7]

[0037]

[Chemical 8]

[0038]

[Chemical 9]

[0039]

[Chemical 10]

[0040]

[Chemical 11]

[0041]

[Chemical 12]

Next, the divalent linking group represented by L in the general formula (I) will be described in detail. L represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a divalent heterocyclic group, -O -, - S -, - NR 10 - (R 10 is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, or (Representing a heterocyclic group), —CO—, —SO ₂ — and the like, which are linked together with a group consisting of one or a combination thereof, and these may be further substituted with a substituent Y. The alkylene group for L is preferably an alkylene group having 1 to 20 carbon atoms, such as methylene, ethylene, trimethylene,
Pentamethylene, octamethylene, propylene, 2-hydroxytrimethylene, 2-buten-1,4-yl, 2
-Butyn-1,4-yl, p-xylylene, cyclopropylene. The alkenylene group is preferably an alkenylene group having 1 to 20 carbon atoms, for example, ethene-
It is 1,2-yl. The alkynylene group is preferably an alkynylene group having 1 to 20 carbon atoms, for example, ethyn-1,2-yl. The arylene group is preferably an arylene group having 6 to 20 carbon atoms, and examples thereof include phenylene and 2,5-naphthylene. The divalent heterocyclic linking group is preferably a heterocyclic group having 1 to 20 carbon atoms, and examples thereof include furan-1,4-diyl and 2,6-pyridinediyl. L is an alkylene group, an alkenylene group, an arylene group, -O-, -S-, -NR ₁₀
-, - CO -, - SO ₂ - groups is preferably made from one or a combination of such an alkylene group, an arylene group, -
_{O -, - NR 10 -,} - CO -, - SO 2 - a group formed from one or a combination of such more preferred. When m is 2 or more, a plurality of Ls may be the same or different. In general formula (I), m is preferably 0 or 1, and more preferably 1. However, when m is 2 or more, L may be coupled not only in series (-L-L-) but also in multiple locations (m locations) in parallel to X or A. Next, the electron donating group A will be described in detail. After the portion A-B is oxidized by contact with light or an oxidant, it undergoes fragmentation to simultaneously generate electrons, radical A. is generated, and radical A. is further oxidized to generate electrons. The process is shown below.

[0043]

[Chemical 13]

Since A is an electron-donating group, it is preferable that the substituents on the aromatic groups of any structure be selected so that A is in the state of electron excess. For example, when the aromatic ring is not electron-rich, an electron-donating group is introduced. Conversely, when the aromatic ring is extremely electron-rich, an electron-withdrawing group is introduced to control the oxidation potential. It is preferable. A preferred group A is represented by the following general formula.

[0045]

[Chemical 14]

(In the general formulas (A-1) and (A-2),
R₁₂And R₁₃Are each independently a hydrogen atom,
Or an unsubstituted alkyl group, aryl group, or heterocyclic group
Represent, R₁₄Represents a substituent having a Hammett σ value of −1 to +1.
You Ar₁Represents an arylene group or a heterocyclic linking group.
Q₂Represents O, S, Se or Te, and m₃And m_FourIs each
Each independently represent 0 or 1, L₂Is NR (where R
Represents a substituted or unsubstituted alkyl group. ), N-A
r (where Ar is a substituted or unsubstituted aryl group or
Represents a heterocyclic group. ), O, S, Se, Te or N
Represents H. R₁₂And R₁₃, R₁₂And Ar₁Or R₁₃And Ar₁
May combine with each other to form a 5- to 8-membered ring. one
The cyclic form of general formula (A-3) is a substituted or unsubstituted 5
~ Represents a 7-membered unsaturated ring. ) For formulas (A-1), (A-2) and (A-3)
Will be described in detail. Where R₁₂And R₁₃Represented by
The alkyl group may have 1 to 10 carbon atoms and may be substituted.
Or an unsubstituted linear or branched alkyl group (for example,
Methyl, ethyl, isopropyl, n-propyl, n-bu
Tyl, t-butyl, 2-pentyl, n-hexyl, n-
Octyl, t-octyl, 2-ethylhexyl, 2-hi
Droxyethyl, 1-hydroxyethyl, diethylami
Noethyl, dibutylaminoethyl, n-butoxymethyi
, Methoxymethyl), substituted with 3 to 6 carbon atoms or
Unsubstituted cyclic alkyl groups (eg cyclopropyl, cyclo)
Ropentyl, cyclohexyl), aryl groups
Is a substituted or non-substituted C 6-12 substituted or unsubstituted
Reel groups (eg unsubstituted phenyl, 2-methylphenyi)
Le). Heterocyclic group has 1 to 10 carbon atoms
A substituted or unsubstituted heterocyclic group (for example, pyridine,
Benzothiazole). General formula (A-1)
And in (A-2), R₁₄Hammet as the group represented by
Any substituent may be used as long as it has a σ value of -1 to +1.
Is preferably a substituent of -0.7 to +0.7. Ingredient
Physically, alkyl groups (eg, methyl, ethyl, isopropyl)
Pill, n-propyl, n-butyl, 2-pentyl, n-
Hexyl, n-octyl, 2-ethylhexyl, 2-hi
Droxyethyl, n-butoxymethyl), COOR₁₅Basis
(For example COOH, COOC₂H_Five. R₁₅Is a hydrogen atom,
It represents a alkyl group or an aryl group. ), Halogen atom (eg
For example, fluorine atom, chlorine atom, bromine atom), N (R₁₅)
₂(For example, N (CH₃)₂, NPh₂), OR₁₅(Eg O
H, OCH₃, OPh), SR₁₅(Eg SCH₃, SP
h), CHO, COR₁₅(Eg COCH₃, COP
h), CON (R₁₅)₂(For example, CONHC₂H_Five , CON
(CH₃) ₂), SO₃R₁₅(Eg SO₃CH₃, SO₃C₃
H₇), SO₂N (R₁₅)₂(Eg SO₂NHCH₃, SO₂
N (CH₃)₂), SO₂R₁₅(Eg SO₂C₂H_Five), SO
R₁₅(Eg SOCH₃), CSR₁₅(Eg CSP
h, CSCH₃) Is mentioned. General formula (A-1) and
And Ar in (A-2)₁Has 6 to 12 carbon atoms
A substituted or unsubstituted arylene group (eg, phenyl
Len, 2-methylphenylene, naphthylene), if substituted
Or an unsubstituted heterocyclic group (eg pyridyl, 3-phenyl
1 hydrogen atom from pyridyl, piperidyl, morpholyl)
Alternatively, a divalent or trivalent group excluding two is mentioned. General
L in formula (A-1)₂For example, NH, NC
H₃, NC_FourH₉ , NC₃H₇(I), NPh, NPh-C
H₃, O, S, Se, Te. General formula (A-
The unsaturated ring of 3) is preferably a 5- to 7-membered unsaturated ring.
Carbocycle, 5-7 membered saturated or unsaturated heterocycle (eg free
, Piperidyl, morpholyl). General formula
R in (A-1) and (A-2)₁₂, R₁₃, R₁₄, A
r₁, L₂, And on the ring in the general formula (A-3),
It may further have a substituent Y or the like. General formula (A-1),
Preferred examples of (A-2) and (A-3) are shown. General
In formulas (A-1) and (A-2), preferably R₁₂, R
₁₃Is a substituted or unsubstituted alkyl having 1 to 6 carbon atoms
A group, or a substituted or unsubstituted C6 to C10 group
Reel base, R₁₄Is a C1-6 substituted or
Unsubstituted alkyl group, alkyl group having 1 to 4 carbon atoms
Substituted or disubstituted amino group, carboxylic acid, halogen
Or a carboxylic acid ester having 1 to 4 carbon atoms, A
r₁Is a substituted or unsubstituted aryl having 6 to 10 carbon atoms.
Len group, Q₂Is O, S or Se, and m₃as well as
m_FourIs 0 or 1, and n_FourIs 1 to 3, and L
₂Is an alkyl-substituted amino group having 0 to 3 carbon atoms
It In formula (A-3), a preferred cyclic form is 5 to 7 members
It is a saturated or unsaturated heterocyclic ring. General formula (A-1)
And (A-2), more preferably R₁₂, R₁₃Is carbon
A substituted or unsubstituted alkyl group of the formulas 1 to 4,
R₁₄Is an unsubstituted alkyl group having 1 to 4 carbon atoms, 1 to 4 carbon atoms
4 monoamino- or diamino-substituted alkyl
Is a radical, Ar₁Is a C6-10 substituted or
Q is an unsubstituted arylene group₂Is O or S
M₃And m_FourIs 0 and n_FourIs 1 and L ₂Is carbon
It is an alkyl-substituted amino group of the numbers 0 to 3. General formula
In (A-3), a more preferable cyclic form is a 5- or 6-membered ring.
It is a heterocycle. A group is an L group (when m = 0, an X group)
The part that binds is Ar₁, R₁₂, R₁₃, R₁₄Or L₂of
Either is fine. Specific examples of the A group used in the present invention are shown below.
For example, the compound used in the present invention is not limited to this.
It is not something that will be done.

[0047]

[Chemical 15]

[0048]

[Chemical 16]

[0049]

[Chemical 17]

[0050]

[Chemical 18]

[0051]

[Chemical 19]

[0052]

[Chemical 20]

Next, the group B will be described in detail. Group B represents a leaving group or a hydrogen atom. Preferred B groups include:
For example, the A group defined by the general formulas (A-1), (A-2) and (A-3) (which may be the same as or different from the A group to be bonded), a hydrogen atom and the following It has a formula.

[0054]

[Chemical 21]

When the group B is a hydrogen atom (this compound is 0 to
Preferably having an oxidation potential of 1.5 V), the acid
The compound undergoes a deprotonation reaction to generate a radical (A.)
Is a compound that can occur (this radical is
It is preferable to have an oxidation potential of 0.6 V or less). This
Deprotonation reaction at the time of may depend on the base in the molecule
However, it may be an extramolecular base. Preferably in the molecule
It has a base. Also, as the base, a proton
Any group can be used as long as it undergoes a oxidization reaction, but preferably about
It is a conjugate base of an acid having a pKa of 1-8. For example carboxy
Rate, sulfate, amine oxide and the like,
More preferably, it is a carboxylate. General formula (B-
2) and (B-3), W is Si, Sn or Ge
Represent, R ₁₆Represents an alkyl group, Ar₂Is an aryl group
Represent The general formulas (B-2) and (B-3) are bonded to the X group.
Can be combined. Formulas (B-2) and (B-
3) will be described in detail. Where R₁₆Represented by
The rukyl group may be substituted or non-substituted having 1 to 6 carbon atoms.
Alternative linear or branched alkyl groups (eg methyl, ether
Chill, isopropyl, n-propyl, n-butyl, t-
Butyl, 2-pentyl, n-hexyl, n-octyl,
t-octyl, 2-ethylhexyl, 2-hydroxyethyl
Chill, 1-hydroxyethyl, n-butoxyethyl, me
Toximethyl), Ar₂The aryl group represented by
A substituted or unsubstituted aryl group having 6 to 12 carbon atoms
(Eg, phenyl, 2-methylphenyl)
It R in the general formulas (B-2) and (B-3)₁₆and
Ar₂May further have the above-mentioned substituent Y and the like.
Preferred examples of the general formulas (B-2) and (B-3) are shown below.
Shown in. Of the general formulas (B-2) and (B-3), preferred
Kuha R₁₆Is a substituted or unsubstituted alkane having 1 to 4 carbon atoms.
A kill group, Ar₂Has 6 to 10 carbon atoms and may be substituted
Is an unsubstituted aryl group, W is Si or Sn
It Of the general formulas (B-2) and (B-3), more preferred
Actually, R₁₆Is a substituted or unsubstituted C1-C3
An alkyl group, Ar₂Is substituted with 6 to 8 carbon atoms
Is an unsubstituted aryl group, and W is Si. Group B
Most preferred as COO of the general formula (B-1)^-
And Si- (R in the general formula (B-2)₁₆)₃And
It In the general formula (I), n is 1 or 2, and preferably
Is 1. However, when n is 2, (AB) is connected in series.
Not only do they match but also connect them in parallel at multiple points (n points) to L
The two (A-B) may be the same or different.
You may stay. Below, the AB group used in the present invention, or
Examples of the compound represented by AB in the case of k = 0 will be given.
However, the present invention is not limited to this.

[0056]

[Chemical formula 22]

[0057]

[Chemical formula 23]

[0058]

[Chemical formula 24]

[0059]

[Chemical 25]

[0060]

[Chemical formula 26]

[0061]

[Chemical 27]

Counterions necessary for the charge balance of the above compounds AB include sodium ion, potassium ion, triethylammonium ion, diisopropylammonium ion, tetrabutylammonium ion,
And tetramethylguanidinium ion. A preferable oxidation potential of AB is 0 to 1.5 V,
It is more preferably 0 to 1.0 V, and further preferably 0.3 to 1.0 V. The preferable oxidation potential (E ₁ ) of the radical A · resulting from the bond cleavage reaction is −0.6.
To -2.5V, and more preferably -0.9 to -2V.
And more preferably in the range of -0.9 to -1.6V. The method for measuring the oxidation potential is as follows. E ₁ can be performed by the cyclic voltammetry method.
The electron donor A is dissolved in a solution of acetonitrile / 0.1M or water containing lithium chlorate in 80% / 20% (volume%). A glassy carbon disk was used as the working electrode, a platinum wire was used as the counter electrode, and a saturated calomel electrode (S
CE) is used for the reference electrode. Measurement is performed at 25 ° C. at a potential scanning rate of 0.1 V / sec. The oxidation potential vs. SCE is taken at the peak potential of the cyclic voltammetry wave. The E ₁ values of these AB compounds are described in EP 93,731 A1. Radical oxidation potential measurements are made by transient electrochemistry and pulse radiolysis. These are described in J. Am. Chem. Soc. , 1988, 11
0,132, 1974,96,1287, 197
4, 96, 1295. Specific examples of the compound represented by formula (I) are shown below, but the compound used in the present invention is not limited thereto.

[0063]

[Chemical 28]

[0064]

[Chemical 29]

[0065]

[Chemical 30]

[0066]

[Chemical 31]

[0067]

[Chemical 32]

[0068]

[Chemical 33]

[0069]

[Chemical 34]

[0070]

[Chemical 35]

[0071]

[Chemical 36]

The compound of the present invention produces a more active radical species when the light-sensitive material of the present invention is irradiated with light or subjected to oxidation treatment, which attacks the sensitizing dye to decolorize the sensitizing dye. By making the sensitizing dye hydrophilic and accelerating the elution of the sensitizing dye from the sensitizing material, the sensitizing dye can be treated even if the silver halide light-sensitive material having the increased amount of the applied sensitizing dye is processed or continuously processed. The resulting stain can be suppressed to a low level. Further, even if the reaction product of the compound of the present invention remains in the light-sensitive material, the influence on the image stability is small. This is a preferable feature in performing development processing with a shortened processing time.

The amount of the compound of the present invention used is 1 m of the light-sensitive material.²
Per 1 x 10^-62 x 10 from mol ^-3mol and is preferred
2 × 10^-61 x 10 from mol^-3mol, especially good
5x10 is better^-65 x 10 from mol^-Fourmol.

The compound of the present invention may be contained in the unexposed silver halide photographic light-sensitive material in advance, or it may be contained in the processing liquid and incorporated by immersing the silver halide photographic light-sensitive material. You may combine both.
Of these, it is preferable to use the compound of the present invention in a treatment liquid prepared as an aqueous solution. The compound of the present invention may be used alone or in combination of two or more compounds.

Any method may be used for incorporating the compound of the present invention into the silver halide photographic light-sensitive material. For example, the method of adding a sensitizing dye described below can be used. In addition, other known dispersion methods can be used. That is, a method for producing a solid particle colloid of a photographically useful compound having a submicron size as described in British Patent No. 1,570,362 and US Pat. No. 2,32
The oil-in-water dispersion method described in No. 2,027 and the like can be mentioned.
The steps and effects of the latex dispersion method and specific examples of latex for impregnation are described in US Pat. No. 4,199,633 and West German Patent Application (OLS) Nos. 2,541,274 and 2,5.
No. 41,230 and European Patent No. 294,104A.

When the compound of the present invention is contained in the processing solution, it can be contained in any processing bath for color development, bleaching, fixing, washing with water, stability, adjustment, black and white development, reversal, pre-bleaching and the like. Further, the compound of the present invention may be contained in any of the tank solution, the replenishing solution, the concentrated replenishing solution and the kit of the above treatment bath. Moreover, the compound of the present invention may be contained in an additive composition. The additive composition has a function of adding photographic performance to a tank solution or a replenisher solution required for processing for forming an image of a silver halide color photographic light-sensitive material before or during processing. It is a composition.

The silver halide photographic light-sensitive material used in the present invention is any of ordinary silver halides such as silver chloride, silver bromide, silver bromoiodide, silver chlorobromide, silver chloroiodide and mixtures thereof. Can also be included. In one embodiment, the light-sensitive material is a high silver chloride light-sensitive material containing at least 50 mol% or more chloride, more preferably at least 90 mol% or more silver chloride, and is used as a color print light-sensitive material.

In another embodiment, the at least one emulsion is predominantly silver bromide (at least 50 mol% silver bromide). Most preferably the photographic silver halide photographic material has one or more color records, each color record having one or more predominantly silver bromide emulsions such as those used in color negative and color reversal films. The silver halide photographic light-sensitive material processed according to the present invention can be a single color element or a multicolor element. The photosensitive material can also have a magnetic recording layer known in the art.

Details of the individual silver halide photographic light-sensitive materials are described in, for example, Research Disclosure (hereinafter abbreviated as RD), and RD17643 23-27.
Pages, RD18716 647-650 pages, RD
307105 Pages 866-868, 873-879
RD 36544 501-541 pages. These are useful silver halide emulsions (negative or positive type) and their preparation methods, various sensitizers, dye-forming couplers, spectral sensitizing dyes, supersensitizers, image dye stabilizers, dyes, ultraviolet absorbers. , Filters, binders, hardeners, plasticizers, lubricants, coating aids, surface-active agents,
Antistatic agent, matting agent, paper and film support,
Alternatively, it relates to various image forming methods for negative image and positive image forming color elements.

Any spectral sensitizing dye and supersensitizer may be used, and examples thereof include those described in RD above.

The spectral sensitizing dyes used are preferably cyanine dyes, merocyanine dyes, rhodacyanine dyes, trinuclear merocyanine dyes, tetranuclear merocyanine dyes, allopolar dyes, hemicyanine dyes and styryl dyes. Cyanine dyes, merocyanine dyes and rhodacyanine dyes are more preferred, and cyanine dyes are particularly preferred. For more information on these dyes,
FM Harmer, “Heterocyclic Compounds-Cyanin
e Dyes and Related Compounds ", John Wiley & Sons-New York, London, 1964, Day M Starmer
(DMSturmer) `` Heterocyclic Compounds-Special topi
cs inheterocyclic chemistry) ", Chapter 18, 14
S., pp. 482-515, John Wiley & Sons, Inc.-New York, London, 1977, "Rods Chemistry of the."
Carbon Compounds (Rodd's Chemistry of Carbon
Compounds) ”2nd.Ed.vol.IV, partB, 1977, 15th
Chapter, pages 369-422, Elsevier Science
Public Company, Inc. (Elsevier Science Pu
blishing Company Inc.), published in New York, etc.

To further explain, pages 23 to 24 of RD17643 and pages 648 of RD18716, right column to 649.
Page right column, RD308119 page 996 right column to page 998 right column, European Patent No. 0565096A1, page 65, pages 7-1.
Those described in line 0 can be preferably used. Also, US Pat. No. 5,747,236 (particularly pages 30 to 39), US Pat. No. 5,340,694 (particularly pages 21 to 60, provided that (XI), (XII), (XII
In the sensitizing dye shown in _{I), n 12, n 1} 5, n 17,
The number of n ₁₈ is not limited and is an integer of 0 or more (preferably 4 or less). The sensitizing dyes represented by the general formulas and specific examples described in 1) can also be preferably used.

Next, cyanine dyes, merocyanine dyes (including trinuclear or tetranuclear merocyanine dyes), and rhodacyanine dyes preferably used in the present invention are shown below by general formulas. General formula (X)

[0084]

[Chemical 37]

In the formula (X), L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ and L
₁₅ , L ₁₆ and L ₁₇ represent a methine group. p ₁₁ and p ₁₂
Represents 0 or 1. n ₁₁ represents 0, 1, 2, 3 or 4. Z ₁₁ and Z ₁₂ represent an atomic group necessary for forming a nitrogen-containing heterocycle. However, the ring may be condensed to these. M ₁₁ represents a charge-balancing counterion, and m ₁₁ represents a number of 0 or more necessary for neutralizing the charge of the molecule. R ₂₁ and R ₂₂ represent an alkyl group, an aryl group, or a heterocyclic group. General formula (XI)

[0086]

[Chemical 38]

In the formula (XI), L ₁₈ , L ₁₉ , L ₂₀ , and L
₂₁ represents a methine group. p ₁₃ represents 0 or 1. q ₁₁ is 0
Or represents 1. n ₁₂ represents 0, 1, 2, 3 or 4.
Z ₁₃ represents an atomic group necessary for forming a nitrogen-containing heterocycle. Z ₁₄ and Z ₁₄ ^'represents a (N-R _{2 4)} heterocyclic ring together with q _11, or acyclic atomic group necessary for forming an acidic end groups. However, the ring may be condensed to Z ₁₃ , and Z ₁₄ and Z ₁₄ ′. M ₁₂ represents a charge balancing counterion,
m ₁₂ represents a number of 0 or more necessary for neutralizing the charge of the molecule. R ₂₃ represents an alkyl group, an aryl group, or a heterocyclic group. R ₂₄ represents a hydrogen atom, an alkyl group, an aryl group, or a heterocyclic group. General formula (XII)

[0088]

[Chemical Formula 39]

In formula (XII), L_{twenty two}, L_{twenty three}, L_{twenty four},
L_{twenty five}, L₂₆, L₂₇, L₂₈, L₂₉And L₃₀Represents the methine group
You p₁₄And p₁₅Represents 0 or 1. q₁₂Is 0 or 1
Represent. n₁₃And n₁₄Represents 0, 1, 2, 3 or 4.
Z₁₅, And Z₁₇Is necessary to form a nitrogen-containing heterocycle
Represents a group of atoms. Z₁₆And Z₁₆'Is (N-R₂₆) Q₁₂With
Represents an atomic group necessary for forming a heterocycle.
However, Z₁₅, Z₁₆And Z₁₆ ^', And Z₁₇The ring is condensed
You may stay. M₁₃Represents a charge-balancing counterion, m₁₃Is a minute
Represents a number of 0 or greater required to neutralize the charge of the offspring.
R_{twenty five}, And R₂₇Is an alkyl group, aryl group, or heterocycle
Represents a group. R₂₆Is a hydrogen atom, an alkyl group, an aryl group,
Or represents a heterocyclic group.

Hereinafter, general formulas (X), (XI), and (X
The methine dye represented by II) will be described in detail.

Regarding a group and the like in the following description, when a specific part is referred to as a “group”, the part may be one or more (up to the maximum possible number) of substituents, even if the part is not itself substituted. It means that it may be substituted with a group.
For example, "alkyl group" means a substituted or unsubstituted alkyl group. Further, the substituent that can be used in the compound of the present invention may be any substituent regardless of the presence or absence of substitution.

When such a substituent is represented by W, the substituent represented by W may be any one, and is not particularly limited. For example, a halogen atom, an alkyl group [cycloalkyl group, a bicycloalkyl group, a trialkyl group, Including a cycloalkyl group, alkenyl group (cycloalkenyl group,
(Including a bicycloalkenyl group) and an alkynyl group. ], Aryl group, heterocyclic group (may be referred to as heterocyclic group), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyl Oxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (including anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group , Alkyl and aryl sulfonylamino groups, mercapto groups, alkylthio groups, arylthio groups, heterocyclic thio groups, sulfamoyl groups, sulfo groups, alkyl and aryl sulfinyl groups, alkyl and aryl sulfonyl groups, acyl groups, aryl groups Xycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imido group, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group , A boronic acid group (-B (OH) ₂ ), a phosphato group (-OPO (O
H) ₂ ), a sulfato group (—OSO ₃ H), and other known substituents can be given as examples.

More specifically, W is a halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom),
Alkyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkyl group. They are alkyl groups (preferably alkyl groups having 1 to 30 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, 2-cyanoethyl, 2-ethylhexyl). A cycloalkyl group (preferably a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, for example, cyclohexyl, cyclopentyl, 4-n-dodecylcyclohexyl), a bicycloalkyl group (preferably having 5 to 30 carbon atoms). A substituted or unsubstituted bicycloalkyl group, ie, having 5 to 3 carbon atoms
It is a monovalent group obtained by removing one hydrogen atom from a bicycloalkane of 0. For example, bicyclo [1,2,2] heptan-2-yl, bicyclo [2,2,2] octane-3-
And a tricyclo structure having many ring structures. The alkyl group in the substituents described below (for example, an alkyl group of an alkylthio group) represents an alkyl group having such a concept, and further includes an alkenyl group and an alkynyl group. ], An alkenyl group [represents a linear, branched, or cyclic substituted or unsubstituted alkenyl group.
They are alkenyl groups (preferably having 2 to 30 carbon atoms).
A substituted or unsubstituted alkenyl group, such as vinyl,
Allyl, prenyl, geranyl, oleyl), a cycloalkenyl group (preferably a substituted or unsubstituted cycloalkenyl group having 3 to 30 carbon atoms, that is, a monovalent group in which one hydrogen atom of a cycloalkene having 3 to 30 carbon atoms is removed. A group of, for example, 2-cyclopenten-1-yl,
2-cyclohexen-1-yl), a bicycloalkenyl group (a substituted or unsubstituted bicycloalkenyl group, preferably a substituted or unsubstituted bicycloalkenyl group having 5 to 30 carbon atoms, that is, a bicycloalkene having one double bond. It is a monovalent group with one hydrogen atom removed.
For example, bicyclo [2,2,1] hept-2-ene-1
-Yl, bicyclo [2,2,2] oct-2-ene-4
-Yl). ], An alkynyl group (preferably a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, for example, ethynyl, propargyl, trimethylsilylethynyl group)], an aryl group (preferably a substituted or unsubstituted C 6 to 30 carbon atom) Aryl groups such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, o-hexadecanoylaminophenyl), heterocyclic groups (preferably 5- or 6-membered substituted or unsubstituted, aromatic or non-aromatic heterocycles). A monovalent group obtained by removing one hydrogen atom from a ring compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms, such as 2-furyl and 2-thienyl. , 2-pyrimidinyl, 2-benzothiazolyl, 1-methyl-2-
It may be a cationic heterocyclic group such as pyridinio or 1-methyl-2-quinolinio. ), A cyano group, a hydroxyl group, a nitro group, a carboxyl group, an alkoxy group (preferably a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, for example, methoxy, ethoxy, isopropoxy, t-butoxy, n-octyl. Oxy, 2-methoxyethoxy), aryloxy group (preferably having 6 carbon atoms)
To 30 substituted or unsubstituted aryloxy groups, such as phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy), silyloxy groups (preferably having a carbon number 3 to 20 silyloxy groups, for example, trimethylsilyloxy, t-butyldimethylsilyloxy), heterocyclic oxy groups (preferably having 2 to 3 carbon atoms).
0-substituted or unsubstituted heterocyclic oxy group, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), acyloxy group (preferably formyloxy group, substituted or unsubstituted alkyl group having 2 to 30 carbon atoms) Carbonyloxy group, substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms, for example, formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy group (preferably A substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy,
Morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), an alkoxycarbonyloxy group (preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms, for example, Methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), an aryloxycarbonyloxy group (preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms, for example, phenoxy. Carbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy), an amino group (preferably an amino group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon atom having 6 to 30 carbon atoms) A substituted anilino group, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino), an ammonio group (preferably an ammonio group, substituted or unsubstituted alkyl having 1 to 30 carbon atoms, aryl, Heterocyclic-substituted ammonio groups, such as trimethylammonio, triethylammonio, diphenylmethylammonio), acylamino groups (preferably formylamino groups, substituted or unsubstituted alkylcarbonylamino groups having 1 to 30 carbon atoms, Having 6 to 30 carbon atoms A substituted or unsubstituted arylcarbonylamino group, for example, formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino), aminocarbonylamino group (preferably A substituted or unsubstituted aminocarbonylamino having 1 to 30 carbon atoms, for example, carbamoylamino,
N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino), an alkoxycarbonylamino group (preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms, for example, methoxycarbonylamino,
Ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-
Methyl-methoxycarbonylamino), an aryloxycarbonylamino group (preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, m-n- Octyloxyphenoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, N −
n-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino having 6 to 30 carbon atoms, for example, methyl Sulfonylamino,
Butylsulfonylamino, phenylsulfonylamino,
2,3,5-trichlorophenylsulfonylamino, p
-Methylphenylsulfonylamino), a mercapto group,
An alkylthio group (preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms, such as methylthio,
Ethylthio, n-hexadecylthio), arylthio group (preferably substituted or unsubstituted arylthio having 6 to 30 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxyphenylthio), heterocyclic thio group (preferably having carbon number) 2 to 30 substituted or unsubstituted heterocyclic thio groups, for example 2-benzothiazolylthio,
1-phenyltetrazol-5-ylthio), a sulfamoyl group (preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N , N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl,
N- (N′-phenylcarbamoyl) sulfamoyl), sulfo group, alkyl and arylsulfinyl group (preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms) Groups such as methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p
-Methylphenylsulfinyl), an alkyl and arylsulfonyl group (preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms, for example, methylsulfonyl, ethylsulfonyl) , Phenylsulfonyl, p-methylphenylsulfonyl), acyl group (preferably formyl group, substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, carbon Number 4 to 3
A heterocyclic carbonyl group linked to a carbonyl group at 0 substituted or unsubstituted carbon atoms, for example acetyl,
Pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl,
2-pyridylcarbonyl, 2-furylcarbonyl), an aryloxycarbonyl group (preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, for example, phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxy). Carbonyl, p
-T-butylphenoxycarbonyl), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl), carbamoyl. A group (preferably a substituted or unsubstituted carbamoyl having 1 to 30 carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N,
N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), aryl and heterocyclic azo groups (preferably a substituted or unsubstituted arylazo group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon atom having 3 to 30 carbon atoms) Substituted heterocyclic azo group such as phenylazo, p-chlorophenylazo, 5-ethylthio-1,3,4-thiadiazol-2-ylazo), imide group (preferably N)
-Succinimide, N-phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably, A substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, for example, phosphinyl,
Dioctyloxyphosphinyl, diethoxyphosphinyl), phosphinyloxy group (preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms,
For example, diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy, a phosphinylamino group (preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, for example, dimethoxyphosphinylamino). , Dimethylaminophosphinylamino), a phospho group, a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms, for example, trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl), a hydrazino group ( Preferably, a substituted or unsubstituted hydrazino group having 0 to 30 carbon atoms, for example, trimethylhydrazino, a ureido group (preferably a substituted or unsubstituted ureido group having 0 to 30 carbon atoms, for example, N, N).
-Dimethylureido).

Further, two Ws may be combined to form a ring (aromatic or non-aromatic hydrocarbon ring or heterocycle. These can be further combined to form a polycyclic condensed ring.
For example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, fluorene ring, triphenylene ring, naphthacene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring. Ring, pyridazine ring, indolizine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring, carbazole ring, phenanthridine ring Ring, acridine ring, phenanthroline ring, thianthrene ring, chromene ring, xanthene ring, phenoxathiine ring, phenothiazine ring, phenazine ring. ) Can also be formed.

Among the above-mentioned substituents W, those having a hydrogen atom may be substituted with the above-mentioned group after removing the hydrogen atom. Examples of such substituents include -CONHS
O ₂ - group (sulfonylcarbamoyl group, a carbonyl sulfamoyl group), - CONHCO- group (carbonylation carbamoyl group), - SO ₂ NHSO ₂ - group (sulfonylsulfamoyl group), and the like. More specifically, an alkylcarbonylaminosulfonyl group (for example, acetylaminosulfonyl), an arylcarbonylaminosulfonyl group (for example, benzoylaminosulfonyl group),
Examples thereof include an alkylsulfonylaminocarbonyl group (for example, methylsulfonylaminocarbonyl) and an arylsulfonylaminocarbonyl group (for example, p-methylphenylsulfonylaminocarbonyl).

General formulas (X), (XI), and (XII)
In the formula, Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₅ and Z ₁₇ each represent a group of atoms necessary for forming a nitrogen-containing heterocycle, preferably a 5- or 6-membered nitrogen-containing heterocycle. However, the ring may be condensed to these. The ring may be either an aromatic ring or a non-aromatic ring. An aromatic ring is preferable, and examples thereof include a hydrocarbon aromatic ring such as a benzene ring and a naphthalene ring, and a heteroaromatic ring such as a pyrazine ring and a thiophene ring.

Examples of the nitrogen-containing heterocycle include thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, oxazoline nucleus, oxazole nucleus, benzoxazole nucleus, selenazoline nucleus,
Selenazole nucleus, benzoselenazole nucleus, tellrazoline nucleus, tellurazole nucleus, benzoterrazole nucleus, 3,3-
Dialkyl indolenine nucleus (eg 3,3-dimethylindolenine), imidazoline nucleus, imidazole nucleus, benzimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus,
2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quinoxaline nucleus, oxadiazole nucleus, thiadiazole nucleus,
Examples thereof include a tetrazole nucleus and a pyrimidine nucleus, but preferably a benzothiazole nucleus, a benzoxazole nucleus, a 3,3-dialkylindolenine nucleus (for example, 3,3-dimethylindolenin), a benzimidazole nucleus, a 2-pyridine nucleus. , 4-pyridine nucleus, 2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline nucleus, more preferably benzothiazole nucleus, benzoxazole nucleus, 3,3-dialkylindolenine nucleus (for example, 3 , 3-Dimethylindolenine) and benzimidazole nuclei, particularly preferably benzoxazole nuclei, benzothiazole nuclei, and benzimidazole nuclei, and most preferably benzoxazole nuclei and benzothiazole nuclei.

These include a substituent represented by the above W,
And the ring may be substituted or condensed. Preferred are alkyl groups, aryl groups, alkoxy groups, halogen atoms, and aromatic ring condensation.

Specific examples of the heterocycle formed by Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₅ and Z ₁₇ include US Pat.
340, 694 Nos. 23 to 24, Z ₁₁ , Z ₁₂ , Z ₁₃ ,
Z _14, and include those similar to those listed as examples of Z _16.

Z ₁₄ and Z ₁₄ ^′ and (N—R ₂₄ ) q ₁₁ together represent an atomic group necessary for forming a heterocyclic ring or an acyclic acidic terminal group. The heterocycle (preferably a 5- or 6-membered heterocycle) may be any, but an acidic nucleus is preferred. Next, the acidic nucleus and the acyclic acidic terminal group will be described. The acidic nuclei and acyclic acidic end groups can take the form of the acidic nuclei and acyclic acidic end groups of any common merocyanine dye. In a preferred form, Z ₁₄ is a thiocarbonyl group, a carbonyl group, an ester group, an acyl group, a carbamoyl group, a cyano group or a sulfonyl group, more preferably a thiocarbonyl group or a carbonyl group. Z ₁₄ ^' represents the remaining atomic group necessary for forming an acidic nucleus and an acyclic acidic end group. When forming an acyclic acidic terminal group, a thiocarbonyl group, a carbonyl group, an ester group, an acyl group, a carbamoyl group, a cyano group, a sulfonyl group and the like are preferable.

Q ₁₁ is 0 or 1, but is preferably 1.

The acidic nucleus and the acyclic acidic terminal group as referred to herein are, for example, "The Theory of the Photographic Process" (edited by James), edited by James.
Theory of the Photograph
ic Process) 4th edition, Macmillan Publishing Company, 1
977, pp. 197-200. Here, the acyclic acidic terminal group means an acidic or electron-accepting terminal group that does not form a ring. The acidic nucleus and the acyclic acidic terminal group are specifically,
U.S. Pat. Nos. 3,567,719, 3,575,86
No. 9, No. 3, 804, 634, No. 3, 837, 862
No. 4, 002, 480, 4, 925, 777
No. 3,167,546, US Pat. No. 5,99.
4,051 and US Pat. No. 5,747,236.

The acidic nucleus forms a heterocycle (preferably a 5-membered or 6-membered nitrogen-containing heterocycle) composed of carbon, nitrogen and / or chalcogen (typically oxygen, sulfur, selenium and tellurium) atoms. Is more preferable, and more preferably, a 5- or 6-membered nitrogen-containing heterocycle consisting of carbon, nitrogen, and / or chalcogen (typically oxygen, sulfur, selenium, and tellurium) atoms is formed. Specifically, for example, the following cores can be mentioned.

2-pyrazolin-5-one, pyrazolidine-3,5-dione, imidazoline-5-one, hydantoin, 2 or 4-thiohydantoin, 2-iminooxazolidin-4-one, 2-oxazoline-5-one,
2-thiooxazolidine-2,5-dione, 2-thiooxazoline-2,4-dione, isoxazoline-5-one, 2-thiazolin-4-one, thiazolidine-4-one, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, Isorhodanine, indane-1,3-dione, thiophen-3-one, thiophen-3-one-1,1-dioxide, indoline-2
-One, indoline-3-one, 2-oxoindazolinium, 3-oxoindazolinium, 5,7-dioxo-6,7-dihydrothiazolo [3,2-a] pyrimidine, cyclohexane-1,3-dione, 3,4 -Dihydroisoquinolin-4-one, 1,3-dioxane-4,6-dione, barbituric acid, 2-thiobarbituric acid, chroman-2,4-dione, indazoline-2-one, pyrido [1,2-a] pyrimidine-1,3-dione , Pyrazolo [1,5-b] quinazolone, pyrazolo [1,5-a]
Benzimidazole, pyrazolopyridone, 1, 2, 3,
4-tetrahydroquinoline-2,4-dione, 3-oxo-2,3-dihydrobenzo [d] thiophene-1,1
-Dioxide, 3-dicyanomethine-2,3-dihydrobenzo [d] thiophene-1,1-dioxide nucleus.

Further, the carbonyl group or thiocarbonyl group forming these nuclei is used as a raw material for a nucleus having an exomethylene structure in which the active methylene position of the acidic nucleus is substituted, and an acyclic acidic terminal group. A nucleus having an exomethylene structure substituted at the active methylene position of an active methylene compound having a structure such as ketomethylene or cyanomethylene, and a nucleus in which this nucleus is repeated.

The acidic nucleus and the acyclic acidic terminal group may be substituted or condensed with the substituent or ring represented by the above-mentioned substituent W.

Z ₁₄ and Z ₁₄ ^′ and (N—R ₂₄ ) q ₁₁ are preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, 2-thiooxazoline-2,4-dione and thiazolidine-2,4. Zeon,
Rhodanine, thiazolidine-2,4-dithione, barbituric acid, and 2-thiobarbituric acid, and more preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, and 2-thiobarbituric acid. It is an acid. Particularly preferred are 2- or 4-thiohydantoin, 2-oxazoline-5-one, and rhodanine.

The heterocyclic ring formed by Z ₁₆ and Z ₁₆ ^' and (N-R ₂₆ ) q ₁₂ includes Z ₁₄ and Z ₁₄ ^' and (N
The same as those mentioned in the description of the heterocycle of —R ₂₄ ) q ₁₁ can be mentioned. Preferably, Z ₁₄ and Z ₁₄ ^' and (NR
₂₄ ) an oxo group from the acidic nucleus described in the explanation of the heterocycle of q ₁₁ ,
Alternatively, it does not include a thioxo group.

More preferably, Z ₁₄ and Z ₁₄ ^′ and (N—R ₂₄ ) q ₁₁ mentioned above are concretely mentioned acidic nuclei from which an oxo group or a thioxo group has been removed, and more preferably hydantoin. 2, or 4-thiohydantoin,
2-oxazoline-5-one, 2-thiooxazoline-2,4-dione, thiazolidine-2,4-dione, rhodanine, thiazolidine-2,4-dithione, barbituric acid, 2-thiobarbituric acid from which oxo group or thioxo group is removed And particularly preferably hydantoin, 2 or 4-thiohydantoin, 2-oxazoline-5-one, rhodanine, barbituric acid, 2-thiobarbituric acid from which an oxo group or a thioxo group has been removed, and most preferably It is 2- or 4-thiohydantoin, 2-oxazoline-5-one, or rhodanine from which an oxo group or a thioxo group has been removed.

Q ₁₂ is 0 or 1, but is preferably 1.

R ₂₁ , R ₂₂ , R ₂₃ , R ₂₅ , and R ₂₇ are an alkyl group, an aryl group, and a heterocyclic group, and R ₂₄ and R ₂₆ are a hydrogen atom, an alkyl group, an aryl group, and a heterocyclic group. It is a cyclic group, preferably an alkyl group, an aryl group, and a heterocyclic group. R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ , R ₂₅ , R ₂₆ ,
Examples of the alkyl group, aryl group and heterocyclic group represented by R ₂₇ include, for example, an unsubstituted alkyl group having 1 to 18, preferably 1 to 7 and particularly preferably 1 to 4 carbon atoms ( For example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, octyl, dodecyl, octadecyl), carbon atoms 1 to 1
8, preferably 1 to 7, and particularly preferably 1 to 4 substituted alkyl groups {for example, the above-mentioned alkyl groups substituted with W can be mentioned. In particular, the above-mentioned alkyl group having an acid group is preferable. Preferably, an aralkyl group (eg, benzyl, 2-phenylethyl), an unsaturated hydrocarbon group (eg, an allyl group, a vinyl group, that is, a substituted alkyl group includes an alkenyl group and an alkynyl group) and hydroxy. Alkyl group (for example, 2-hydroxyethyl, 3-hydroxypropyl), carboxyalkyl group (for example, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl, carboxymethyl), alkoxyalkyl group (for example, 2-methoxy) Ethyl, 2- (2-methoxyethoxy) ethyl), aryloxyalkyl group (for example, 2-phenoxyethyl,
2- (1naphthoxy) ethyl), alkoxycarbonylalkyl group (eg ethoxycarbonylmethyl, 2-benzyloxycarbonylethyl), aryloxycarbonylalkyl group (eg 3-phenoxycarbonylpropyl), acyloxyalkyl group (eg 2-acetyloxy) Ethyl), an acylalkyl group (eg 2-acetylethyl), a carbamoylalkyl group (eg 2-morpholinocarbonylethyl), a sulfamoylalkyl group (eg N, N-dimethylsulfamoylmethyl),
Sulfoalkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl,
2- [3-sulfopropoxy] ethyl, 2-hydroxy-3-sulfopropyl, 3-sulfopropoxyethoxyethyl), sulfoalkenyl group, sulfatoalkyl group (for example, 2-sulfatoethyl group, 3-sulfatopropyl) , 4-sulfatobutyl), a heterocyclic-substituted alkyl group (for example, 2- (pyrrolidin-2-one-1-yl) ethyl, tetrahydrofurfuryl), an alkylsulfonylcarbamoylalkyl group (for example, methanesulfonylcarbamoylmethyl group), an acyl group. Lucarbamoylalkyl group (eg acetylcarbamoylmethyl group), acylsulfamoylalkyl group (eg acetylsulfamoylmethyl group), alkylsulfonylsulfamoylalkyl group (eg methanesulfonylsulfamoylmethyl group)}, carbon number 6 An unsubstituted or substituted aryl group having 20 to 20 carbon atoms, preferably 6 to 10 carbon atoms, and more preferably 6 to 8 carbon atoms (examples of the substituent include the aforementioned W. For example, phenyl group, 1 naphthyl group, p -Methoxyphenyl group, p-methylphenyl group, p-chlorophenyl group, etc.), carbon number 1 to 20, preferably carbon number 3 to 10, and more preferably carbon number 4.
To 8 unsubstituted or substituted heterocyclic groups (the above-mentioned W is mentioned as an example of the substituent. For example, 2-furyl group, 2-thienyl group, 2-pyridyl group, 3-pyrazolyl group, 3-isoxazolyl group, 3-isothiazolyl group. 2-Imidazolyl, 2-oxazolyl, 2-thiazolyl, 2-pyridazyl, 2-pyrimidyl, 3-pyrazyl, 2- (1,3,5-triazolyl), 3- (1,2,4-triazolyl), 5-tetrazolyl, 5-methyl-2-thienyl Group, 4-methoxy-2-pyridyl group, etc.).

R_{twenty one}, R_{twenty two}, R_{twenty three}, R_{twenty four}, R_{twenty five}, R₂₆, And
And R₂₇The substituent represented by is preferably an unsubstituted alkyl
Group and a substituted alkyl group, which are preferable as a substituted alkyl group.
Preferred is an alkyl group having the above-mentioned acid group. As an acid group
And preferably a sulfo group, a carboxyl group, or -CONH
SO₂-Group, -CONHCO- group, -SO₂NHSO ₂
-Group, particularly preferably sulfo group, carboxyl
A group, most preferably a sulfo group.

Here, the acid group will be described. The acid group is a group having a dissociative proton. Specifically, for example, a sulfo group, a carboxyl group, a sulfato group, -CO
NHSO ₂ -group (sulfonylcarbamoyl group, carbonylsulfamoyl group), -CONHCO- group (carbonylcarbamoyl group), -SO ₂ NHSO ₂ -group (sulfonylsulfamoyl group), sulfonamide group, sulfamoyl group, phosphato group , Phosphono group, boronic acid group,
Phenolic hydroxyl groups, such as these pka and surrounding p
Depending on H, a group capable of dissociating a proton may be mentioned. For example, a proton-dissociable acidic group capable of dissociating 90% or more between pH 5 and 11 is preferable.

More preferably, it is a sulfo group, a carboxyl group, a -CONHSO ₂ -group, a -CONHCO- group, or -S.
It is an O ₂ NHSO ₂ — group, particularly preferably a sulfo group or a carboxyl group, and most preferably a sulfo group.

L ₁₁ , L ₁₂ , L ₁₃ , L ₁₄ , L ₁₅ , L ₁₆ , L
₁₇ , L ₁₈ , L ₁₉ , L ₂₀ , L ₂₁ , L ₂₂ , L ₂₃ , L ₂₄ ,
L ₂₅ , L ₂₆ , L ₂₇ , L ₂₈ , L ₂₉ , and L ₃₀ each independently represent a methine group. The methine group represented by L _{1 to} L ₃₀ may have a substituent, and examples of the substituent include W described above. For example, a substituted or unsubstituted C1 to C1
An alkyl group having 5, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms (eg, methyl, ethyl, 2
-Carboxyethyl), a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms, more preferably 6 to 10 carbon atoms (eg phenyl, o-
Carboxyphenyl), a substituted or unsubstituted C3 to C20, preferably C4 to C15, more preferably C6 to C10 heterocyclic group (for example, N, N-dimethylbarbituric acid group), a halogen atom. (For example, chlorine, bromine, iodine, fluorine), C1 to C15, preferably C1 to C10, more preferably C1 to C5 alkoxy group (eg methoxy, ethoxy), C0 to C15, preferably Is an amino group having 2 to 10 carbon atoms, more preferably 4 to 10 carbon atoms (eg, methylamino, N,
N-dimethylamino, N-methyl-N-phenylamino, N-methylpiperazino), an alkylthio group having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms (eg, methylthio, ethylthio). , 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms
2, more preferably an arylthio group having 6 to 10 carbon atoms (eg, phenylthio, p-methylphenylthio) and the like. It may form a ring with another methine group, or may form a ring together with Z _{11 to} Z ₁₇ and R _{11 to} R ₁₇ .

L ₁₁ , L ₁₂ , L ₁₆ , L ₁₇ , L ₁₈ , L ₁₉ , L
₂₂ , L ₂₃ , L ₂₉ , and L ₃₀ are preferably unsubstituted methine groups.

N ₁₁ , n ₁₂ , n ₁₃ and n ₁₄ each independently represent 0, 1, 2, 3 or 4. Preferably 0,
1, 2, 3 and more preferably 0, 1, 2;
It is particularly preferably 0 or 1. When n ₁₁ , n ₁₂ , n ₁₃ and n ₁₄ are 2 or more, the methine groups are repeated but need not be the same.

P ₁₁ , p ₁₂ , p ₁₃ , p ₁₄ and p ₁₅ each independently represent 0 or 1. It is preferably 0.

M ₁₁ , M ₁₂ , and M ₁₃ are included in the formula to indicate the presence of cations or anions when required to neutralize the ionic charge of the dye. Typical cations include hydrogen ions (H ⁺ ), alkali metal ions (eg sodium ion, potassium ion,
Inorganic cations such as lithium ion) and alkaline earth metal ions (eg calcium ion), ammonium ions (eg ammonium ion, tetraalkylammonium ion, triethylammonium ion, pyridinium ion, ethylpyridinium ion, 1,8
-Diazabicyclo [5.4.0] -7-undecenium ion) and the like. The anion may be an inorganic anion or an organic anion, a halogen anion (eg, fluorine ion, chlorine ion, iodine ion), a substituted aryl sulfonate ion (eg, p-toluene sulfonate ion, p-ion). Chlorbenzenesulfonate ion), aryldisulfonate ion (for example, 1,3-benzenesulfonate ion, 1, 5
-Naphthalenedisulfonate ion, 2,6-naphthalenedisulfonate ion), alkylsulfate ion (for example, methylsulfate ion), sulfate ion, thiocyanate ion,
Examples include perchlorate ion, tetrafluoroborate ion, picrate ion, acetate ion, and trifluoromethanesulfonate ion. Furthermore, an ionic polymer or another dye having a charge opposite to that of the dye may be used. Also,
CO ₂ ⁻ and SO ₃ ⁻ can also be expressed as CO ₂ H and SO ₃ H when they have a hydrogen ion as a counter ion.

M ₁₁ , m ₁₂ , and m ₁₃ represent a number of 0 or more necessary for balancing the charges, preferably a number of 0-4, more preferably a number of 0-1 and a molecule It is 0 when a salt is formed therein.

Next, specific examples of the sensitizing dye of the present invention are shown below, but of course, the sensitizing dye of the present invention is not limited to these.

[0122]

[Chemical 40]

[0123]

[Chemical 41]

[0124]

[Chemical 42]

[0125]

[Chemical 43]

The dye of the present invention is F.M.Harmer.
(FM Harmer) "Heterocyclic Compounds-
Cyanine soybean and related compounds
(Heterocyclic Compounds-Cyanine Dyes and Related C
ompounds) ", John Willie & Sons (Joh
n Wiley & Sons) -New York, London, 196
4 Years, DMSturmer, "Heterocyclic Compounds-Special Topics in Heterocyclic Chemistry (Heter
ocyclic Compounds-Special topics in heterocyclic c
hemistry) ", Chapter 18, Section 14, 482-51
Page 5, John Wiley and Sons
& Sons) -New York, London, 1977,
"Rodd's Chemistry of Carbon Compounds" 2nd.Ed.v
ol.IV, partB, 1977, Chapter 15, 369-42
Page 2, Elsevier Science Publishing Company In
c.) It can be synthesized based on the method described in the publisher, New York, etc.

In the present invention, one kind of sensitizing dye may be used, but two or more kinds may be used, and a combination of sensitizing dyes is often used particularly for the purpose of supersensitization. Typical examples thereof are US Pat. Nos. 2,688,545 and 2,977,
No. 229, No. 3,397,060, No. 3,522,0
No. 52, No. 3,527, 641, No. 3, 617, 29
No. 3, No. 3,628,964, No. 3,666,480
Issue 3, Issue 3,672,898, Issue 3,679,428
No. 3,303,377, No. 3,769,301
Nos. 3,814,609 and 3,837,862
No. 4,026,707, British Patent 1,344,2
No. 81, No. 1,507, 803, Japanese Patent Publication No. 43-493
No. 36, No. 53-12375, JP-A No. 52-1106.
18 and 52-109925.

Along with the sensitizing dye, a dye having no spectral sensitizing action itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion.

Supersensitizers useful in spectral sensitization in the present invention (for example, pyrimidylamino compounds, triazinylamino compounds, azolium compounds, aminostyryl compounds, aromatic organic acid formaldehyde condensates, azaindene compounds, cadmium salts). , And a combination of a supersensitizer and a sensitizing dye are described in, for example, US Pat. No. 3,511,66.
No. 4, No. 3,615, 613, No. 3, 615, 632
Issue No. 3,615,641 Issue No. 4,596,767
No. 4,945,038, 4,965,182
No. 4,965,182, 2,933,390
Issue No. 3,635,721 Issue 3,743,510
No. 3,617,295, No. 3,635,721, etc., and the method described in the above-mentioned patent is also preferable for the usage thereof.

In the present invention, the time for adding a sensitizing dye (also for a supersensitizer) to the silver halide emulsion of the present invention has been found to be useful until now. Any of the steps may be performed. For example,
US Pat. Nos. 2,735,766 and 3,628,960
Nos. 4,183,756, 4,225,666
No. 58-184142 and 60-19674.
No. 9, etc., the time before the grain formation step of silver halide and / or before desalting, during the desalting step and / or after the desalting and before the start of chemical ripening, JP 58
As disclosed in JP-A-113920, it may be added at any time or step immediately before the chemical ripening or during the step, or after the chemical ripening and before the coating until the emulsion is coated. Also, US Pat. No. 4,225,666
As disclosed in JP-A No. 58-7629 and the like, the same compound alone or in combination with a compound having a different structure can be used, for example, during the grain forming step and during the chemical ripening step or after the completion of the chemical ripening step. Or may be added in divided portions such as before chemical ripening or before and after chemical ripening, or may be added by changing the kind of compound and combination of compounds to be added in divided portions. .

In the present invention, the addition amount of the sensitizing dye (the same applies to the supersensitizer) varies depending on the shape and size of the silver halide grains, and any addition amount may be used. Per mol, preferably 1 x 1
0 ^-8 to 8 × 10 ^-1 mol, more preferably 1 × 10 ^-6 to 8
It can be used at × 10 ^-3 mol. For example, when the size of silver halide grains is 0.2 to 1.3 μm, the addition amount of 2 × 10 ^{−6 to} 3.5 × 10 ⁻³ mol is preferable per mol of silver halide, and 7.5 mol is preferable. × 10 ^{-6 to} 1.5 × 10
^A more preferred amount is ^-3 mol.

In the present invention, the sensitizing dye (also for the supersensitizer) can be directly dispersed in the emulsion. Further, these may be first dissolved in a suitable solvent such as methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine or a mixed solvent thereof, and added to the emulsion in the form of a solution. At this time, additives such as a base, an acid, and a surfactant can be coexistent. Ultrasonic waves can also be used for dissolution. As a method of adding this compound, as described in US Pat. No. 3,469,987, the compound is dissolved in a volatile organic solvent, and the solution is dispersed in a hydrophilic colloid to prepare a dispersion of this compound. The method of adding to the emulsion,
As described in JP-B-46-24185, a method of dispersing in a water-soluble solvent and adding this dispersion into an emulsion, as described in US Pat. No. 3,822,135,
A method in which a compound is dissolved in a surfactant and the solution is added to the emulsion, a method in which a compound for red-shifting is used to dissolve the compound and the solution is added to the emulsion as described in JP-A-51-74624. As described in JP-A-50-80826, a method in which a compound is dissolved in an acid containing substantially no water and the solution is added to the emulsion is used. In addition, U.S. Pat. No. 2,912,343 is used for addition to the emulsion.
Issue 3, Issue 3,342,605, Issue 2,996,287
No. 3,429,835 and the like.

In the present invention, any known processing composition can be used for each processing bath such as color development, bleaching, fixing, washing, stabilizing, adjusting, black and white developing, reversal and pre-bleaching. Details thereof are described in, for example, JP 2001-92090 A.
No., page 32, right column, line 9 to page 38, right column, line 30,
JP-A-2001-109117, page 30, right column 34
Lines to page 37, right column, line 37.

In addition to the above treatment bath, a treatment bath containing the compound of the present invention may be separately provided. This bath will be referred to as an absorption bath. The absorbing bath or the composition thereof may simply be an aqueous solution of the compound of the present invention, or a composition according to the washing composition and the stable composition. It is a preferred embodiment to add a compound which increases the solubility of the compound of the present invention to the absorption bath or its composition. For example, ethylene glycols, alkanolamines, aryl sulfonic acids,
Alkyl sulfonic acids or JP-A-11-17464
The urea compound described in 3 or the like can be added. Further, a surface active agent such as polyethylene glycol, a block polymer of polyethylene glycol and polypropylene glycol, an alkyl ethoxylate or an alkylnaphthalene sulfonic acid can be added.

Of these, polyethylene glycol having an average molecular weight of 300 to 2000, a block polymer of polyethylene glycol and polypropylene glycol, and ethylene urea are particularly preferable. When a compound which increases the solubility is added, its concentration is 0.1 to 100 g / L, preferably 0.5 to 50 g / L, more preferably 1 to 20.
g / L.

The concentration of the compound of the present invention in the working solution is 0.05 to 20 mmol / L, preferably 0.1.
5 to 15 mmol / L, more preferably 0.2 to 10 m
It is mol / L. When the treatment composition containing the compound of the present invention is used after being diluted with water or another treatment composition, the concentration in the treatment composition is a value obtained by multiplying the concentration in the working solution by the concentration factor. .

Light irradiation or contact with an oxidizing agent is carried out after the silver halide photographic light-sensitive material incorporates the compound of the present invention. A known light source can be used for light irradiation. That is, various fluorescent lamps, incandescent lamps, halogen lamps, deuterium lamps, mercury lamps, xenon lamps, flash lamps, sodium lamps and the like can be mentioned. In addition, tank-stain lamps and flash lamps for photography can also be mentioned. Further, US Pat. No. 4,500,6 such as a light emitting diode, a laser light source, and a CRT light source used as a light source for recording an image on a photosensitive material.
The light source described in No. 26, column 56 can also be used. The light irradiation amount is usually 1 × 10 ⁴ to 4 × 10 ⁶ lux · second, preferably 2 × 10 ⁴ to 2 × 10 ⁶ lux · second, more preferably 5 × 10 ⁴ to 1 × 10 ⁶ lux · second. is there.

Of these, ultraviolet light (wavelength is usually 400 nm
Hereinafter, it is preferably 250 to 375 nm light. A), that is, a fluorescent lamp, a deuterium lamp, and a xenon lamp are preferable, and a fluorescent lamp and a xenon lamp are particularly preferable. Japanese Patent Laid-Open No. 5-
The optical fixing device of the color thermal printer disclosed in JP-A-155135 and JP-A-6-40057 is a preferred embodiment for irradiating the light-sensitive material with light in the present invention. The light irradiation time is several milliseconds to several tens of seconds depending on the intensity of the light source.

Light irradiation to the silver halide photographic light-sensitive material is carried out after the absorption step of incorporating the compound of the present invention into the silver halide photographic light-sensitive material. Preferred specific examples of the treatment process will be given below, but the treatment process is not limited thereto. Color development-bleach-fix-washing-stability-absorption-light irradiation-dry color development-bleach-fix-wash-absorption-light irradiation-stable-dry color development-bleach-fix-stable-absorption-light irradiation-dry color Development-bleaching-fixing-absorption-light irradiation-stable-dry color development-bleaching-fixing-water washing-absorption-light irradiation-dry color development-bleaching-fixing-absorption-light irradiation-water washing-drying color development-bleaching-fixing -Washing-Absorption-Light irradiation-Water washing-Drying and the desilvering process consisting of bleaching and fixing, bleach-fixing and bleaching-
Either bleach-fixing or bleach-fixing-fixing may be used. Further, black and white development and reversal may be performed as a pre-process of color development.

Next, contact with an oxidizing agent will be described. Any oxidizing agent may be used for this oxidative treatment, and for example, those described in the following documents can be preferably used. Specific examples include manganese compounds (for example, potassium permanganate and manganese dioxide), chromic acid compounds (for example, CrO ₃ ), osmium tetroxide, ruthenium tetroxide, and other metal oxidizers described in the literature ( For example, lead oxide, lead acetate, mercury oxide, mercury acetate, silver carbonate, silver oxide, silver nitrate, thallium acetate, thallium nitrate, copper chloride, copper acetate, palladium chloride, iron chloride, potassium ferricyanide, VOCl ₃ , V ₂
O ₅ , cerium acetate, ammonium cerium nitrate (CA
N), sodium bismuthate, nickel peroxide, peracids and peroxides (eg, metachloroperbenzoic acid (MCPBA), perbenzoic acid, oxidation with organic compounds (eg, dimethylsulfoxide / oxalyl chloride, dimethylsulfoxide / Trifluoroacetic anhydride, dimethyl sulfoxide / dicyclohexylcarbodiimide, quinones (2,3-dichloro-5,6-dicyano-1,4-
Benzoquinone, etc.), nitrobenzene, p-nitrosodimethylaniline, dimethylaminopyridine N-oxide,
Triphenylmethyl cation, diethyl azodicarboxylate, diphenyl nitroxide, tetrabutylammonium periodate, 2-sulfonyloxaziridine, iodosobenzenediacetate), oxygen, ozone, selenium dioxide, chlorine, bromine, iodine, bromine- Hexamethylphosphoramide, sodium hypochlorite, sodium chlorite,
Sodium chlorate, sodium hypobromite, orthoperiodic acid, nitric acid, nitrous acid, nitrogen dioxide, potassium nitrosodisulfonate, ammonium persulfate, microorganisms and enzymes, electrode (anodic) oxidation, etc. For example hydrogen peroxide and its adducts (eg NaBO ₂ .H ₂
O ₂ · 3H ₂ O, 2NaCO ₃ · 3H ₂ O ₂ , Na ₄ P ₂ O ₇ ·
_{2H 2 O 2, 2Na 2 SO} 4 · H 2 O 2 · 2H 2 O), peroxy acid salt _{(e.g., K 2 S 2 O 8,} K 2 C 2 O 6, K 2 P
₂ O ₈ ), a peroxy complex compound (for example, K ₂ [Ti
(O ₂ ) C ₂ O ₄ ] ・ 3H ₂ O, 4K ₂ SO ₄・ Ti (O ₂ )
OH ・ SO ₄・ 2H ₂ O, Na ₃ [VO (O ₂ ) (C _{2
H 4) 2] · 6H 2} O), K 2 Cr 2 O 7, potassium periodate, potassium hexacyanoferrate ferric acid, thiosulfonates, peracetic acid, N- bromosuccinimide, chloramine T, chloramine B, Fe (III) 1,3-PDTA, F
e (III) EDTA and the like. The electron-donor type radical generator of the present invention reacts with these oxidizing agents to generate active radical species, and the radical species attack the sensitizing dye to cause the sensitizing dye to be decolored to leave the sensitizing dye in the sensitizing material. Reduce color. Jerry March, Advanced Organic Chemistry (Advan)
ced Organic Chemistry, John Wiley and Sons (John Wiley)
& Sons), New York
Chapter 19, Oxidati (1992)
ons And Reductions, p. 1158
~ 1238, edited by The Chemical Society of Japan, 4th edition Experimental Chemistry Lecture, Volume 23, Organic Synthesis V, Oxidation Reaction, Maruzen (1991).

When the silver halide photographic light-sensitive material containing or incorporating the compound of the present invention is brought into contact with an oxidizing agent, the oxidizing agent may be supplied in any form, and it is particularly preferable to supply it as a solution. The oxidizing agent solution may be brought into contact with the silver halide photographic light-sensitive material by any method such as spraying or spraying with a line jet, coating with a roller or a sheet, adhesion with a sheet, and dipping similar to a usual photographic processing step. Here, the sheet means a polymer fiber cloth capable of holding an oxidant solution. The concentration of the oxidant solution is preferably 0.005 to 3.0 mol / L, more preferably 0.01 to 1.5 mol / L, and further preferably 0.02 to 0.5 mol / L. When the treating composition containing an oxidizing agent is used after being diluted with water or another treating composition, the concentration in the treating composition is the concentration in the working solution multiplied by the concentration factor.

It is a preferred embodiment that the silver halide photographic light-sensitive material is immersed in a processing bath containing the oxidant in order to bring the silver halide photographic light-sensitive material into contact with the oxidizing agent in the developing step. This bath will be called an oxidation bath. The oxidizing bath or the composition thereof may be simply an aqueous solution of the oxidizing agent, or may be a composition according to the washing composition and the stable composition. It is a preferred embodiment to add a compound that increases the solubility of the compound of the present invention to the oxidation bath or its composition. Examples of organic oxidizing agents include ethylene glycols, alkanolamines, aryl sulfonic acids,
Alkyl sulfonic acids or JP-A-11-17464
It is useful to add the urea compound described in 3 above. Further, a surface active agent such as polyethylene glycol, a block polymer of polyethylene glycol and polypropylene glycol, an alkyl ethoxylate or an alkylnaphthalene sulfonic acid can be added.

Further, an arbitrary buffer may be added to the oxidizing bath in order to adjust the oxidizing power and solubility of the oxidizing agent.
Examples of the inorganic buffering agents include carbonates, bicarbonates, phosphates, borates, tetraborates and the like, and potassium salts, sodium salts or ammonium salts are preferable. As the organic buffer, succinic acid, maleic acid, glycolic acid, malonic acid, fumaric acid, succinic acid, sulfosuccinic acid,
Organic acids such as acetic acid or organic bases such as imidazole and dimethylimidazole can be preferably used.

The oxidation bath treatment of the silver halide photographic light-sensitive material is carried out after the absorption step of incorporating the compound of the present invention into the silver halide photographic light-sensitive material. Preferred specific examples of the treatment process will be given below, but the treatment process is not limited thereto. Color development-bleaching-fixing-washing-stability-absorption-oxidation-drying Color development-bleaching-fixing-washing-absorption-oxidation-stable-drying color development-bleaching-fixing-stable-absorption-oxidation-drying color development-bleaching -Fixing-Absorption-Oxidation-Stable-Dry color development-Bleach-Fixing-Water washing-Absorption-Oxidation-Dry color development-Bleach-Fixing-Absorption-Oxidation-Water washing-Dry color development-Bleach-Fixing-Water washing-Absorption-Oxidation -Washing-Drying, and desilvering process consisting of bleaching and fixing, bleach-fixing and bleaching-
Either bleach-fixing or bleach-fixing-fixing may be used. Further, black and white development and reversal may be performed as a pre-process of color development.
Furthermore, it is possible to combine both oxidation and bleaching as follows. Color development-washing-absorption-bleaching (oxidation) -fixing-washing-drying Color development-washing-absorption-bleaching (oxidation) -fixing-stable-drying

[0145]

Examples The following shows that the sensitizing dye stain can be reduced by irradiating a silver halide photographic light-sensitive material with light in the presence of the compound of the present invention or by bringing it into contact with an oxidizing agent.
The present invention will be described in more detail by way of examples, but the present invention is not limited thereto.

Example 1 [Preparation of Photosensitive Material Sample] After corona discharge treatment was applied to the surface of a support whose both sides were coated with polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided, and Apply the first to seventh layers in order,
Silver halide color photographic light-sensitive material P having the following layer structure
-1 was created. The coating liquid for each photographic constituent layer was prepared as follows.

Preparation of fifth layer coating solution 250 g of cyan coupler (ExC), color image stabilizer (Cp
d-1) 250 g, color image stabilizer (Cpd-14) 30
g, color image stabilizer (Cpd-15) 100 g, color image stabilizer (Cpd-16) 80 g, color image stabilizer (Cpd-17)
50 g and 10 g of color image stabilizer (Cpd-18) are dissolved in 230 g of solvent (Solv-5) and 350 ml of ethyl acetate, and this liquid is emulsified and dispersed in 6500 g of 10% gelatin aqueous solution containing 25 g of sodium dodecylbenzenesulfonate. Dispersion C was prepared. On the other hand, silver chlorobromide emulsion C
(Cube, 5: 5 mixture of large size emulsion C having an average grain size of 0.40 μm and small size emulsion C having a grain size of 0.30 μm (silver mole ratio). Coefficients of variation of grain size distribution are 0.09 and 0.11, respectively. For each size emulsion, 0.5 mol% of silver bromide was localized on a part of the grain surface based on the silver chloride emulsion). In this emulsion, after-sensitized red sensitizing dyes G and H were added to the large-sized emulsion C per mol of silver in an amount of 9.0 × 10 ^-5 mol and the small-sized emulsion C respectively.
12.0 × 10 ⁻⁵ mol, respectively. The chemical ripening of this emulsion was optimally performed by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion C and the silver chlorobromide emulsion C were mixed and dissolved to prepare a coating solution for the fifth layer having the following composition. The emulsion coating amount indicates a coating amount equivalent to silver.

The coating solutions for the first to fourth layers, the sixth layer, and the seventh layer were prepared in the same manner as the coating solution for the fifth layer. As the gelatin hardening agent for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. A for each layer
b-1, Ab-2, Ab-3, and Ab-4, respectively, in a total amount of 15.0 mg / m ² , 60.0 mg / m ² , 5.0.
It was added as a mg / m ² and 10.0 mg / m ^2.

[0149]

[Chemical 44]

The following spectral sensitizing dyes were used in the silver chlorobromide emulsion of each photosensitive emulsion layer. Blue-sensitive emulsion layer

[0151]

[Chemical formula 45]

(Sensitizing dyes A and C, respectively, per mol of silver halide, 0.42 × 1 for a large-sized emulsion)
0 ^-4 mol, and 0.50 × 10 ^-4 mol for a small size emulsion. Sensitizing dye B is added per mol of silver halide,
3.4 × 10 ⁻⁴ mol was added to the large size emulsion and 4.1 × 10 ⁻⁴ mol was added to the small size emulsion. )

Green-sensitive emulsion layer

[0154]

[Chemical formula 46]

(Sensitizing dye D was added per mol of silver halide in an amount of 3.0 × 10 ^-4 mol for a large size emulsion and 3.6 × 10 ^-4 mol for a small size emulsion. Sensitizing dye E was added per mol of silver halide in an amount of 4.0 × 10 ⁻⁴ mol for a large-sized emulsion and 7.0 × 10 ⁻⁵ mol for a small-sized emulsion. F is 2.0 × per mol of silver halide for large-sized emulsions.
10 ⁻⁴ mol, and 2.8 × 10 ⁻⁴ mol was added to the small size emulsion. )

Red-sensitive emulsion layer

[0157]

[Chemical 47]

(Sensitizing dyes G and H were used per mol of silver halide of 9.0 × 10 for a large-sized emulsion.
^-5 mol, and 12.0 × 10 ^-5 mol was added to the small size emulsion. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ^-3 mol per mol of silver halide. )

[0159]

[Chemical 48]

Blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer
1- (3-methylureidophenyl) -5 for the emulsion layer
-Mercaptotetrazole was added to each silver halide.
3.3 x 10 per le^-FourMole, 1.0 × 10^-3Mole and
And 5.9 x 10^-FourMol added. Second layer, fourth layer, sixth layer
0.2mg / m for each layer and 7th layer², 0.2
mg / m², 0.6 mg / m², 0.1 mg / m² Becomes
So added. For blue-sensitive emulsion layer and green-sensitive emulsion layer
4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene per mol of silver halide
1 x 10 ^-FourMole, 2 × 10^-FourMol added. Red sensitive emulsion
Copolymer latex of methacrylic acid and butyl acrylate
Cousin (mass ratio 1: 1, average molecular weight 200,000-400)
000) is 0.05 g / m²Was added. Second layer, fourth layer
And catechol-3,5-disulfonic acid dina
Thorium 6mg / m², 6 mg / m², 18m
g / m²Was added. Irradiation prevention
In order to add the following dyes (the amount in parentheses indicates the coating amount):
Added

[0161]

[Chemical 49]

(Layer Structure) Each layer structure is shown below. Numbers indicate coating materials (g / m ² ). The silver halide emulsion shows the equivalent amount of silver coating. [White pigment polyethylene resin of the first layer side (TiO _2: content of 16 wt%, ZnO: content of 4 wt%] Support Polyethylene resin laminated paper with a fluorescent whitening agent (4,4'-bis (5- Methylbenzoxazolyl)
Stilbene content 0.03% by mass, containing bluish dye (ulterior blue)] First layer (blue sensitive emulsion layer) Silver chlorobromide emulsion A (cubic, large size emulsion A with an average grain size of 0.74 μm and 0) 5: 5 mixture with 0.65 μm small size emulsion A (molar ratio of silver) .Coefficients of variation of grain size distribution are 0.08 and 0.10, respectively. 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) ) 0.04 Color image stabilizer (Cpd-3) 0.07 Solvent (Solv-1) 0.21

[0163] Second layer (color mixing prevention layer)       Gelatin 0.99       Color mixing inhibitor (Cpd-4) 0.09       Color mixing prevention aid (Cpd-5) 0.018       Stabilizer (Cpd-6) 0.13       Color mixing inhibitor (Cpd-7) 0.01       Solvent (Solv-1) 0.06       Solvent (Solv-2) 0.22

[0164] Third layer (green sensitive emulsion layer)     Silver chlorobromide emulsion B (cubic, large-sized emulsion B having an average grain size of 0.45 μm 1: 3 mixture with 0.35 μm small size emulsion B (silver molar ratio). Particle size distribution The coefficient of variation of is 0.10 and 0.08, respectively. Salt size 0.4 mol% silver bromide The silver halide was locally contained in a part of the surface of the grain having the base material. )                                                 0.14       Gelatin 1.36       Magenta coupler (ExM) 0.15       UV absorber (UV-1) 0.05       Ultraviolet absorber (UV-2) 0.03       Ultraviolet absorber (UV-3) 0.02       Ultraviolet absorber (UV-4) 0.04       Color image stabilizer (Cpd-2) 0.02       Color mixing inhibitor (Cpd-4) 0.002       Stabilizer (Cpd-6) 0.09       Color image stabilizer (Cpd-8) 0.02       Color image stabilizer (Cpd-9) 0.03       Color image stabilizer (Cpd-10) 0.01       Color image stabilizer (Cpd-11) 0.0001       Solvent (Solv-3) 0.10       Solvent (Solv-4) 0.20       Solvent (Solv-5) 0.20       Solvent (Solv-8) 0.05

[0165] Fourth layer (color mixing prevention layer)       Gelatin 0.71       Color mixing inhibitor (Cpd-4) 0.06       Color mixing prevention aid (Cpd-5) 0.013       Stabilizer (Cpd-6) 0.10       Stabilizer (Cpd-12) 0.01       Color mixing inhibitor (Cpd-7) 0.007       Solvent (Solv-1) 0.04       Solvent (Solv-2) 0.16

[0166] Fifth layer (red sensitive emulsion layer)     Silver chlorobromide emulsion C (cube, large size emulsion C having an average grain size of 0.40 μm 5: 5 mixture with 0.30 μm small size emulsion C (silver molar ratio). Particle size distribution Coefficient of variation is 0.09 and 0.11. Salt size 0.5 mol% silver bromide The silver halide was locally contained in a part of the surface of the grain having the base material. )                                                 0.20       Gelatin 1.11.       Cyan coupler (ExC) 0.25       Color image stabilizer (Cpd-1) 0.25       Color image stabilizer (Cpd-14) 0.03       Color image stabilizer (Cpd-15) 0.10       Color image stabilizer (Cpd-16) 0.08       Color image stabilizer (Cpd-17) 0.05       Color image stabilizer (Cpd-18) 0.01       Solvent (Solv-5) 0.23

[0167] Sixth layer (UV absorption layer)       Gelatin 0.46       Ultraviolet absorber (UV-1) 0.14       UV absorber (UV-2) 0.05       Ultraviolet absorber (UV-3) 0.04       UV absorber (UV-4) 0.05       Ultraviolet absorber (UV-5) 0.02       Solvent (Solv-7) 0.25

[0168] Seventh layer (protective layer)       Gelatin 1.00       Acrylic modified copolymer of polyvinyl alcohol       (Modification degree 17%) 0.04       Liquid paraffin 0.02       Surfactant (Cpd-13) 0.01

[0169]

[Chemical 50]

[0170]

[Chemical 51]

[0171]

[Chemical 52]

[0172]

[Chemical 53]

[0173]

[Chemical 54]

[0174]

[Chemical 55]

[0175]

[Chemical 56]

[0176]

[Chemical 57]

[0177]

[Chemical 58]

The photosensitive material sample P-1 was subjected to imagewise exposure and the steps such as the following development processing were sequentially carried out.

[0179] [Processing process]       Treatment process temperature time       Color development 38.5 ℃ 45 seconds       Bleach-fixing 38.0 ° C 45 seconds       Washing with water 38.0 ° C for 10 seconds       Absorption room temperature 30 seconds       Light irradiation room temperature 20 seconds       Rinsing at room temperature 10 seconds       Dry 80 ℃

The composition of each processing liquid is as follows. [Color developer]       800 mL of water       Triisopropanolamine 8.8g       Ethylenediaminetetraacetic acid 4.0 g       Sodium sulfite 0.10g       Potassium chloride 10.0g       4,5-dihydroxybenzene-       Sodium 1,3-disulfonate 0.50 g       Disodium-N, N-bis (sulfonate       Ethyl) hydroxylamine 8.5 g       4-amino-3-methyl-N-ethyl-N-       (Β-methanesulfonamidoethyl) aniline       ・ 3/2 Sulfate ・ Monohydrate 4.8g       26.3 g potassium carbonate       Add water to a total volume of 1000 mL       pH (25 ° C, adjusted with sulfuric acid and KOH) 10.15

[0181] [Bleaching fixer]       400 mL of water       Ammonium thiosulfate (750 g / mL) 110 mL       Ethylenediaminetetrairon (III) acetate ammonium 42g       Ethylenediamine tetraacetic acid 5g       Ammonium sulfate 12g       Imidazole 10g       Ethylenediaminetetraacetic acid 9.0g       Ammonium sulfite 45g       m-carboxybenzenesulfinic acid 8g       Add water to a total volume of 1000 mL       pH (25 ° C, adjusted with nitric acid and ammonia water) 6.50

[0182] [Absorbing liquid]       Compounds of the invention Table 1       Additives Table 1       Add water to a total volume of 1000 mL

[Light Irradiation] The photosensitive material was irradiated with light of 4 × 10 ⁵ lux · sec using a three-wavelength type daylight color (40 type) fluorescent lamp.

[Evaluation] The reflection spectrum of the minimum density portion was measured using a U-3500 type spectrophotometer manufactured by Hitachi Ltd. equipped with a 150 mmΦ integrating sphere for the photosensitive material sample which was imagewise exposed and developed. Then 450
The absorbance at nm was designated as D _B. Next, each sample was washed with distilled water at 40 ° C. for 5 minutes, dried and then subjected to the same measurement.
The absorbance at 450 nm at this time was _defined as D _Bw . ΔD _BW was calculated based on the following formula, and the degree of stain due to the residual sensitizing dye was evaluated. A smaller ΔD _B means that the residual sensitizing dye is smaller and the stain reducing effect is larger. ΔD _B = D _B −D _BW

No absorbing liquid was used in the processing step, and instead, the compounds (I-1) and (I-9) of the present invention were added to the first layer (blue-sensitive emulsion layer) per mol of silver halide. 5.0 × 10 for large emulsion and small emulsion
^-4 moles of Samples 18 and 19 added (I-48) instead of the sensitizing dyes A, B and C of the first layer (blue sensitive emulsion layer),
A sample 20 using (I-45) and (I-46) was prepared. The results are shown in Table 1.

[0186]

[Table 1]

[0187] PEG300: Polyethylene glycol average molecular weight 300 EU: Ethylene urea

In Samples 11 to 17, Samples 13 to 15 and 17 prepared by adding the compound of the present invention to Samples 11, 12 and 16 in which the compound of the present invention was not added to the absorption bath.
Showed that the yellow density was lowered and the sensitizing dye stain was reduced. Further, the stain reducing effect can be enhanced by adding an additive to the absorption bath to increase the concentration of the compound of the present invention. Further, in Samples 18 to 20 containing the compound of the present invention in the light-sensitive material in advance,
It was shown that the yellow density was lowered and the sensitizing dye stain was reduced.

Example 2 The same photosensitive material was prepared as in Example 1 except that the processing steps were changed as follows, and the same evaluation was performed. The results are shown in Table 2.

[0190] [Processing process]       Treatment process temperature time       Color development 38.5 ℃ 45 seconds       Bleach-fixing 38.0 ° C 45 seconds       Washing with water 38.0 ° C for 10 seconds       Absorption room temperature 20 seconds       Oxidation room temperature 20 seconds       Rinsing at room temperature 10 seconds       Dry 80 ℃

The oxidizing solution was prepared as follows. [Oxidizing liquid]       Oxidizing agent (sodium hypochlorite) addition amount 10mmol       Add water to a total volume of 1000 mL       pH (25 ℃, adjusted with sulfuric acid and sodium hydroxide) 8.5

[0192]

[Table 2]

[0193] PEG300: Polyethylene glycol average molecular weight 300 EU: Ethylene urea

From Table 2, even when an oxidizing bath is used,
Similar to Example 1, when the compound of the present invention is present,
It was shown that the yellow density was lowered and the sensitizing dye stain was reduced.

Example 3 Fuji Color Superior Zoom Master 800 manufactured by Fuji Photo Film Co., Ltd. exposed imagewise was subjected to Process CN-16L manufactured by the same. Next, the compound of the present invention was added to the stabilizing bath of Process CN-16L, and Process CN-16L was applied to the above light-sensitive material. Using a U-3500 type spectrophotometer manufactured by Hitachi, Ltd., the transmission absorption measurement of the minimum density part was performed, and the absorbances D ₅₀₀ ⁰ and D ₅₅₅ ⁰ at ₅₀₀ nm and 555 nm of the two processed color negative films were obtained. . This Macbeth product
6 in UV mode of The Judge Model No. JR4-20I
After irradiation with light for 0 seconds, the transmission absorption was measured again. The absorbances at 500 nm and 555 nm at this time are designated as D ₅₀₀ and D ₅₅₅ . Differences in stain before and after light irradiation, ΔD ₅₀₀ and ΔD _555, were calculated by the following equation. The larger the values of ΔD ₅₀₀ and ΔD ₅₅₅ , the greater the stain reduction effect. The results are shown in Table 3.
Shown in. ΔD ₅₀₀ = D ₅₀₀ ⁰ -D ₅₀₀ ΔD ₅₅₅ = D ₅₅₅ ⁰ -D ₅₅₅

[0196]

[Table 3]

From this, it was shown that the stain was reduced by the light irradiation in the sample 32 which was treated with the stabilizing solution containing the compound of the present invention as compared with the sample 31 which was subjected to the usual treatment. . Further, as in the first and second embodiments,
When the compound of the present invention was contained in the light-sensitive material in advance, or when the compound was treated with an oxidizing bath instead of light irradiation, the stain was similarly reduced.

Example 4 Fujichrome Provia 100 manufactured by Fuji Photo Film Co., which was imagewise exposed, was subjected to the process CR-56P manufactured by the same company. Next, the compound of the present invention was added to the stabilizing bath of Process CR-56P, and the above light-sensitive material was subjected to Process CR-56P. Using a U-3500 spectrophotometer manufactured by Hitachi, Ltd., the transmission absorption measurement of the minimum density portion was performed, and the absorbance D _{540 of the} two treated color reversal films at 540 nm was measured.
I asked for ⁰ . This Judge model manufactured by Macbeth
After irradiating light for 60 seconds in the UV mode of No. JR4-20I,
The transmission absorption was measured again. The absorbance at 540 nm at this time is defined as D ₅₄₀ . The difference ΔD ₅₄₀ in stain before and after the light irradiation was calculated by the following formula. ΔD ₅₄₀ means that the larger the value, the greater the stain reduction effect. The results are shown in Table 4. ΔD ₅₄₀ = D ₅₄₀ ⁰ −D ₅₄₀

[0199]

[Table 4]

From this, it was shown that the stain was reduced by the light irradiation in the sample 42 which was treated with the stabilizing solution containing the compound of the present invention as compared with the sample 41 which was subjected to the usual treatment. Further, in the same manner as in Examples 1 and 2, when the compound of the present invention is contained in the light-sensitive material in advance, or
When the treatment was performed with an oxidizing bath instead of the light irradiation, the stain was similarly reduced.

[0201]

From Examples 1 to 4, it can be seen that according to the present invention, the stain caused by the residual sensitizing dye of the light-sensitive material can be reduced after the processing of the silver halide photographic light-sensitive material.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ identification code FI theme code (reference) G03C 7/407 G03C 7/407 7/42 7/42 11/00 11/00 501 501 F term (reference) 2H016 BD00 BK03 BL00 BL01 BL02 BL03 BL04 BL05 2H023 CD00

Claims (4)

[Claims] 1. A silver halide photographic light-sensitive material imagewise exposed to at least one of the following general formulas (I)
A method for processing a silver halide photographic light-sensitive material, which comprises irradiating with light in the presence of a compound represented by In formula (I) (X) _k- (L) _m- (AB) _n , X represents a silver halide adsorbing group or a light absorbing group.
L represents a divalent linking group. A represents an electron-donating group, B represents a leaving group or a hydrogen atom, and after oxidation, it is eliminated or deprotonated to generate a radical A. k and m each represent an integer of 0 to 3, and n represents 1 or 2. 2. A silver halide photographic light-sensitive material, which comprises bringing a silver halide photographic light-sensitive material into contact with an oxidizing agent in the presence of at least one compound represented by the general formula (I) according to claim 1. Material processing method. 3. The method for processing a silver halide photographic light-sensitive material according to claim 1, wherein the compound represented by the general formula (I) is used as an aqueous solution. 4. A processing composition for a silver halide photographic light-sensitive material, comprising a compound represented by the general formula (I).