JP2553907B2 - Silver halide photographic material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic light-sensitive material, and more specifically, it is photographically useful as a silver image (hereinafter abbreviated as image) in a development processing step. The present invention relates to a silver halide photographic light-sensitive material containing a compound that releases a functional group.

(Prior Art) It is known that the performance of a photographic image is remarkably improved by releasing a photographically useful reagent in a silver image-like manner simultaneously with the formation of a silver image.

For example, there are DIR couplers in the field of color photographic light-sensitive materials. The DIR coupler releases the development inhibitor by the coupling reaction with the oxidized color developer during development, thereby improving the graininess of the color image, improving the sharpness by the edge effect, and diffusing the inhibitor to other layers. Has the function of improving color reproducibility and the like and is described in detail in the following patent specifications.

U.S. Pat.Nos. 3,227,554, 4,248,962, Japanese Patent Publication 58
-9942, 51-16141, JP-A-52-90932, 56-11494
6, ibid 57-154234, ibid 58-188035, ibid 57-151944, ibid 58
-217932 etc.

Further, in recent years, improvement of graininess of a color image or increase of sensitivity can be achieved by using a coupler which releases a competing compound, a development accelerator or a fogging agent by a coupling reaction with an oxidized color developing agent. It is described in the book. British Patent No. 1,546,837, U.S. Patent No. 3,408,194, JP-A-57-138636, 57-150845,
59-50439, 59-170840, etc.

Alternatively, in a colored coupler having an azo dye moiety as a releasing group, a coupling reaction with an oxidized product of a color developing agent causes an azo dye to be released in an imagewise manner, and the azo dye flows out into a processing solution and is removed. By contrast, colored couplers having an azo dye are left in a reverse image to improve the color reproducibility by a masking effect. For example, JP-A-51
-26034, 51-110328, U.S. Pat. No. 4,0049,29, British Patent Nos. 1443875, 1443661, and the like.

As described above, the functional coupler that releases a photographically useful reagent greatly contributes to the improvement of the image quality and sensitivity of the Raler image. However, these functional couplers cannot be used in the fields of black-and-white photographic light-sensitive materials or diffusion transfer photographic fields without using color developers because the method of releasing photographically useful reagents is a coupling reaction with oxidized color developers. It has a theoretical drawback. Also the second
One of the drawbacks is that the azomethine dye formed has an unfavorable influence on the color reproduction of a color image, and in this regard, a colorless DIR coupler such as JP-A-49-77,
Nos. 635 and 50-20725) or dye efflux type couplers (for example, JP-A-59-168444) have been proposed.
Problems such as low coupling activity or remarkable contamination of the treatment liquid have not been solved yet.

Although the redox compound which solves the drawbacks of the functional coupler and releases the photographically useful reagent regardless of the kind of the developing agent has been earnestly developed, it must be said that it is still insufficient.

For example, JP-A-49-129536 and U.S. Pat.
No. 3,620,746, No. 4,332,878, No. 4,377,634 and the like, DIR-hydroquinones: DIR-aminophenols described in JP-A-52-57828 and the like: p-nitrobenzyl described in EP45,129 Derivatives; hydrazine derivatives described in U.S. Pat. No. 4,684,604 and the like; redox compounds having at least one carbonyl group described in JP-A-61-213847 are disclosed as known compounds, but they are specifically described in these patents. In many compounds, the release of the photographically useful reagent from the oxidant is as fast as practically possible, and those with fast release have poor storage stability. It was difficult to achieve both sexes.

(Object of the Invention) Therefore, a first object of the present invention is to provide a redox compound capable of releasing a photographically useful reagent regardless of the kind of the developing agent. A second object of the present invention is to provide a redox compound which is excellent in storage stability and has a fast release of a photographically useful reagent from an oxidant. A third object of the present invention is to provide a silver halide photographic light-sensitive material having improved image quality. A fourth object of the present invention is to provide a highly sensitive silver halide photographic light-sensitive material.

(Means for Solving Problems) Such an object is achieved by the present invention described below.

That is, the present invention provides a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer,
A silver halide photographic light-sensitive material containing at least one photographic reagent represented by the following general formula (I).

General formula (I) (In the formula, X represents a hydrogen atom or a group capable of becoming a hydrogen atom by a hydrolysis reaction. Time represents a divalent linking group, t represents 0 or 1. PUG represents a photographically useful group. V is a carbonyl group, a sulfonyl group, a sulfoxy group, (R ₀ represents an alkoxy group or an aryloxy group), an iminomethylene group, a thiocarbonyl group, or (W represents an electron-withdrawing group). R represents a hydrogen atom, an aliphatic group, an aromatic group, or Represents

 Hereinafter, a specific configuration of the present invention will be described in detail.

When X represents a group which can be converted into a hydrogen atom by a hydrolysis reaction, there can be mentioned some already known as a block group of a photographic reagent.

For example, JP-B-48-9968, JP-A-52-8,828,
No. 57-82,834, U.S. Pat.No. 3,311,476, JP-B-47-44,80
Those utilizing a block group such as an acyl group and a sulfonyl group described in US Pat. No. 3,615,617; JP-B-55-17369 (US Pat. No. 3,888,677), JP-B-55-9696
(U.S. Pat.No. 3,791,830), U.S. Pat.No. 55-34,927 (U.S. Pat.
No. 7,175), Nos. 59-105,642, and 59-105,640, those utilizing a block group that releases a photographically useful reagent by the so-called reverse Michael reaction, JP-B-54-39,727, U.S. Pat.No. 3,674,478, ibid. No. 3,932,480, No. 3,993,66
1, JP-A-57-135,944, 57-135,945, 57-1
JP-A No. 55-53,330, which uses a block group which releases a photographically useful reagent with the formation of a quinone methide or a quinone methide compound by intramolecular electron transfer described in 36,640;
Utilizing the intramolecular ring closure reaction described in JP-A-57-76,541 (US Pat. No. 4,335,200).
Nos. 57-135,949, 57-179,842, 59-137,
Nos. 945, 59-140,445, 59-219,741, 60-41,
Utilizing the 5- or 6-membered ring cleavage described in No. 034,
JP-A-59-201,057, 61-43,739, 61-95,346
Utilizing a block group which releases a photographic reagent by the Michael reaction described in JP-A No. 61-95347;
Examples thereof include those utilizing a block group such as imidomethyl group described in No. 158,638.

Time represents a divalent linking group and may have a timing adjusting function. t represents 0 or 1, and when t = 0, it means that PUG is directly bonded to V.

The divalent linking group represented by Time represents a group that releases PUG from Time-PUG released from the oxidized form of the redox mother nucleus through a one-step reaction or a reaction in more steps.

Examples of the divalent linking group represented by Time include a photographically useful group (PUG) obtained by an intramolecular ring-closing reaction of a p-nitrophenoxy derivative described in US Pat. No. 4,248,962 (JP-A-54-145,135). Emitting; U.S. Pat. No. 4,31
Nos. 0,612 (JP-A-55-53,330) and 4,358,525 which release PUG by an intramolecular ring closure reaction after ring cleavage; US Pat. Nos. 4,330,617, 4,446,216, and
4,483,919, succinic acid monoesters described in JP-A-59-121,328 and the like, which release PUG in association with the formation of an acid anhydride by the carboxyl group intramolecular ring closure reaction of the succinic acid monoester; U.S. Pat. No. 4,409,323 , 4,421,845, Research Journal, No. 21,228 (December 1981)
U.S. Pat. No. 4,416,977 (JP-A-57-135,944).
No.), JP-A Nos. 58-209,736 and 58-209,738, etc. to produce quinomonomethane or an analog thereof by electron transfer through a double bond conjugated with an aryloxy group or a heterocyclic oxy group. Detecting PUG; U.S. Pat. No. 4,420,554 (JP-A-57-136,640), JP-A-57-13
5,945, 57-188,035, 58-98,728 and 58
-209,737 PUG from the γ-position of the enamine by electron transfer of the portion having an enamine structure of the nitrogen-containing heterocyclic ring described in
Releasing PUG by an intramolecular ring-closing reaction of an oxy group generated by electron transfer to a carbonyl group conjugated with a nitrogen atom of a nitrogen-containing heterocycle described in JP-A-57-56,837; US Patent No. 4,146,396 (JP-A-52-909
32), JP-A-59-93,442, JP-A-59-75475, etc., which release PUG with formation of aldehydes; JP-A-51-146,828; JP-A-57-179,842; Same as 59-10
Those releasing PUG accompanied by decarboxylation of carboxyl group as described in JP 4,641; -O-COOCR _a R _b have the structure of -PUG, those which release PUG with the formation of aldehydes and subsequent decarboxylation Release of PUG with formation of isocyanate described in JP-A-60-7,429; U.S. Pat. No. 4,438,1
Examples thereof include those releasing PUG by a coupling reaction with an oxidant of a color developing agent described in JP-A No. 93 and the like.

Time is a divalent linking group (for example, a general formula (T-
1) to (T-10)) may be combined.

As the group represented by Time, the following general formula (T-1)
Those represented by (T-10) are preferred.

Here, (*) represents a site that binds to V in the general formula (I), and (*) (*) represents a site that binds to PUG.

General formula (T-1) In the formula, Q ₁ is (*)-O-, _{(*) - O-CH 2} -O -, (*) - O-CH 2 -, (*) -
O-CH ₂ -S-, Represents

Here, R ₁ represents a hydrogen atom, an aliphatic group, an aromatic group or a heterocyclic group.

X ₁ is a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, —O
-R ₂ , -SR ₂ , -CO-R _2, represents -SO-R _2, a cyano group, a halogen atom (e.g. fluorine, chlorine, bromine, iodine) and or nitro group.

Here, R ₂ and R ₃ may be the same or different and each represents a group having the same meaning as R ₁ . X ₂ represents the group described for R ₁ .

q represents an integer of 1 to 4. When q is 2 or more, X ₁
The substituents represented by may be the same or different. q
When there are two or more, X _1's may be linked to each other to form a ring.

 m represents 0, 1 or 2.

The group represented by formula (T-1) is described in, for example, US Pat.
4,248,962.

General formula (T-2) In the formula, Q ₁ , X ₁ , X ₂ and q have the same meaning as defined in formula (T-1).

General formula (T-3) In the formula, Q ₂ is (*)-O-, Represents

n is an integer of 1 to 4, preferably 1, 2 or 3.

R ₁ and X ₂ have the same meaning as defined in formula (T-1).

General formula (T-4) In the formula, Q ₃ is (*)-O-, _{(*) - O-CH 2} -O- or (*) - O-CH represent ₂ -S-.

R ₁ , R ₂ , R ₃ , X ₁ and q have the same meaning as defined in formula (T-1). The group represented by formula (T-4) is, for example, a timing group described in US Pat. No. 4,409,323.

General formula (T-5) In the formula, Q ₃ , R ₂ , R ₃ , X ₁ and q have the same meanings as defined in formula (T-4).

General formula (T-6) In the formula, X ₃ is selected from the group consisting of carbon, nitrogen, oxygen and sulfur, is a combination of at least one atom, and is an atomic group necessary for forming a 5-membered to 7-membered heterocycle. This heterocycle may be further condensed with a benzene ring or a 5- to 7-membered heterocycle. Preferred heterocycles include, for example, pyrrole, pyrazole, imidazole, triazole, furan, oxazole, thiophene, thiazole, pyridine, pyridazine, pyrimidine, pyrazine,
Examples include azepine, oxepin, indole, benzofuran and quinoline.

Q ₃ , X ₁ , q, R ₂ and R ₃ have the same meanings as defined in formula (T-4). The group represented by formula (T-6) is, for example, a timing group described in British Patent No. 2,096,783.

General formula (T-7) In the formula, X ₄ is a combination of at least one atom selected from carbon, nitrogen, oxygen or sulfur and is an atomic group necessary for forming a 5-membered to 7-membered heterocyclic group. X ₅ and X ₆ Or -N =. Here, R ₄ represents a hydrogen atom, an aliphatic group or an aromatic group. This heterocycle may be condensed with a benzene ring or a 5- to 7-membered heterocycle.

Preferred heterocycles include pyrrole, imidazole,
Examples thereof include triazole, furan, oxazole, oxadiazole, thiophene, thiazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, azepine, oxepin and isoquinoline.

Q ₃ , X ₁ and q have the same meanings as defined in formula (T-4).

General formula (T-8) In the formula, X ₉ is an atomic group necessary for forming a 5-membered to 7-membered heterocyclic ring, which is composed of a combination of at least one atom selected from carbon, nitrogen, oxygen and sulfur. X ₇ and X ₈ Alternatively, it is N-. This heterocycle may be condensed with a benzene ring or a 5- to 7-membered heterocycle. Preferred heterocycles include, for example, pyrrolidine, piperidine, benzotriazole and the like, in addition to those described in formula (T-6).

Q ₁ , X ₁ , X ₂ , m and q have the same meanings as defined in formula (T-1).

General formula (T-9) In the formula, X ₁₀ has the same meaning as X ₉ defined in formula (T-8). Q ₃ has the same meaning as defined in formula (T-4).

Preferred heterocycles are, for example, those shown below.

Here, X ₁ and q have the same meanings as defined in formula (T-1), and X ₁₁ represents a hydrogen atom, an aliphatic group, an aromatic group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, or a sulfamoyl group. Represents a heterocyclic group or a carbamoyl group. l represents 0 or 1.

General formula (T-10) In the formula, X ₁ and X ₂ are the general formula (T-1), and Q ₃ is the general formula (T-
It has the same meaning as defined in 4). n has the same meaning as defined in formula (T-3), preferably 1
Or 2.

In the above general formulas (T-1) to (T-10), X ₁ ,
When X ₂ , R ₁ , R ₂ , R ₃ and R ₄ contain a moiety of an aliphatic group,
It preferably has 1 to 20 carbon atoms and may be saturated or unsaturated, substituted or unsubstituted, linear or cyclic, linear or branched. X ₁ , X ₂ , R ₁ , R ₂ , R ₃ and R _{4 above}
Has a carbon atom number of 6 to 20, preferably 6 to 10, and more preferably a substituted or unsubstituted phenyl group. When X ₁ , X ₂ , R ₁ , R ₂ , R _{3 and} R ₄ each include a heterocyclic group moiety, a five-membered member containing at least one of a nitrogen atom, an oxygen atom or a sulfur atom as a hetero atom, or It is a six-membered heterocycle. The heterocyclic group is preferably a pyridyl group, a furyl group, a thienyl group, a triazolyl group, an imidazolyl group, a pyrazolyl group, a thiadiazolyl group, an oxadiazolyl group or a pyrrolidinyl group. The divalent linking group is preferably, for example, one shown below.

T- (33) (*) - O-CH 2 - (*) (*) PUG (denotes a group photographically useful as (Time _t PUG or PUG.

Examples of the photographically useful group include a development inhibitor, a development accelerator, a fogging agent, a coupler, a coupler releasing coupler, a diffusible or non-diffusible dye, a desilvering accelerator, a desilvering inhibitor, a silver halide solvent, Competitive compound, developer, auxiliary developer, fixing accelerator, fixing inhibitor, image stabilizer, toning agent, processing dependence improving agent, halftone improving agent, color image stabilizing agent, photographic dye, interface It represents an activator, a hardener, an ultraviolet absorber, a fluorescent whitening agent, a desensitizer, a contrast enhancer, a chelating agent, or the precursors thereof.

Since these photographically useful groups often overlap in terms of usefulness, representative examples will be specifically described below.

When PUG is a development inhibitor, the development inhibitor is a known development inhibitor that has a heteroatom and is attached through the heteroatom, such as CEKMees and theta.・ ETCH JAMES (THJa
mes) "The Theory of the Photographic Pro
cess "3rd edition, published by Macmillan, 1966, 3
It is described on pages 44 to 346.

As an example of the development inhibitor, a compound having a mercapto group bonded to a heterocycle, for example, a substituted or unsubstituted mercaptoazole (specifically, 1-phenyl-5-mercaptotetrazole, 1- (4-carboxyphenyl))
-5-mercaptotetrazole, 1- (3-hydroxyphenyl) -5-mercaptotetrazole, 1- (4-
Sulfophenyl) -5-mercaptotetrazole, 1-
(3-Sulfophenyl) -5-mercaptotetrazole, 1- (4-sulfamoylphenyl) -5-mercaptotetrazole, 1- (3-hexanoylaminophenyl) -5-mercaptotetrazole, 1-ethyl-5
-Mercaptotetrazole, 1- (2-carboxyethyl) -5-mercaptotetrazole, 2-methylthio-
5-mercapto-1,3,4-thiadiazole, 2- (2-
Carboxyethylthio) -5-mercapto-1,3,4-thiadiazole, 3-methyl-4-phenyl-5-mercapto-1,2,4-triazole, 2- (2-dimethylaminoethylthio) -5- Mercapto-1,3,4-thiadiazole, 1- (4-n-hexylcarbamoylphenyl)
-2-mercaptoimidazole, 3-acetylamino-
4-methyl-5-mercapto-1,2,4-triazole,
2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole,
2-mercapto-6-nitro-1,3-benzoxazole, 1- (1-naphthyl) -5-mercaptotetrazole, 2-phenyl-5-mercapto-1,3,4-oxadiazole, 1- {3 -(3-Methylureido) phenyl} -5-mercaptotetrazole, 1- (4-nitrophenyl) -5-mercaptotetrazole, 5- (2-
Ethylhexanoylamino) -2-mercaptobenzimidazole, etc.) and substituted or unsubstituted mercaptoazaindenes (specifically, 6-methyl-4-mercapto-1,3,3a, 7-tetrazaindene, 6 -Methyl-2-benzyl-4-mercapto-1,3,3a, 7-tetrazaindene, 6-phenyl, -4-mercaptotetrazaindene, 4,6-dimethyl-2-mercapto-1,3,3a , 7-Tetrazaindene etc.), substituted or unsubstituted mercaptopyrimidines (specifically 2-mercaptopyrimidine,
2-mercapto-4-methyl-6-hydroxypyrimidine, 2-mercapto-4-propylpyrimidine and the like). Heterocyclic compounds capable of producing imino silver, for example, substituted or unsubstituted benzotriazoles (specifically, benzotriazole, 5-nitrobenzotriazole, 5-methylbenzotriazole, 5,6-dichlorobenzotriazole, 5-bromo) Benzotriazole, 5
-Methoxybenzotriazole, 5-acetylaminobenzotriazole, 5-n-butylbenzotriazole, 5-nitro-6-chlorobenzotriazole, 5,6
-Dimethylbenzotriazole, 4,5,6,7-tetrachlorobenzotriazole, etc.) Substituted or unsubstituted indazoles (specifically, indazole, 5-nitroindazole, 3-nitroindazole, 3-chloro-5-
Nitroindazole, 3-cyanoindazole, 3-n
-Butylcarbamoylindazole, 5-nitro-3-
Methanesulfonylindazole, etc.), substituted or unsubstituted benzimidazoles (specifically, 5-nitrobenzimidazole, 4-nitrobenzimidazole,
5,6-dichlorobenzimidazole, 5-cyano-6-
Chlorbenzimidazole, 5-trifluoromethyl-
6-chlorobenzimidazole) and the like. Further, the development inhibitor becomes a compound having a development inhibitory property after being released from the redox mother nucleus of the general formula [I] by the substitution reaction following the redox reaction in the development processing step,
Further, it may be a compound which has substantially no development inhibitory property or a compound in which development is significantly reduced.

Thus, the development inhibitor whose development inhibitory property changes can be represented by the general formula [II].

Formula [II] -AF-CCD In formula [II], the group represented by AF is preferably the following. It is shown with the replacement position of CCD.
(*) (*) (*) Indicates the binding position to Time.

General formula (P-1) General formula (P-2) General formula (P-3) General formula (P-4) General formula (P-5) In the formula, G ₁ is a hydrogen atom, a halogen atom, an alkyl group (eg, methyl group, ethyl group, etc.), an acylamino group (eg, benzamide group, hexanamide group), an alkoxy group (eg, methoxy group, benzyloxy group), a sulfonamide group (Eg, methanesulfonamide group, benzenesulfonamide group), aryl group (eg, phenyl group, 4-
Chlorophenyl group), alkylthio group (eg methylthio group, butylthio group), alkylamino group (cyclohexylamino group, etc.), anilino group (anilino group, 4-methoxycarbonylanilino group, etc.), amino group, alkoxycarbonyl group (methoxycarbonyl group) Group, butoxycarbonyl group, etc.), acyloxy group (eg, acetyl group, butanoyl group, benzoyl group, etc.), nitro group, cyano group, sulfonyl group (butanesulfonyl group, benzenesulfonyl group, etc.), aryloxy group (phenoxy group, naphthyl group) Oxy group), hydroxy group, thioamide group (butanethioamide group, benzenethiocarbonamide group, etc.), carbamoyl group (carbamoyl group, N-arylcarbamoyl group, etc.), sulfamoyl group (sulfamoyl group, N-amino group, etc.) Such as over Rusuru Hua moil group),
It represents a carboxyl group, a ureido group (ureido group, N-ethylureido group, etc.) or an aryloxycarbonyl group (phenoxycarbonyl group, 4-methoxycarbonyl group, etc.).

In the formula, G ₂ represents a divalent group among the substituents listed for G ₁ .

In the formula, G ₃ is a substituted or unsubstituted alkylene group or a substituted or unsubstituted arylene group, on the way, an ether bond, an ester bond, a thioether bond, an amide bond, a ureido bond, an imide bond, a sulfone bond, a sulfonamide bond, A carbonyl group or the like may be interposed, or a plurality of these bonding groups, alkylene groups, and arylene groups may be linked to form a divalent group as a whole.

In the formula, V ₁ represents a nitrogen atom or a methine group, V ₂ represents an oxygen atom, a sulfur atom, Or Represents

In the formula, G ₄ is a substituent listed in G ₁ or (G ₃ ) h-CCD
Represents G ₅ represents a hydrogen atom, an alkyl group (eg, methyl group, ethyl group) or an aryl group (eg, phenyl group, naphthyl group).

In the formula, f represents an integer of 1 or 2 and h represents 0 or 1
Represents When f is 2, two G _1's may be the same or different. In the general formulas (P-4) and (P-5),
At least one of the groups represented by V ₂ and G ₄ is a group containing CCD.

General formula (P-1), (P-2), (P-3), (P-
4) and (P-5), G ₁ , G ₂ , G ₃ , G ₄ or G ₅
Is an alkyl group, the alkyl group has 1 to 1 carbon atoms.
22, preferably 1-10 substituted or unsubstituted, linear or branched, linear or cyclic, saturated or unsaturated. Further, when G ₁ , G ₂ , G ₃ , G ₄ or G ₅ contains a moiety of an aryl group, the aryl group has 6 to 10 carbon atoms.
And preferably a substituted or unsubstituted phenyl group.

The group represented by CCD in the general formula (II) is preferably (D-1), (D-2) and the following (D-3),
(D-16).

General formula (D-1) -COOR _d1 General formula (D-2) R _d1 and R _d2 are substituted or unsubstituted alkyl (preferably having 1 to 10 carbon atoms, for example, methyl, ethyl, 2,3-dichloropropyl, 2,2,3,3-tetrafluoropropyl, butoxycarbonyl Methylcyclohexylaminocarbonylmethyl, methoxyethyl, flopargyl group and the like) Substituted or unsubstituted aryl group (preferably having 6 to 6 carbon atoms)
10 is, for example, phenyl, 3,4-methyleneoxyphenyl, p-methoxyphenyl, p-cyanophenyl, m
-Nitrophenyl, groups, etc.) Substituted and unsubstituted aralkyl groups (preferably having 7 to 12 carbon atoms, such as benzyl, p-nitrobenzyl groups, etc.)
Is.

General formula (D-3) General formula (D-4) General formula (D-5) In the formula, Z ₁ or Z ₂ represents a bond with AF or the following group; a hydrogen atom, an alkylamino group (for example, CH ₃ —NH—, Alkyl group (for example, methyl group, propyl group, methoxymethyl group, benzyl group), aryl group (for example, phenyl group, 4-chlorophenyl group, naphthyl group, 4-methoxyphenyl group, 4-butanamidephenyl group), An acylamide group (nitrogen atom may be substituted; for example, acetamide group, benzamide group) or a 4- to 7-membered substituted or unsubstituted hetero group containing a hetero atom selected from nitrogen atom, sulfur atom and oxygen atom Cyclic group (for example, 2-pyridyl group, 2-pyrrolidinyl group, 4-imidazolyl group, 3-chloro-5-pyrazolyl group, etc.).

In the formula, Z ₃ is a hydrogen atom, a halogen atom, an alkyl group (eg, methyl group, propyl group, etc.), an aryl group (eg, phenyl group, 4-chlorophenyl group, naphthyl group, etc.), a heterocyclic group (nitrogen as a hetero atom). 4-membered to 7-membered heterocyclic group containing one selected from an atom, a sulfur atom and an oxygen atom; for example, a 2-pyridyl group, a 2-pyrrolidinyl group), an alkoxy group (for example, a methoxy group, a butoxy group), an acyl group (for example, Acetyl group, benzoyl group),
Carbamoyl group (nitrogen atom may be substituted; for example, N-butylcarbamoyl group, N-phenylcarbamoyl group), sulfamoyl group (nitrogen atom may be substituted; for example, N-phenylsulfamoyl group) ), A sulfonyl group (eg, propanesulfonyl group, benzenesulfonyl group), an alkoxycarbonyl group (eg, ethoxycarbonyl group), an acylamino group (eg, acetamide group, benzamide group), a sulfonamide group (eg, benzenesulfonamide group), an alkylthio group ( For example, butylthio group) or ureido group (nitrogen atom may be substituted; for example, 3-phenylureido group, 3-butylureido group). Z ₁ and Z ₃ may combine with each other to form a ring.

 Z in the general formula (D-5)_FourIs a 5 or 6 member
A group of atoms forming a saturated heterocycle (carbon atom, hydrogen atom, nitrogen
Selected from elementary atom, oxygen atom or sulfur atom)
Represent, X_d Is an organic sulfonate anion, an organic carvone
Acid anion, halogen ion, or inorganic anion
(For example, tetrafluoroborate). Z_Fourof
Examples of the heterocycles to be constructed are as follows. next
Z in the example₁Bind at substitutable positions.

In the formula, Z ₇ has the same meaning as the substituents listed for Z ₁ or Z ₂ above, and Z ₆ represents an oxygen atom or a sulfur atom.

General formula (D-6) Here, Z ₁ and Z ₂ are as described above, and Z ₅ is Forming a 5- to 7-membered ring together, and Represents an atom group selected from a carbon atom, an oxygen atom and a nitrogen atom which does not give aromaticity to, preferably an alkylene group (which may be substituted; for example,-(CH ₂ ))
₄ -), an alkenylene group (which may be substituted; for example _{-CH 2 -CH = CH-CH 2} -, Groups, etc.

In formulas (D-3), (D-4), (D-5) and (D-6), when Z ₁ , Z ₂ , Z ₃ or Z ₇ contains an alkyl group moiety, the alkyl group is carbon. Number 1-16, preferably 1-10 substituted or unsubstituted, straight or branched,
It may be linear or cyclic, saturated or unsaturated. Further, when Z ₁ , Z ₂ , Z ₃ or Z ₇ contains an aryl group moiety, the aryl group has 6 to 10 carbon atoms and is preferably a substituted or unsubstituted phenyl group.

General formula (D-7) General formula (D-8) General formula (D-9) General formula (D-10) In the general formulas (D-7) to (D-10), Z ₁₁
At least one of Z to Z ₁₇ is the above-mentioned AF group or a group containing an AF group.

In the formula, Z ₁₁ and Z ₁₂ each represent a hydrogen atom, an alkyl group or an aryl group, or an AF group.

In the formula, Z ₁₃ , Z ₁₄ , Z ₁₅ and Z ₁₆ are each a hydrogen atom, an alkyl group, an aryl group, a halogen atom (for example, a chlorine atom), an alkoxy group (for example, a methoxy group, a butoxy group), an aryloxy group (for example, Phenoxy group, p
-Carboxyphenoxy group), arylthio group (eg phenylthio group), alkylthio group (eg methylthio group, butylthio group), alkoxycarbonyl group (eg ethoxycarbonyl group, octylcarbonyl group) aryloxycarbonyl group (eg phenoxycarbonyl group) Group), alkanesulfonyl group (eg methanesulfonyl group), sulfamoyl group (eg sulfamoyl group, methylsulfamoyl group), carbamoyl group (eg carbamoyl group, N-phenylcarbamoyl group), ureido group (eg N-methylureido group) Group), acyl group (eg acetyl group, benzoyl group), acylamino group (eg acetamide group, benzamide group), arylsulfonyl group (eg benzenesulfonyl group), heterocyclic group (nitrogen as hetero atom) Child, 5-membered ring or 6-membered ring selected from chlorine atom or sulfur atom, for example, imidazolyl group, 1,2,4-triazolyl group, thiadiazolyl group or oxadiazolyl group), acyloxy group (eg acetyloxy group), Nitro group, cyano group, carboxyl group, thiocarbamoyl group (eg phenylthiocarbamoyl group), sulfamoylamino group (eg N-phenylsulfamoylamino group), diacylamino group (eg diacetylamino group) or ari It represents a lidene amino group (for example, a benzylidene amide group) or an AF group.

Z ₁₇ represents the following group.

In Z ₁₇ , AF may be linked via a divalent group among the following groups: halogen atom, alkoxycarbonyl group, aryloxycarbonyl group, alkanesulfonyl group, sulfamoyl group, carbamoyl group, acyl group. , A diacylamino group, an arylsulfonyl group, a heterocyclic group, a nitro group, a cyano group, a carboxyl group or a sulfonamide group. Specific examples are given for Z ₁₃ to Z ₁₆ .

In formulas (D-7), (D-8), (D-9) and (D-10), Z ₁₁ , Z ₁₂ , Z ₁₃ , Z ₁₄ , Z ₁₅ , Z ₁₆ or Z ₁₇ is an alkyl group. When the alkyl group is included, the alkyl group has 1 to 16 carbon atoms, preferably 1 to 8 substituted or unsubstituted,
It may be linear or branched, linear or cyclic, saturated or unsaturated. Furthermore Z ₁₁ , Z ₁₂ , Z ₁₃ , Z
_{When 14} , Z ₁₅ , Z ₁₆ or Z ₁₇ contains an aryl group moiety, the aryl group has 6 to 10 carbon atoms and is preferably a substituted or unsubstituted phenyl group.

In formula (D-9), Z ₁₅ and Z ₁₆ may each be divalent and connected to each other to form a ring (for example, a benzene ring).

In the general formula (D-10), Z ₁₅ and Z ₁₇ may each be a divalent group and connected to each other to form a ring (for example, a benzothiazolindene group).

General formula (D-11) General formula (D-12) General formula (D-13) General formula (D-14) In the formula, Z ₂₁ represents a saturated or unsaturated 6-membered ring, and K
₁ , K ₂ is an electron-withdrawing group (for example, , Etc., and K ₃ is (Wherein R _d3 represents an alkyl group, preferably one having 6 or less carbon atoms).

General formula (D-15) (However, in the above general formulas (P-1) to (P-5), h = 0) General formula (D-16) (However, in the above general formulas (P-1) to (P-5), h = 0) In the formula, Z ₃₁ is a 5-membered or 6-membered lactone ring or 5
Represents a group forming a membered ring imide.

Specific examples of PUG represented by the general formula [II] include, for example, 1- (3-phenoxycarbonylphenyl) -5-
Mercaptotetrazole, 1- (4-phenoxycarbonylphenyl) -5-mercaptotetrazole, 1-
(3-maleimidophenyl) 5-mercaptotetrazole, 5- (phenoxycarbonyl) benzotriazole, 5- (p-cyanophenoxycarbonyl) benzotriazole, 2-phenoxycarbonylmethylthio-
5-mercapto-1,3,4-thiadiazole, 5-nitro-3-phenoxycarbonylindazole, 5-phenoxycarbonyl-2-mercaptobenzimidazole,
5- (2,3-dichloropropyloxycarbonyl) benzotriazole, 5-benzyloxycarbonylbenzotriazole, 5- (butylcarbamoylmethoxycarbonyl) benzotriazole, 5- (butoxycarbonylmethoxycarbonyl) benzotriazole, 1- (4
-Benzoyloxyphenyl) -5-mercaptotetrazole, 5- (2-methanesulfonylethoxycarbonyl) -2-mercaptobenzothiazole, 1- {4-
(2-Chloroethoxycarbonyl) phenyl} -2-mercaptoimidazole, 2- [3- {thiophen-2-
Ilcarbonyl} propyl] thio-5-mercapto-1,
3,4-thiadiazole, 5-cinnamoylaminobenzotriazole, 1- (3-vinylcarbonylphenyl)
-5-mercaptotetrazole, 5-succinimidomethylbenzotriazole, 2- {4-succinimidophenyl} -5-mercapto-1,3,4-oxadiazole, 3- {4- (benzo-1,2-iso) Thiazole-3-
Oxo-1,1-dioxy-2-yl) phenyl} -5-
Mercapto-4-methyl-1,2,4-triazole, 6-
Examples thereof include phenoxycarbonyl-2-mercaptobenzoxazole.

Examples of high-performance photochemicals when PUG is a diffusible or non-diffusible dye-Structural function and application prospect-
(CMC, 1985) pp. 197 to 211 can be mentioned. Specifically, arylidene dyes, styryl dyes, butadiene dyes, oxanol dyes, cyanine dyes, merocyanine dyes,
Hexianine dye, stilbene dye, chalcone dye, coumarin dye, azo dye, azomethine dye, azopyrazolone dye, indoaniline dye, indophenol dye, anthraquinone dye, triarylmethane dye, diarylmethane dye , Alizarin, nitro dyes, quinoline dyes, indico dyes, and phthalocyanine dyes. In addition, those leuco compounds, those whose absorption wavelength is temporarily shifted, and absorber precursors such as tetrazolium salt are also included.
Further, these dyes may form chelate dyes with suitable metals. Regarding these dyes, for example, U.S. Pat. Nos. 3,880,658; 3,931,144; 3,932,380;
No. 3,932,381 and No. 3,942,987.

 The main dyes are shown below.

As an example when PUG is a development accelerator, the following general formula (I
II] can be mentioned.

General formula [III] (*) (*) (*)-L ₁ L _{2 k} A In the formula, (*) (*) (*) marks represent the bonding position to Time.

L ₁ represents a group which can be further released than the released Time during the development processing. L ₂ is a divalent linking group and k is 0 or 1
Represents an integer. A is a group exhibiting a fogging effect on the silver halide emulsion in the developing solution.

Preferred examples of L _1, an aryloxy group, heterocyclic oxy group, an arylthio group, an alkylthio group, a heterocyclic thio group, and an azolyl group.

The following shows a specific example of L _1.

(*) (*) (* ) - S- (CH 2) 2 -, (*) (*)
_{(*) - S- (CH 2} ) 4 -, Alkylene Examples of L _2, alkenylene, arylene, a divalent heterocyclic group, -O -, - S-, imino, -CO
O -, - CONH -, - NHCONH -, - NHCOO -, - SO 2 NH-,
—CO—, —SO ₂ —, —SO—, —NHSO ₂ NH— and the like, and composites thereof can be mentioned.

Preferred specific examples of A include, for example, a reducing group (for example, a partial structure of hydrazine, hydrazide, hydrazone, hydroxylamine, polyamine, enamine, hydroquinone, catechol, p-aminophenol, o-aminophenol, aldehyde, acetylene). Group) or a group capable of acting on silver halide during development to form a developable silver sulfide nucleus (eg thiourea, thioamide, thiocarbamate, dithiocarbamate, thiohydantoin,
Examples thereof include groups having a partial structure such as rhodanine) and quaternary salts (for example, pyridinium salts).

Particularly useful groups among the groups represented by A are represented by the following general formula [I
V] is a group represented by

General formula (IV) In the formula, A ₁ and A ₂ are both hydrogen atoms or one is a hydrogen atom and the other is a sulfinic acid residue or (Wherein R ¹ ₀₀ is an alkyl group, an alkenyl group, an aryl group,
It represents an alkoxy group or an aryloxy group, and n represents an integer of 1 or 2. ) Is represented. R ₀₀ represents a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, an azo group or a heterocyclic group. G is a carbonyl group, a sulfonyl group, a sulfoxy group, (R ² ₀₀ represents. An alkoxy group or an aryloxy group), or an iminomethylene group. L ₀₀ represents an arylene group or a divalent heterocyclic group.

_l4 represents 0 or 1.

Specific examples of PUG represented by the general formula [III] are shown below. (*) (*) (*) Represents the binding position to Time.

Examples of the case where PUG is a fogging agent include, in addition to the above, a leaving group moiety released from a coupler described in JP-A-59-170840.

When PUG is a silver halide solvent, examples thereof include JP-A-60-163,042, U.S. Pat.No. 4,003,910, mesoionic compounds described in U.S. Pat.No. 4,378,424, and JP-A-57-202,531. Examples thereof include mercaptoazoles or azolethiones having the amino group as a substituent, and more specific examples thereof include those described in JP-A-61-230135. Other PUG
Japanese Patent Application No. 60-71,768, U.S. Pat.No. 4,248,962
No. etc. can be referred to.

V is a carbonyl group, a sulfonyl group, a sulfoxy group, (R ₀ represents an alkoxy group or an aryloxy group), an iminomethylene group, a thiocarbonyl group, or (W represents an electron-withdrawing group. W is preferably a group having a σ _para value of a hamet of more than 0.3, for example, a cyano group, a nitro group, a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. (For example, methylcarbamoyl group, ethylcarbamoyl group, 4-methoxyphenylcarbamoyl group, N-methyl-N-octadecylcarbamoyl group, 3- (2,4-di-t-pentylphenoxy) propylcarbamoyl group, pyrrolidino Carbonyl group, hexadecylcarbamoyl group, di-n-octylcarbamoyl group, etc.), a substituted or unsubstituted sulfamoyl group having 1 to 30 carbon atoms (for example, methylsulfamoyl group, diethylsulfamoyl group, 3- (2, 4-di-t-pentylphenoxy) propylcarbamoyl group, phenylsulfamoyl group, pyrrolidinosulfoni Group, morpholino sulfonyl group), a substituted or unsubstituted alkoxycarbonyl group having 1 to 30 carbon atoms (e.g., methoxycarbonyl group,
Ethoxycarbonyl group, phenoxycarbonyl group, 2-
Methoxyethoxycarbonyl group, hexadecyloxycarbonyl group, etc.), substituted or unsubstituted sulfonyl group having 1 to 30 carbon atoms (eg, methanesulfonyl group, 4-methylphenylsulfonyl group, dodecylsulfonyl group, etc.), carbon number 1 ~ 30 substituted or unsubstituted acyl group (for example, acetyl group, hexanoyl group, benzoyl group,
4-chlorobenzoyl group), trifluoromethyl group, carboxyl group, substituted or unsubstituted heterocyclic residue having 1 to 30 carbon atoms (for example, benzoxazol-2-yl group, 5,5-dimethyl-2-oxazoline) -2-yl group, etc.), and particularly preferably a carbamoyl group,
Examples include an alkoxycarbonyl group and a sulfamoyl group. ) Is represented.

 V is preferably a carbonyl group.

R is a hydrogen atom, an aliphatic group, an aromatic group or Represents

The aliphatic group represented by R is a linear, branched or cyclic alkyl group, alkenyl group, or alkynyl group.

The aromatic group represented by R is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.

R may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted.

For example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, sulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, alkylthio. Group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group, carboxyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamido group, sulfonamide group, nitro group Groups, alkylthio groups, arylthio groups, and the like.

When possible, these groups may be linked to each other to form a ring.

Preferred as R is a hydrogen atom, an alkyl group or an aryl group, and a hydrogen atom is particularly preferred.

Although the mechanism of PUG release from the compound represented by formula (I) of the present invention is not clear, Journal of Organic Chemistry Vol. 30, p. 1203 (1965)
Year)) and the reaction mechanism described in JP-A No. 61-213,847. That is, in the compound of the present invention, the reactivity of the functional group V with the nucleophile is increased as the redox core is changed from the electron donating property to the electron withdrawing property by the oxidation of the redox core. As a result, it is understood that the nucleophile directly attacks V and PUG is released by the subsequent cleavage of the bond or the cleavage of the bond by the intramolecular ring closure reaction.

 This is shown in Scheme I.

Specific examples of the compound of the present invention are listed below, but the present invention is not limited thereto.

The specific synthesis examples of the compound of the present invention are shown below.

1- (1) Synthesis of compound 1-B After dissolving 22.2 g of 4-nitrophenyl chlorocarbonate in 30 ml of acetonitrile, 1-hydroxymethyl-
4-phenyl-2-tetrazoline-5-thione (-A)
Add a solution of 20.8 g dissolved in 200 ml of acetonitrile,
Further, 16.2 ml of pyridine is added dropwise. After reacting at room temperature for 5 hours, the mixture is extracted with diluted hydrochloric acid / ethyl acetate, and the organic layer is separated. The organic layer was dried over anhydrous magnesium sulfate and then recrystallized from ethyl acetate / n-hexane to obtain 30.1 g of white solid 1-B. (Yield 80.7%) 1- (2) Synthesis of Compound 1 After adding 7.46 g of Compound 1-B obtained in 1- (1) and 2.3 g of hydroxylamine hydrochloride to 50 ml of acetonitrile,
4.4 ml of N-methylmorpholine are added dropwise. After stirring at room temperature for 50 minutes, the mixture is extracted with diluted hydrochloric acid / ethyl acetate and the organic layer is separated. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure, and the resulting crude product was purified by silica gel column chromatography (developing solvent; methanol / chloroform = 1/9).
(Vol / Vol)) and further recrystallized from an ethyl acetate / n-hexane solvent to obtain 3.2 g of a white solid. (yield
59.9%) 2- (1) Synthesis of compound 2-B 22.2 g of 4-nitrophenyl chlorocarbonate was dissolved in 30 ml of acetonitrile, and then 1-hydroxymethyl-
A solution of 19.3 g of 5-nitroindazole (2-A) dissolved in 190 ml of acetonitrile was added dropwise, and pyridine 1
Add 6.2 ml dropwise. After reacting for 4 hours at room temperature, the mixture is extracted with diluted hydrochloric acid / ethyl acetate, and the organic layer is separated. The organic layer was dried over anhydrous magnesium sulfate and then recrystallized from ethyl acetate / n-hexane to give 29.0 g of white solid 2-B.
Obtained. (Yield 81.0%) 2- (2) Synthesis of Compound 2 After adding 7.19 g of compound 2-B obtained in 2- (1) and 2.3 g of hydroxylamine hydrochloride to 50 ml of acetonitrile,
4.4 ml of N-methylmorpholine are added dropwise. After stirring at room temperature for 1 hour, the white solid (3.4 g) was obtained by purifying by the same operation as 1- (2). (Yield 67.5%) 3- (1) Synthesis of compound 10-B 4-nitrophenyl chlorocarbonate 22.2 g, compound 10-A 29.1 g pyridine 16.2 ml, acetonitrile 200 ml were used, and a reaction similar to the synthesis method of 1- (1), By purification, 32.8 g of white solid 10-B was obtained. (Yield 71.9%%) 3- (2) Synthesis of Compound 10 After adding 9.12 g of compound 3-B obtained in 3- (1) and 2.3 g of hydroxylamine hydrochloride to 70 ml of acetonitrile,
4.4 ml of N-methylmorpholine are added dropwise. After stirring at room temperature for 1 hour, the white solid (3.60 g) was obtained by purification by the same operation as in 1- (2). (Yield 51.4%) 4- (1) Synthesis of Compound 27-A A solution of 2,3-dichloropropionyl chloride (15.7 g) in tetrahydrofuran (30 ml) was cooled to 5 ° C. or lower and stirred with 18.6 g of 1-dodecanol and 12.1 g of N, N-dimethylaniline in tetrahydrofuran. Add 60 ml solution dropwise. After stirring at room temperature for 14 hours, the mixture was concentrated under reduced pressure to give an oil (27-
A) 26.5 g was obtained. (Yield (87.8%) 4- (2) Synthesis of Compound 27-B Sodium 1-phenyl-1-H-tetrazole-5
-Dissolve 20 g of thiolate in 400 ml of acetone and, under stirring, 4
-26.5 g of compound 17-A obtained in (1) is added dropwise. After refluxing for 3 days under a nitrogen atmosphere, the mixture is cooled to room temperature and extracted with ethyl acetate / saturated saline. The organic layer was separated and dried over anhydrous magnesium sulfate, the solvent was distilled off, and an oily substance (27-
28.1 g of B) was obtained. (Yield 73.0%) 4- (3) Synthesis of Compound 27 3.85 g of Compound 27-B obtained in 4- (2), 6.95 g of hydroxylamine hydrochloride, and 3.90 g of N, N diisopropylethylamine were dissolved in 100 ml of tetrahydrofuran. The mixture was stirred and refluxed for 10 hours. The solvent is distilled off under reduced pressure and the product is purified by silica gel column chromatography (developing solvent: methanol / chloroform = 1/9 (Vol / Vol)) to give an oil.
2.38 g of 27 was obtained. (Yield 53.0%) The compound of the general formula [I] of the present invention is cross-oxidized by redox reaction with an oxidized product of a developing agent or an auxiliary developing agent which imagewise develops during development. Alternatively, a compound of the general formula [I] directly reduces a silver salt,
It is presumed that when it is oxidized, it emits a photographically useful substance in an imagewise manner and changes into a colorless oxidant.

The compounds of the present invention release photographically useful groups image-wise quickly, in a timely manner and efficiently, so that they can be used in infinite applications.For example, if a development inhibitor is released, image-wise development is possible. Suppress, finer image, softening image tone, improving sharpness of image, improving color reproduction, etc.
Shows the DIR effect. If a diffusible or non-diffusible dye is released, a color image can be formed. The compound of the general formula [I] of the present invention has a remarkably high activity compared with a conventionally known compound having the same action as described below, and has a surprising photographic effect by acting efficiently. Show.

The compound of the present invention is added to the silver halide emulsion layer, to the hydrophilic colloid layer provided above or below the emulsion layer, or to both layers to achieve the intended purpose. When the compound of the general formula [I] of the present invention is used for the above-mentioned various purposes, a suitable leaving group PU is selected depending on each purpose.
It is necessary to select G, but the amount added will differ depending on the type of photographic light-sensitive material and the properties of PUG selected. Generally, the addition amount is 1 × 10 ^-7 per mol of silver halide.
The range of mol to 1 × 10 ³ mol is preferable.

For example, when PUG is a development inhibitor, it is preferable to use the compound of the present invention in an amount of 1 × 10 ^-7 mol to 1 × 10 ^-1 mol, and particularly 1 × 10 ^-6 mol to 5 ×, per mol of silver halide. It is preferably used in the range of 10 ^-2 mol. When the PUG is a development accelerator or a fogging agent, the same amount as the above-mentioned development inhibitor is preferable. Furthermore, for example, PUG is a dye,
When used for image formation, the compound of the present invention is preferably used in an amount of 1 × 10 ⁻³ mol to 1 × 10 mol, and particularly 1 × 10 ⁻² mol to 4 mol per mol of silver halide. Preferably.

For the addition to the silver halide emulsion layer and / or the other hydrophilic colloid layer, a conventional method is applied. That is, the compound soluble in water may be dissolved in water or added as it is to the aqueous gelatin solution. Compounds that are insoluble or poorly soluble in water are dissolved in a solvent miscible with water and mixed with an aqueous gelatin solution.
The method described in 322,027 or the like is used. For example, alkyl phthalates (such as dibutyl phthalate and dioctyl phthalate), phosphates (such as diphenyl phthalate, triphenyl phthalate, tricresyl phthalate, and dioctyl butyl phthalate), and citrates (such as acetyl) Tributyl citrate), benzoic acid esters (eg, octyl benzoate), alkyl amides (eg, diethyl lauryl amide), fatty acid esters (eg, dibutoxyethyl succinate, diethyl azelate), trimesic acid esters (eg, tributyl trimesate) Or an organic solvent having a boiling point of about 30 ° C. to 150 ° C., for example, lower alkyl acetates such as ethyl acetate and butyl acetate, ethyl propionate, secondary butyl alcohol, methyl isobutyl ketone, β-ethoxy After being dissolved in ethyl acetate, methyl cellosolve acetate, etc., it is dispersed in a hydrophilic colloid. The high boiling point organic solvent and the low boiling point organic solvent may be mixed and used.

The compound of the general formula [I] of the present invention can be used by emulsifying and dispersing it in combination with a reducing substance such as hydroquinone and its derivative, catechol and its derivative, aminophenol and its derivative, ascorbic acid and its derivative. .

Any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used as the photosensitive silver halide in the photographic emulsion layer of the photographic light-sensitive material used in the present invention.

The average grain size of the silver halide grains in the photographic emulsion (the grain diameter in the case of spherical grains or grains close to spheres, the edge length in the case of cubic grains, and the average based on the projected area) is particularly required. Although not present, it is preferably 3 μm or less.

The grain size distribution may be narrow (so-called "monodisperse" emulsion) or wide.

Silver halide grains in photographic emulsions are cubic, octahedral,
Those with regular (regular) crystal bodies such as tetradecahedral and rhombohedral dodecahedrons, and those with irregular (irregular) crystal bodies such as spheres and plates, or those of these crystal forms It may be a composite type. It may consist of a mixture of particles of different crystal forms.

Further, an emulsion may be used in which ultra-flat tabular silver halide grains having a grain diameter of 5 times or more the thickness thereof occupy 50% or more of the total projected area. For details, see JP-A-58-127921 and 58-58.
-113927 and the like.

The silver halide grains may have different phases between the inside and the surface layer. Further, the particles may be such that the latent image is mainly formed on the surface, or may be the particles that are mainly formed inside the particle.

The photographic emulsion used in the present invention is described by P. Glafkides, "Chemie et Physique Photographique" by P. Glafkides, Paul Montel (1967), G.E.
Photographic Emulsio, by GF Duffin
n Chemistry "The Focal Pre
ss, 1966), bu el zuerikuman (VLZeli
kman et al) by Making and coating
Photograph Ituk Emulation'Making and Coati
ng Photographic Emulsion ”, The Focal Press (published by The Focal Press, 1964) and the like. That is, any of an acidic method, a neutral method, an ammonia method and the like may be used, and as a method of reacting a soluble silver salt and a soluble halogen salt, any of a one-sided mixing method, a simultaneous mixing method and a combination thereof may be used. Good.

A method of forming grains in the presence of excess silver ions (so-called reverse mixing method) can also be used. PA in the liquid phase in which silver halide is formed as a form of simultaneous mixing method.
How to keep g constant, that is, so-called controlled
The double jet method can also be used.

According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

Two or more kinds of silver halide emulsions formed separately may be mixed and used.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, lead salt, thallium salt, iridium salt or its complex salt, rhodium salt or its complex salt, iron salt or iron complex salt, gold salt or its complex salt and the like may coexist.

The silver halide emulsion may or may not be chemically sensitized. For chemical sensitization, for example,
H.Frieser polarized Die Grundlagen der ("Die Grundlagen der")
Photographischen Prozesse mit Silberhalogenigd
en ") Akademische Verlagsgesellschaft.1968 675-73
The method described on page 4 can be used.

That is, a sulfur sensitization method using a sulfur-containing compound capable of reacting with active gelatin or silver (eg, thiosulfate, thioureas, mercapto compounds, rhodanins); a reducing substance (eg, first tin salt, Amine, hydrazine derivative, formamidine sulfinic acid, silane compound) reduction sensitization method; precious metal compound (eg, gold complex salt, Pt,
A noble metal sensitization method using a group VIII metal of the periodic table such as Ir or Pd) can be used alone or in combination.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. That is, azoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles,
Mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines Thioketo compounds such as oxadrinthione; azaindenes, such as triazaindenes, tetrazaindenes (particularly 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes), pentaazaindenes, etc. Many compounds known as antifoggants or stabilizers such as benzenethiosulphonic acid, benzenesulphonic acid, benzenesulphonic acid amide and the like can be added.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkylaryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycols). Non-ionic interfaces such as alkyl amines or amides, polyethylene oxide adducts of silicones), glycidol derivatives (eg alkenyl succinic acid polyglycerides, alkyl phenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Activator: alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene Anionic surfactants containing an acid group of a carboxy group, a sulfo group, a phospho group, a sulfate group, a phosphate group sugar, such as alkyl phosphates; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfate or Amphoteric surfactants such as phosphates, alkyl betaines, and amine oxides; alkylamine salts,
Aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and cationic surfactants such as phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

The photographic emulsion layer of the photographic light-sensitive material of the present invention contains, for example, polyalkylene oxide or an ether compound thereof, thiomorpholine compounds, quaternary ammonium salt compounds, urethane derivatives, urea derivatives, and imidazole for the purpose of increasing sensitivity, increasing contrast, or promoting development. Derivatives, 3-pyrazolidones and the like may be included.

The photographic light-sensitive material used in the present invention includes a photographic emulsion layer and other hydrophilic colloid layers for the purpose of improving dimensional stability.
It may comprise a dispersion of water insoluble or sparingly soluble synthetic polymer. For example, alkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycidyl (meth)
Acrylate, (meth) acrylamide, vinyl ester (for example, vinyl acetate), acrylonitrile, olefin, styrene, etc., alone or in combination, or with acrylic acid, methacrylic acid, α, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth) acrylate. A polymer having a monomer component of a combination of sulfoalkyl (meth) acrylate, styrene sulfonic acid and the like can be used.

The photographic emulsion used in the present invention may be spectrally sensitized with methine dyes or the like. The dyes used include
Cyanine dye, merocyanine dye, complex cyanine dye,
Included are complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes and hemioxonol dyes. Particularly useful dyes are cyanine dyes,
It is a dye belonging to a merocyanine dye and a composite merocyanine dye. Any of the nuclei normally used for cyanine dyes as a basic heterocyclic nucleus can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiazoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus and the like; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and these A nucleus in which an aromatic hydrocarbon ring is fused, that is, an indolenine nucleus, a benzindolenine nucleus, an indole nucleus, a benzoxazole nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benz Imidazole nucleus, quinoline nucleus, etc. can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, 2-thiooxazolidine-
A 2,4-dione nucleus, a thiazolidine-2,4-dione nucleus, a rhodanine nucleus and the like can be applied.

The photographic emulsion layer of the photographic light-sensitive material prepared by using the present invention contains a dye-forming coupler, that is, an aromatic primary amine developing agent (for example, a phenylenediamine derivative or an aminophenol derivative) in the color development processing. A compound capable of developing color by oxidative coupling may be used together.
For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides), and the like. Examples of cyan couplers include naphthol couplers and phenol couplers. These couplers are preferably non-diffusible ones having a hydrophobic group called a ballast group in the molecule, or polymerized ones. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ions. Further, it may be a colored coupler having a color correcting effect, or a coupler (so-called DIR coupler or DAR coupler) which releases an immediate development inhibitor or a development accelerator upon development.

In addition to the DIR coupler, the product of the coupling reaction may be colorless and may contain a colorless DIR coupling compound that releases a development inhibitor.

In addition to the DIR coupler, a compound which releases a development inhibitor upon development may be contained in the light-sensitive material.

The couplers and the like can be used in combination of two or more kinds in the same layer in order to satisfy the characteristics required for the light-sensitive material, and it is of course possible to add the same compound to two or more different layers.

The photographic light-sensitive material of the present invention may contain an inorganic or organic hardener in the photographic emulsion layer and other hydrophilic colloid layers. For example, chromium salts (chromium deuterium, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylolurea, methyloldimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane) Etc.), active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, 1,3-vinylsulfonyl-2-propanol, etc.), active halogen compounds (2,4-dichloro-6-hydroxy-s). -Triazine, etc.), mucohalogen acids (mucochloric acid, mucophenoxycycloric acid, etc.), and the like can be used alone or in combination.

As the binder or protective colloid that can be used in the emulsion layer or hydrophilic colloid layer (eg, protective layer, intermediate layer) of the light-sensitive material of the present invention, it is advantageous to use gelatin, but other hydrophilic substances are used. Colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers such as polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole and polyvinylpyrazole Can be. In addition, lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin and the like can be used.

Various other additives may be used in the silver halide photographic light-sensitive material of the present invention. For example, whitening agents, dyes, desensitizing agents, coating aids, antistatic agents, plasticizers, slip agents, matting agents, development accelerators, mordants, ultraviolet absorbers, anti-fading agents,
Color antifoggants, etc.

Regarding these additives, specifically, Research Disclosure No. 176, Nos. 22-31
Pages (RD-17643) (Dec., 1978) can be used.

For the photographic processing of the silver halide photographic light-sensitive material of the present invention, any known method such as wet processing and heat development can be used.

A known treatment liquid can be used for the wet treatment. The processing temperature is usually selected between 18 ° C and 50 ° C, but may be lower than 18 ° C or higher than 50 ° C. Depending on the purpose, either a developing process for forming a silver image (black-and-white photographic process) or a color photographic process including a developing process for forming a dye image can be applied.

The developing solution used for black and white photographic processing may contain a conventionally known developing agent. Examples of developing agents include dihydroxybenzenes (for example, hydroquinone) and 3-pyrazolidones (for example, 1-phenyl-3).
-Pyrazolidone), aminophenols (eg N-
Methyl-p-aminophenol), 1-phenyl-3-
Pyrazolines, ascorbic acid, and U.S. Patent 4,067,87
The heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline ring and indrene ring described in No. 2 may be used alone or in combination. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants, and the like, and if necessary, dissolution aids, color tones, development accelerators, surfactants, defoamers, A water softener, a film hardening agent, a viscosity imparting agent and the like may be contained.

As the fixer, one having a commonly used composition can be used. As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known to be effective as a fixing agent can be used. The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

Conventional methods can be applied to form a dye image. For example, the negative-positive method (for example, Journal of the Society of Motion Picture PICTURE and TV Engineers “Journal of the Society of
Motion Picture and Television Engineers "Volume 61 (19
53), pp. 667-701), to develop a negative silver image by developing with a developer containing a black-and-white developing agent, followed by at least one uniform exposure or other suitable fog treatment. , A color reversal method for obtaining a positive dye image by subsequent color development, a silver image bleaching process in which a photographic emulsion layer containing the dye is exposed and then developed to form a silver image, and this is used as a bleach catalyst to bleach the dye. To be

The color developer generally comprises an alkaline aqueous solution containing a color developing agent. Color developing agents are known primary aromatic amine developers such as phenylenediamines (eg 4-
Amino-N, N-diethylaniline, 3-methyl-4-amino-N, N-diethylaniline, 4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-
4-amino-N-ethyl-N-β-hydroxyethylaniline, 3-methyl-4-amino-N-ethyl-N-β
-Methanesulfoamidoethylaniline, 4-amino-N
-Methyl-N-ethyl-N-β-methoxyethylaniline).

226-229 from The Focal Press (1966) Photographic Processing Chemistr by Photographic Processing Chemistr by LFA Mason
Page, U.S. Pat.Nos. 2,193,015 and 2,592,364, JP-A-48-
For example, those described in No. 64933 may be used.

The color developer may further contain a pH buffering agent such as alkali metal sulfite, carbonate, borate and phosphate, a development inhibitor or an antifoggant such as bromide, iodide and an organic antifoggant. it can. If necessary, a water softener, a preservative such as hydroxylamine, an organic solvent such as benzyl alcohol and diethylene glycol, a polyethylene glycol, a quaternary ammonium salt, a development accelerator such as amines, a dye-forming coupler, a competitive coupler, Fogging agents such as sodium borohydride, auxiliary developing agents such as 1-phenyl-3-pyrazolidone, viscosity imparting agents, polycarboxylic acid type chelating agents described in U.S. Pat. Antioxidants and the like may be included.

The photographic emulsion layer after color development is usually bleached. The bleaching process may be performed at the same time as the fixing process, or may be performed individually. As the bleaching agent, compounds of polyvalent metals such as iron (III), cobalt (III), chromium (VI) and copper (II), peracids, quinones and nitroso compounds are used. For example, an organic complex salt of ferricyanide, dichromate, iron (III) or cobalt (III), for example, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid, nitrilotriacetic acid, 1,3-diamino-2-propanoltetraacetic acid or citric acid. , Complex salts of organic acids such as tartaric acid and malic acid; persulfates, permanganates; nitrosphenol and the like can be used. Of these, potassium ferricyanide, sodium ethylenediaminetetraacetate (III) acetate and ammonium ethylenediaminetetraacetate (III) ammonium salt are particularly useful. Ethylenediaminetetraacetic acid iron (II
I) Complex salts are useful both in independent bleaching solutions and in one-bath bleach-fixing solutions.

For bleaching or bleach-fixing solution, U.S. Patent 3,042,520,
In addition to the bleaching accelerators described in JP-B No. 3,241,966, JP-B-45-8506, JP-B-45-8836 and the thiol compound described in JP-A-53-65732, various additives can be added.

The compound of the general formula [I] of the present invention can be applied to various silver halide photographic light-sensitive materials. An example is given below.

(1) For example, the compound of the present invention has a layer of silver chlorobromide or silver chloroiodobromide emulsion containing at least 60% of silver chloride and 0 to 5% of silver iodide (the emulsion must be monodisperse). Is preferable), and is effective for improving the quality of the silver halide photographic light-sensitive material for photoengraving containing a polyalkylene oxide. For example, when the PUG of the compound [I] is a development inhibitor, halftone gradation can be improved (lengthened) without deteriorating halftone dot quality. Further, when PUG is a development accelerator, it is effective for sensitization and improvement of halftone dot quality. In these cases, the compounds according to the invention are preferably 1 × per mol of silver halide.
10 ^-7 mol to 1 × 10 ^-1 mol, especially 1 × 10 ^-6 mol to 1 × 10 ^-2
Used in the molar range.

The polyalkylene oxide compound used here may be added with either a silver halide photographic light-sensitive material, a developing solution, or both a silver halide photographic light-sensitive material and a developing solution.

The polyalkylene oxide compound is an alkylene oxide having 2 to 4 carbon atoms, for example, ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, and the like, preferably a polyalkylene oxide having at least 10 units of ethylene oxide. , A condensate with a compound having at least one active hydrogen atom such as water, an aliphatic alcohol, an aromatic alcohol, a fatty acid, an organic amine, and a hexitol derivative, or a block copolymer of two or more polyalkylene oxides. That is, as the polyalkylene oxide compound, specifically, polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene glycol aryl ethers, polyalkylene glycol (alkylaryl)
Esters, polyalkylene glycol esters, polyalkylene glycol fatty acid amides, polyalkylene glycol amines, polyalkylene glycol / block copolymers, polyalkylene glycol graft polymers, and the like can be used.

Those having a molecular weight of 500 to 10,000 are preferably used.

Specific examples of the polyalkylene oxide compound preferably used in the present invention are as follows.

Examples of polyalkylene oxide compounds 1. HO (CH ₂ CH ₂ O) ₉ H 2. C ₁₂ H ₂₅ O (CH ₂ CH ₂ O) ₁₅ H 3. C ₈ H ₁₇ CH = CHC ₈ H ₁₆ O (CH ₂ CH ₂ O) ₁₅ H 5. C ₁₁ H ₂₃ COO (CH ₂ CH ₂ O) ₈₀ H 6. C ₁₁ H ₂₃ CONH (CH ₂ CH ₂ O) ₁₅ H 8. C ₁₄ H ₂₉ N (CH ₂ ) (CH ₂ CH ₂ O) ₂₄ H These polyalkylene oxide compounds may be used alone or in combination of two or more.

When the above-mentioned polyalkylene oxide compound is added to a silver halide photographic light-sensitive material, it is sensitized in the range of 5 × 10 ⁻⁴ g to 5 g, preferably 1 × 10 ⁻³ g to 1 g per mol of silver halide. It can be added to the material. When the above-mentioned polyalkylene oxide compound is added to the developer, it can be added in the range of 0.1 g to 10 g per developer.

(2) Further, the compound of the general formula [I] of the present invention can be prepared by the method described in U.S. Pat. Nos. 4,224,401, 4,168,977, 4,241,164 and
4,311,781, 4,272,606, 4,221,857, 4,24
No. 3,739, No. 4,272,614, No. 4,269,929, etc.
The halftone gradation of a photographic light-sensitive material having a monodisperse silver halide emulsion layer capable of forming a super-high contrast negative image with a stable developer by the action of a hydrazine derivative is improved without deteriorating the halftone dot quality ( Effective). In the above, a stable developer means a developer containing at least 0.15 mol / sulfite ion as a preservative and having a pH of 10.0 to 12.3. Since this developer can contain a large amount of preservative, it is more stable than a normal lith developer (which can contain only a very small amount of sulfite ion), and has a relatively low pH. It is less susceptible to air oxidation than the developer (pH = 12.8) of the high contrast image forming system described in 2,419,975 and is stable. In this case, the compound of the general formula [I] of the present invention having a development inhibitor as a PUG is preferably 1, per mol of the silver halide is × 10 ^-5 mol to 8 × 10 ^-2 mol, particularly 1 × 10 ^- It is used in the range of ⁴ mol to 5 × 10 ^-2 mol.

The hydrazine derivative used above is represented by the following general formula [V].

General formula [V] In the formula, Y ₅ represents an aliphatic group, an aromatic group or a heterocyclic group. A ₅₁ and A ₅₂ are both hydrogen atoms or one is a hydrogen atom and the other is a sulfinic acid residue or (In the formula, R ₅₀₀ represents an alkyl group, an alkenyl group, an aryl group, an alkoxy group, or an aryloxy group,
n'represents an integer of 1 or 2. ) Is represented. R ₅₀ is a hydrogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an alkoxycarbonyl group,
It represents an aryloxycarbonyl group, a carbamoyl group, an azo group or a heterocyclic group.

G is a carbonyl group, a sulfonyl group, a sulfoxy group, Alternatively, it represents an iminomethylene group.

In the general formula [V], the aliphatic group represented by Y ₅ is a linear, branched or cyclic alkyl group, alkenyl group or alkynyl group.

The aromatic group represented by Y ₅ is a monocyclic or bicyclic aryl group, and examples thereof include a phenyl group and a naphthyl group.

The heterocycle of Y ₅ is a 3- to 10-membered saturated or unsaturated heterocycle containing at least one of N, O, or S atoms, which may be a single ring, or other A condensed ring may be formed with an aromatic or hetero ring. The heterocycle is preferably a 5- or 6-membered aromatic heterocyclic group, for example, a pyridine group, an imidazolyl group, a pyrimidyl group, a pyrazolyl group, an isoquinolinyl group,
A thiazolyl group and a benzthiazolyl group are preferred.

Y ₅ may be substituted with a substituent. Examples of the substituent include the followings. These groups may be further substituted.

For example, alkyl group, aralkyl group, alkenyl group, alkynyl group, alkoxy group, aryl group, substituted amino group, acylamino group, asulfonylamino group, ureido group, urethane group, aryloxy group, sulfamoyl group, carbamoyl group, aryl group, Alkylthio group, arylthio group, sulfonyl group, sulfinyl group, hydroxy group, halogen atom, cyano group, sulfo group and carboxyl group, aryloxycarbonyl group, acyl group, alkoxycarbonyl group, acyloxy group, carbonamido group, sulfonamide group, Examples thereof include a nitro group, an alkylthio group and an arylthio group.

When possible, these groups may be linked to each other to form a ring.

Preferred as Y ₅ is an aromatic group, more preferably an aryl group.

Of the groups represented by R ₅₀ , preferred is a hydrogen atom, an alkyl group (eg, methyl group, trifluoromethyl group, 3-hydroxypropyl group, 3-methanesulfonamidopropyl group, etc.) when G ₅₀ is a carbonyl group. ), An aralkyl group (eg, o-hydroxybenzyl group), an aryl group (eg, phenyl group, 3,5-dichlorophenyl group, o-methanesulfonamidephenyl group, 4-methanesulfonylphenyl group, etc.), alkoxy Groups (eg,
Methoxy group, etc.), aryloxy group (eg, phenoxy group, p-nitrophenoxy group, p-chlorophenoxy group, etc.), amino group (eg, methylamino group, phenylamino group, p-nitrophenylamino group, p-methoxyf group) An enylamino group), an alkoxycarbonyl group (eg, an ethoxycarbonyl group), an aryloxycarbonyl group (eg, a phenoxycarbonyl group),
A carbamoyl group (eg, an unsubstituted carbamoyl group, a methylcarbamoyl group, etc.), an azo group (eg, a phenylazo group, etc.), a heterocyclic group (eg, a nitrogen-containing heterocyclic group such as a pyridyl group, a quinolyl group, etc.), particularly hydrogen. Atoms are preferred.

When G ₅₀ is a sulfonyl group, R ₅₀ is an alkyl group (eg, methyl group) or an aralkyl group (eg, o-
A hydroxyphenylmethyl group etc.), an aryl group (eg phenyl group etc.) or a substituted amino group (eg dimethylamino group etc.) and the like are preferable.

When G ₅₀ is a sulfoxy group, preferred R ₅₀ is cyanobenzyl group, methylthiobenzyl group and the like.

G ₇ In the case of, R ′ ₅₀ is a methoxy group, an ethoxy group,
A butoxy group and a phenyl group are preferable, and a phenoxy group is particularly preferable.

When G ₅₀ is an N-substituted or unsubstituted iminomethylene group, preferred R ₅₀ is a methyl group, an ethyl group, a substituted or unsubstituted phenyl group.

Most preferably, G ₅₀ is a carbonyl group.

As the substituent for R _50, the substituents listed for Y ₅ can be applied.

These substituents may be further substituted with these substituents. Also, if possible, these units may form a ring connected to each other.

Y ₅ or R ₅₀ is a group X ₅₀ L which promotes the adsorption of the compound represented by the general formula [V] on the surface of the silver halide grain.
_It may have _{50 m0} .

Here, X ₅₀ is an adsorption promoting group to silver halide, and L ₅₀
Is a divalent linking group. _m0 is 0 or 1.

Preferred examples of the adsorption promoting group for silver halide represented by X ₅₀ include a thioamide group, a mercapto group, a group having a disulphide bond or a 5- or 6-membered nitrogen-containing heterocyclic group.

The thioamide adsorption promoting group represented by X ₅₀ is A divalent group represented by amino-, which may be a part of a ring structure or an acyclic thioamide group. Useful thioamide adsorption promoting groups include, for example, U.S. Pat.
030,925, 4,031,127, 4,080,207, 4,245,0
No. 37, 4,255,511, 4,266,013, and 4,276,36
No. 4 and "Research Day Closure" (Res
earch Disclosure), Volume 151, No.15162 (November 1976)
Month), and No. 17626, No. 17626 (December 1978).

Specific examples of the acyclic thioamide group include, for example, a thioureido group, a thiourethane group, a dithiocarbamate group, and a specific example of the cyclic thioamide group.
For example, 4-thiazoline-2-thione, 4-imidazoline-2-thione, 2-thiohydatoin, rhodanine, thiobarbituric acid, tetrazoline-5-thione, 1,2,4-
Triazoline-3-thione, 1,3,4-thiadiazoline-
2-thione, 1,3,4-oxadiazoline-2-thione,
Examples thereof include benzimidazoline-2-thione, benzoxazoline-2-thione and benzthiazoline-2-thione, which may be further substituted.

The mercapto group of X ₅₀ is an aliphatic mercapto group, an aromatic mercapto group or a heterocyclic mercapto group (when the carbon atom to which the --SH group is bonded is a nitrogen atom next to it, a cyclic thioamide having a tautomeric relationship with this) Synonymous with the group, and specific examples of this group are the same as those listed above).

Examples of the 5-membered to 6-membered nitrogen-containing heterocyclic group represented by X ₅₀ include 5-membered to 6-membered nitrogen-containing heterocycles consisting of a combination of nitrogen, oxygen, sulfur and carbon. Of these, preferred are benzotriazole,
Examples include triazole, tetrazole, indazole, benzimidazole, imidazole, benzothiazole, thiazole, benzoxazole, oxazole, thiadiazole, oxadiazole, and triazine. These may be further substituted with appropriate substituents.

As the substituent, those mentioned as the substituent for Y ₅ can be mentioned.

The divalent linking group represented by L ₅₀ includes C, N,
An atom or atomic group containing at least one of S and O. Specifically, for example, an alkylene group, an alkenylene group, an alkynylene group, an arylene group, -O-, -S-,
-NH -, - N =, - CO -, - SO 2 - ( Some have these groups having a substituent) is made either alone, or a combination thereof and the like.

A ₅₁ and A ₅₂ are a hydrogen atom, an alkylsulfonyl group having 20 or less carbon atoms, and an arylsulfonyl group (preferably a phenylsulfonyl group or a sum of substituent constants of a hamet is −0.5.
A phenylsulfonyl group substituted as described above), (Preferably as R ₅₀₀ , a linear, branched, or cyclic alkyl group, alkenyl group, or aryl group having 30 or less carbon atoms (preferably phenyl group, or substituted so that the sum of the substituent constants of Hamet is -0.5 or more). been phenyl group), an alkoxy group (e.g., ethoxy), an aryloxy group (preferably monocyclic) and the like, these groups as the substituent may have a substituent Y ₅ And the sulfinic acid residues represented by A ₅₁ and A ₅₂ are specifically described in US Pat. No. 4,478,
Represents that described in No. 928.

Most preferably, A ₅₁ and A ₅₂ are hydrogen atoms.

Specific examples of the compound represented by the general formula [V] are shown below. However, the present invention is not limited to the following compounds.

The method of synthesizing the compound represented by the general formula [V] used in the present invention is described in, for example, JP-A Nos. 53-20,921 and 53-20,922.
No. 53, No. 53-66,732, No. 53-20,318, No. 56-67,843
No. 62-178,246, No. 62-180,361, Japanese Patent Application No. 62-26
No. 8,249, No. 62-58,513, No. 62-67,508, No. 62-67,
No. 509, No. 62-130,819, No. 62-143,469, U.S. Pat. Nos. 4,459,347, 4,478,928, and 4,560,638.

In the present invention, when the compound represented by the general formula [V] is contained in the photographic light-sensitive material, it is preferably contained in the silver halide emulsion layer, but other non-photosensitive hydrophilic colloid layers (eg protective layer). , Intermediate layer, filter layer, anti-halation layer, etc.). Specifically, when the compound to be used is water-soluble, as a water solution, and when it is poorly water-soluble, as a solution of water-miscible organic solvent such as alcohols, esters, and ketones, a hydrophilic colloid solution. Can be added to. When it is added to the silver halide emulsion layer, it may be added at any time from the start of chemical ripening to before coating, but it is preferably added after the completion of chemical ripening and before coating. In particular, it is preferable to add it to the coating solution prepared for coating.

The content of the compound represented by the general formula [V] of the present invention is the grain size of the silver halide emulsion, the halogen composition, the method and degree of chemical sensitization, the relationship between the layer containing the compound and the silver halide emulsion layer, It is desirable to select an optimum amount depending on the kind of the antifoggant compound, etc., and a test method for the selection is well known to those skilled in the art. Usually, preferably 10 ^-6 to 1 x 10 ^-1 mol per mol of silver halide,
In particular, it is used in the range of 10 ⁻⁵ to 4 × 10 ⁻² mol.

(3) The compound of the general formula [I] of the present invention can be applied to a multi-layered multicolor photographic material having at least two different spectral sensitivities on a support, mainly for improving graininess, improving sharpness, improving color reproducibility, and improving color reproducibility. It can be applied for the purpose of sensitivity enhancement. Multilayer natural color photographic materials are usually a red-sensitive emulsion layer, a green-sensitive emulsion layer, a
And at least one blue-sensitive emulsion layer. The order of these layers can be arbitrarily selected as required. The preferred order of the layer arrangement is red sensitivity, green sensitivity, blue sensitivity or blue sensitivity, red sensitivity, and green sensitivity from the support side. Each of the above emulsion layers may be composed of two or more emulsion layers having different sensitivities, and a non-photosensitive layer may be present between two or more emulsion layers having the same sensitivity. Usually, a cyan-forming coupler is contained in the red-sensitive emulsion layer, a magenta-forming coupler is contained in the green-sensitive emulsion layer, and a yellow-forming coupler is contained in the blue-sensitive emulsion layer, but different combinations can be used depending on circumstances.

The compound of the present invention can be used in combination with a coupler and added to the same emulsion layer as the coupler, or can be added as an independent emulsion dispersion to a photographic auxiliary layer such as an intermediate layer.

The compound of the present invention is used in a color light-sensitive material in which the yellow coupler in the blue-sensitive layer, the magenta coupler in the green-sensitive layer or the cyan coupler in the red-sensitive layer and the coupler in each light-sensitive layer are each contained in an amount of 0.1 to 50. Mol%, preferably
It is recommended to use 0.3 to 15 mol%. Further, it is preferable to use 1 × 10 ⁻⁵ mol to 8 × 10 ⁻² mol, particularly 1 × 10 ⁻⁴ mol to 5 × 10 ⁻² mol, per 1 mol of silver halide in the layer to be added.

(4) The compound of the general formula [I] of the present invention contains 0% silver chloride.
A black-and-white photographic light-sensitive material having a silver iodobromide or silver chloroiodobromide emulsion layer containing up to 50 mol% of silver iodide in an amount of up to 15 mol% on one side or both sides of the support, particularly X-ray sensitization It is effective for improving photographic performance such as sharpness of material. In this case, the acting amount is 1 × 10 ^-6 per mol of silver halide.
The range of 1 to 10 × ¹ mol, particularly 1 × 10 ^{−5 to} 5 × 10 ⁻² mol is preferable.

(5) The compound of the general formula [I] of the present invention can be advantageously used in the color diffusion transfer method as a highly active and highly efficient dye-donating substance.

The compound of the general formula [I] of the present invention is used in various other applications such as electron beam, high resolution black and white, diffusion transfer black and white, color X ray, and photothermographic material (including color). Applicable to

(Example) Next, the present invention will be described in more detail with reference to Examples.
It is not limited to this.

The preparation of the emulsions used in Examples 1 to 3 and the composition of the processing liquid are summarized below.

Preparation of emulsion (A) Highly monodisperse silver iodobromide was prepared by simultaneously adding an aqueous solution of silver nitrate and an aqueous solution of a mixture of potassium iodide and potassium bromide to an aqueous gelatin solution maintained at 50 ° C by keeping the pAg at 7.5 by the double jet method. An emulsion was prepared. The obtained silver iodobromide grains were cubic and had an average grain size of 0.26 μm and a silver iodide content of 2 mol%.

This emulsion was washed with water in a conventional manner to remove soluble salts, and then sodium thiosulfate was added for chemical sensitization.

Preparation of emulsion (B) Addition and mixing of an aqueous solution of silver nitrate and an aqueous solution of halogen salt are carried out at 60 ° C.
A monodispersed silver chlorobromide emulsion was obtained in the same manner as the emulsion (A) except that the addition was carried out in the presence of potassium hexachloroiridium (III) ate corresponding to 4 × 10 ^-7 mol per mol of silver. It was washed with water and chemically sensitized in the same manner as the emulsion (A). The prepared silver chlorobromide grains are cubic and have an average grain size of 0.28 μm.
The silver chloride content was 30 mol%.

Preparation of Emulsion (C) A monodisperse silver chlorobromide emulsion was prepared by simultaneously adding and mixing a silver nitrate aqueous solution and a halogen salt aqueous solution at a pAg of 7.8 in a gelatin aqueous solution maintained at 50 ° C. by the double jet method.
This emulsion was washed with settling water according to a conventional method to remove soluble salts, and then sodium thiosulfate was added in the same manner as in the emulsion (A) for chemical sensitization. The silver chlorobromide grains of the emulsion thus obtained were cubic and had an average grain size of 0.30 μm and a silver bromide content of 30 mol%.

Preparation of Emulsion (D) Add 5 × 10 5 silver nitrate aqueous solution and halogen salt aqueous solution.
Monodisperse silver chlorobromide emulsion (average grain size is the same as Emulsion (C)) except that silver chlorobromide grains are formed in the presence of rhodium ammonium chloride corresponding to ^-6 mol / mol silver. 0.30 μm, silver bromide content 30 mol%) was prepared.
This emulsion was washed with water as in the case of Emulsion (C), and then chemically sensitized by adding sodium thiosulfate and potassium chloroaurate.

Example 1 In emulsion (D), 4-hydroxy-6-methyl-1,3,3 was added.
a, 7-Tetrazaindene, polyethyl acrylate dispersion, polyethylene glycol (average molecular weight 1000), 1,
3-bisvinylsulfonyl-2-propanol, sensitizing dye (a) and compound V-5 of general formula [V] are added, and then compounds of general formula [I] of the present invention shown in Table 1 below are added. and then, coating amount of silver on a polyethylene terephthalate film is 3.50 g / m ^2, as the coating amount of gelatin 2.00 g / m ^2, further surfactants as a main component of gelatin, coating aids such as thickeners An aqueous solution containing the above is coated on the side far from the support simultaneously so that the amount of gelatin is 1.10 g / m ² and the sample (101-1
12) was created. Furthermore, samples (113 to 117) were prepared with the same formulation except that the compound of the general formula [I] was replaced with the comparative compounds (b) to (f).

The film thus obtained was passed through an exposure wedge for sensitometry and further exposed using a gray skeletoner negative contact screen No. 2, 150 L manufactured by Dainippon Screen Co., Ltd., and then a developer of the developer composition (E) was used. Developed at 38 ° C. for 30 seconds, fixed, washed with water and dried.

 The results obtained are shown in Table 1.

In Table 1, the halftone dot quality is visually evaluated on a scale of 5 levels, with "5" being the best and "1" being the poorest. Only "5" and "4" can be practically used as halftone dot original plates for plate making. "4.5" represents an intermediate quality between "4" and "5".

The halftone is the difference in the logarithmic value of the exposure amount that gives a blackened area of 5% and 95%, respectively, and the larger the difference, the softer the halftone.

As is clear from Table 1, by using the compound represented by the general formula [I] of the present invention, it is possible to obtain a better halftone dot quality and a softer halftone scale as compared with the case of using the compound other than the present invention. The key is obtained.

Example 2 In Emulsion A, 4-hydroxy-6-methyl-1,3,3a, 7-
Tetrazaindene, dispersion of polyethyl acrylate,
Polyethylene glycol (average molecular weight 1000), 1,3-bisvinylsulfonyl-2-propanol, sensitizing dye (a) (used for the samples shown in Table 2-1) or (a ')
(Used in the samples shown in Table 2-2) and the compounds of the general formula [V] shown in Tables 2-1 and 2-2 and potassium iodide were added, and then Tables 2-1 and 2- After adding the compound of the general formula [I] of the present invention shown in Table ² , the coating amount of silver was 3.5 g / m ² and the coating gelatin amount was 2.0 g / m ² on the polyethylene terephthalate film, and further gelatin was added. Samples (201 to 209) were prepared by simultaneously coating an aqueous solution containing a coating agent such as a surfactant and a thickener on the side far from the support so that the amount of coated gelatin would be 1.1 g / m ² . .

The film thus obtained was passed through an exposure wedge for sensitometry, and further exposed using a gray skeletoner negative contact screen No. 2, 150L manufactured by Dainippon Screen Co., Ltd., and then the developer composition (E) or (F). ) Developer
It was developed at 30 ° C. for 30 seconds, fixed, washed with water and dried.

 The obtained results are shown in Tables 2-1 and 2-2.

Sensitizing dye (a): the same compound as described in Example 1 The halftone gradation values shown in Tables 2-1 and 2-2 are the logarithmic values of the exposure amount giving the blackened areas of the halftone dots of 5% and 95%, as described in the first embodiment. It is a difference, and the larger the difference, the softer the halftone gradation.

As is clear from Tables 2-1 and 2-2, by using the compound represented by the general formula [I] of the present invention, a soft halftone gradation can be obtained as compared with the case where it is not used. Comparing Example 1 and Example 2, the halftone gradation softening effect of the compound of the present invention is remarkable, although there are differences in degree depending on the emulsion composition, the nucleating agent and the type of processing liquid. I knew it was.

Example 3 Samples (301 to 310) (using sensitizing dye (a) and compound V-5 of the general formula [V]) were used in the same manner as in Example 1 for emulsion (B) or (C). )created. After exposing this in the same manner as in Example 1, the developer (E) was used at 38 ° C. for 30 minutes.
It was developed for a second, fixed, washed with water and dried.

 The results obtained are shown in Table 3.

The halftone values shown in Table 3 are, as described in the first embodiment, the difference in the logarithmic value of the exposure amount which gives the blackened areas of halftone dots of 5% and 95%.

As is clear from Table 3, by using the compound represented by the general formula [I] of the present invention, the halftone gradation softening effect can be obtained even if the halogen composition of the silver chlorobromide emulsion is different.
It turns out to be remarkable.

Example 4 In order to evaluate the effectiveness of the compound of the present invention, JP-A-62-62
The undercoat layer was provided on the cellulose triacetate film support produced by the production method described in -115035 to prepare a multilayer color light-sensitive material 401 composed of each layer having the following composition.

 The emulsion coating amount represents the coating amount of silver.

(Sample 401) (1) Emulsion layer …… 1.6 g / m ² Coupler CO [below] …… 0.9 g / m ² Compound (1) of the present invention …… 0.009 g / m ² tricresyl phosphate …… 0.6 g / m ² included Gelatin layer (2) Protective layer Gelatin: 2.5 g / m ² 2,4-dichloro-6-hydroxy-s-triazine sodium: 0.13 g / m ² (Samples 402 to 405) Sample 401 of the compound of the present invention ( Sample 40 except that 1) was replaced with compounds (2) and (27) of the present invention in equimolar amounts
Samples 402 and 403 were prepared in the same manner as in 1.

Further, instead of the compound (1) of the present invention of the sample 401, samples 404 and 405 were prepared in the same manner as the sample 401 except that the compounds (b) and (c) for comparison were replaced by equimolar amounts.

These samples were exposed to forced deterioration conditions (45 ° C, 80% for 3 days) (B condition) and those not maintained (A condition) by imagewise exposure for sensitometry, and then subjected to the next color development processing. Done. The density of the obtained developed sample was measured with a red filter. The photographic properties obtained are summarized in Table 4. The development process used here was carried out at 38 ° C. as described below.

1 color development 3 minutes 15 seconds 2 bleaching 6 minutes 30 seconds 3 water washing 3 minutes 15 seconds 4 fixing 6 minutes 30 seconds 5 water washing 3 minutes 15 seconds 6 stability 3 minutes 15 seconds each The composition of the treatment liquid used in the process is as follows.

Color developer Sodium nitrilotriacetate 1.0 g Sodium sulfite 4.0 g Sodium carbonate 30.0 g Potassium bromide 1.4 g Hydroxylamine sulfate 2.4 g 4- (N-ethyl-N-β-hydroxyethylamino)
2-Methylaniline sulfate 4.5g Water added 1 Bleach Ammonium bromide 160.0g Ammonia water (28%) 25.0cc Ethylenediamine-sodium tetraacetate iron salt 130.0g Glacial acetic acid 14.0cc Water added 1 Fixer Tetra Sodium polyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0cc Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin 8.0cc Add water 1 From Table 4, samples 401 to 403 using the compound of the present invention
It is clear that there is almost no change in photographic performance before and after forced deterioration as compared with the sample using the conventional compound.

Example 5 A transparent support triacetyl cellulose film support prepared by a solution casting method was used to prepare a multi-layer color light-sensitive material (501) comprising each layer having the following composition.

1st layer: Anti-halation layer Black colloidal silver …… 0.15g / m ² UV absorber U-1 …… 0.08g / m ² U-2 …… 0.12g / m ² containing gelatin layer 2nd layer: Intermediate Layer 2,5-di-t-pentadecylhydroquinone ... 0.18g / m
² coupler C-1: gelatin layer containing 0.11 g / m ² 3rd layer: 1st red-sensitive emulsion layer …… 1.2 g / m ² Sensitizing dye I …… 1.4 × 10 ^-4 mol per mol silver Ⅱ II …… 0.4 × 10 ^-4 mol per mol silver Ⅲ …… against 1 mol silver Te 5.6 × 10 ^-4 mol same IV ...... 1 mol of silver relative to 4.0 × 10 ^-4 mol coupler C-2 ...... 0.45 g / m 2 coupler C-3 ...... 0.035g / m ² coupler C-4 ... Gelatin layer containing 0.025 g / m ² 4th layer: 2nd red-sensitive emulsion layer ...... 1.0 g / m ² sensitizing dye I ...... 1 mol of silver to 1.5 × 10 ^-5 mol same III ...... 1 mol of silver relative to 5.2 × 10 ^-5 m ² the II ...... silver mole with respect to On the other hand, 2.1 × 10 ^-4 moles Same IV …… 1.5 × 10 ^-5 moles per mole of silver Coupler C-2 …… 0.050 g / m ² coupler C-5 …… 0.070 g / m ² coupler C-3 ...... Gelatin layer containing 0.035 g / m ² Fifth layer: intermediate layer 2,5-di-t-pentadecylhydroquinone ...... 0.08 g / m
^2nd gelatin layer containing 6th layer: 1st green emulsion layer ...... 0.80g / m ² Sensitizing dye V ...... 4.0 × 10 ^-4 moles to 1 mole of silver VI ...... 3.0 × 10 ^-5 moles to 1 mole of silver VII ............ to 1 mole of silver 1.0 × 10 ^-4 mol Coupler C-6 ...... 0.45g / m ² Coupler C-7 ...... 0.13g / m ² Coupler C-8 ...... 0.02g / m ² Coupler C-4 ...... 0.04g / m Gelatin layer containing ^2nd 7th layer: 2nd green-sensitive emulsion layer …… 0.85 g / m ² Sensitizing dye V …… 2.7 × 10 ^-4 moles to 1 mole silver Same VI …… 1.8 × 10 ^-5 moles to 1 mole silver VII …… To 1 mole silver 7.5 × 10 ^-5 mol Coupler C-6 …… 0.095 g / m ² Coupler C-7 ・ ・ ・ Gelatin layer containing 0.015 g / m ² 8th layer: Yellow filter layer Yellow colloidal silver …… 0.08 g / m ² 2,5-di-t-pentadecylhydroquinone ... 0.090g /
Gelatin layer containing m ² 9th layer: 1st blue emulsion layer ...... 0.37 g / m ² Sensitizing dye VIII 4.4 × 10 ^-4 mol coupler relative ...... silver mole C-9 ...... 0.71g / m ² Coupler C-4 ...... 0.07g / m ² 10th Layer : Second blue-sensitive emulsion layer ...... 0.55g / m ² Sensitizing dye VIII ...... 1 mol of silver Gelatin layer 11th layer containing 3.0 × 10 ^-4 mol Coupler C-9 ...... 0.23g / m ² with respect to: a first protective layer ultraviolet absorbing Gelatin layer containing agent U = 1 ...... 0.14 g / m ² same U-2 ...... 0.22 g / m ² 12th layer: 2nd protective layer ...... 0.25 g / m ² polymethacrylate particles (diameter 1.5 µ) ...... 0.10 g / m ² containing gelatin layer Each layer was coated with gelatin hardener H-1 and a surfactant in addition to the above composition.

Structure of compounds used in Examples (Sample 502) A sample 502 was prepared in the same manner as the sample 501 except that the compound (32) of the present invention was applied in an amount of 0.008 g / m ² instead of the coupler C-4 in the sixth layer of the sample 501.

The samples were exposed for sensitometry and subjected to the same color development process as in Example 4. The density of the developed sample was measured with a green filter to obtain photographic data. Further, after exposing through a filter whose density was changed stepwise, the color development treatment was carried out, and the graininess was measured with a green filter. Granularity was measured by the conventional RMS method. The measurement aperture used was a 48 μ aperture.

 The results are shown in Table 5.

According to Table 5, the sample 502 using the compound of the present invention has almost the same sensitivity and gamma as the sample 501 using the conventional DIR coupler for comparison, but the RMS
It can be seen that the granularity represented by the value is long.

Example 6 Preparation of Photosensitive Silver Halide A silver iodobromide emulsion (iodine content: 2 mol%) having an average particle size of 1.3 μ was prepared from silver nitrate, potassium bromide and potassium iodide by a usual ammonia method. Chemical sensitization was carried out by a gold / sulfur sensitization method using chloroauric acid and sodium thiosulfate, followed by washing by an ordinary precipitation method, and 4-hydroxy-6-methyl-1,3,3a, as a stabilizer 7-Tetrazaindene was added to obtain a photosensitive silver iodobromide emulsion.

Preparation of Samples 601 to 627 An emulsion prepared by adding the compound represented by the general formula [I] of the present invention shown in Table 6 or the comparative compounds (b) and (c) to the photosensitive silver halide emulsion prepared by the above method. Samples 601 to 627 were prepared in which the layer and the protective layer of the aqueous gelatin solution were uniformly and sequentially coated on both surfaces of the polyester base subjected to the subbing process.

The coating amount at this time was the same on each side, the coating silver amount on both sides was 8.0 g / m ² , and the gelatin coating amount on the protective layer was 2.6 g / m ² The gelatin coating amount was 5.2 g / m ² .

These samples were sandwiched on both sides with a fluorescent intensifying screen containing calcium tungstate, and an aluminum rectangular wave chart was brought into close contact as an object, and X-ray exposure was performed so that the density became 1.0, and then the developer of the following formulation The sample was developed at 35 ° C. for 25 seconds, then fixed, washed with water and dried, and the CTF was measured with a microphotometer. The results obtained are shown in Table 6.

(Developer formulation) Potassium hydroxide 29.14g Glacial acetic acid 10.96g Potassium sulfite 44.20g Sodium bicarbonate 7.50g Boric acid 1.00g Diethylene glycol 28.96g Ethylenediaminetetraacetic acid 1.67g 5-Methylbenzotriazole 0.06g 5-Nitroindazole 0.25g Hydroquinone 30.00g 1-phenyl-3-pyrazolidone 1.50g glutaraldehyde 4.93g sodium metabisulfite 12.60g Add water to finish 1 As is apparent from Table 6, the photographic light-sensitive material containing the compound of the present invention is added. It can be seen that the CTF value is larger and the sharpness is improved as compared with the non-comparative sample. The results are larger than those of the comparative compounds (b) and (c), and the usefulness of the compound of the present invention is clear.

Example 7 A photosensitive sheet was prepared by sequentially coating the following layers on a transparent polyester support.

(1) Yellow dye-releasing redox compound (1.1 g / m ² ) having the following structure, tricyclohexyl phosphate (1.6 g / m ² ).
m ² ), and a layer containing gelatin (1.4 g / m ² ).

(2) internal latent image type direct reversal silver bromide emulsion of the blue sensitive (1.08 g / m ² in an amount of silver, gelatin 1.2 g / m ^2), nucleating agents the following (0.0
5 mg / m ² ) and a layer containing sodium pentadecyl hydroquinone sulfonate (0.18 g / m ² ).

(3) A layer containing gelatin (1.0 g / m ² ).

Sample 702, which was the same as sample 701, was prepared except that the sample containing the yellow redox compound of layer (1) of the above sheet was 701 and this redox compound was substituted.

702; sample containing 1.1 g / m ^{2 of the} compound (24) Next, a photosensitive sheet was prepared by sequentially coating the following layers on a transparent polyester support.

(4) Magenta dye-releasing redox compound (0.93 g / m ² ) and tricyclohexyl phosphate (1.
A layer containing 3 g / m ² ) and gelatin (2.0 g / m ² ).

(5) Green (1.11 g / m ² in an amount of silver, gelatin 1.23 g / m ²⁾ internal latent image type direct reversal silver bromide emulsion sensitivity, the same nucleating agent as a layer (2) (0.04 mg / m ² ) and the layer containing the 2-sulfo -5-n-pentadecylhydroquinone sodium salt (0.22g / m ^2).

(6) A layer containing gelatin (1.1 g / m ² ).

Sample 704, which was the same as sample 703 except that the sample containing the magenta redox compound of layer (4) of the sheet was 703 and the magenta redox compound was substituted, was prepared.

704 is a sample containing 0.03 g / m ^{2 of the} compound (34).

0.8 g of the treatment liquid having the following composition was filled in a rupturable container.

3) Composition of treatment composition: 1-drill-4-hydroxymethyl-4-methyl-3-
Pyrazolidinone 12 g Methylhydroquinone 0.4 g 5-Methylbenzotriazole 5.0 g Sodium sulfite (anhydrous) 2.0 g Hydroxyethyl cellulose 40 g Potassium hydroxide 56 g Benzyl alcohol 1.5 ml Water to make the total amount 1 kg On transparent polyester support, Mordant (3.0g
/ m ² ) and gelatin (3.0 g / m ² ) containing a mordant layer to prepare an image-receiving sheet.

After exposure, Samples 701, 702, 703, and 704 were integrated with a container containing the treatment liquid and a mordant sheet, and the treatment liquid was spread to a thickness of 80 μm by a pressing member at 15 ° C. and 25 ° C. After 5 minutes, the mordant sheet was peeled off to obtain a transfer color image. The results are shown in Table 7.

As is clear from Table 7, the compounds of the present invention release the dye with higher activity and higher efficiency than the conventionally known compounds, so that the maximum concentration is improved and the concentration changes due to the difference in the treatment temperature. Can be reduced.

Example 8 Preparation of Sample (801) A multi-layer color light-sensitive material having the following composition was prepared on a cellulose triacetate film support.

First layer: Anti-halation layer (AHL) Gelatin layer containing black colloidal silver Second layer: Intermediate layer Gelatin layer containing emulsion dispersion of 2,5-di-t-octylhydroquinone Third layer: First red-sensitive emulsion Layer (RL ₁ ) Silver iodobromide emulsion (silver iodide: 5 mol%) …… Silver coating amount 1.79 g / m ² Sensitizing dye I …… 6 × 10 ^-5 mol sensitizing dye per 1 mol silver II ...... 1.5 × 10 ^-5 moles to 1 mole silver Coupler A ...... 0.04 moles to 1 mole silver Coupler C-1 ...... 0.0015 moles to 1 mole silver Coupler C-2 ...... 1 mole silver 0.0015 mol to the compound of the present invention (30) ... 0.0006 mol to 1 mol of silver Fourth layer: second red-sensitive emulsion layer (RL ₂ ) Silver iodobromide emulsion (silver iodide: 4 mol%) ...... Silver coating amount 1.4 g / m ² Sensitizing dye I ・ ・ ・ 3 × 10 ^-5 mol Sensitizing dye II ・ ・ ・ 1.2 × 10 ^-5 mol coupler A ・ ・ ・Per mole of silver 0.005 mol Coupler C-1 ... 0.0008 mol per mol of silver Coupler C-2 ... 0.0008 mol per mol of silver Compound (30) of the present invention ... 0.00006 mol per mol of silver Fifth layer : Middle layer (ML) Same as the second layer Sixth layer: First green-sensitive emulsion layer (GL ₁ ) Silver iodobromide emulsion (silver iodide: 4 mol%) .. Coating silver amount 1.5 g / m
² Sensitizing dye III: 3 × 10 ^-5 mol per mol of silver Sensitizing dye IV: 1 × 10 ^-5 mol of coupler per mol of silver Coupler B: 0.05 mol of coupler per mol of silver M-1: 0.008 mol per mol of silver Compound of the present invention (30): 0.0015 mol per mol of silver Seventh layer: second green-sensitive emulsion layer (GL ₂ ) Silver iodobromide emulsion ( Silver iodide: 5 mol%) …… Coating silver amount 1.6 g / m
² Sensitizing dye III: 2.5 × 10 ^-5 mol per mol of silver Sensitizing dye IV: 0.8 × 10 ^-5 mol per mol of silver Coupler B: 0.02 mol coupler per mol of silver M-1: 0.003 mol per mol of silver Compound of the present invention (30): 0.0003 mol per mol of silver Eighth layer: yellow filter layer (YEL) Yellow colloidal silver and 2. 5-di-t
A gelatin layer comprising an emulsified dispersion of octyl hydroquinone.

9th layer: 1st blue-sensitive emulsion layer (BL ₁ ) Silver iodobromide emulsion (silver iodide: 6 mol%) ...... Coating silver amount 1.5 g / m ² Coupler Y-1 ...... for 1 mol of silver 0.25 mol 10th layer: 2nd blue-sensitive emulsion layer (BL ₂ ) Silver iodobromide (silver iodide: 6 mol%) ...... Coating amount of silver 1.1 g / m ² Coupler Y-1 ...... For 1 mol of silver 0.06 mol 11th layer: Protective layer (PL) Polymethylmethanoacrylate particles (Coated with a gelatin layer containing 1.5 μm in diameter.

In addition to the above composition, a gelatin hardening agent and a surfactant were added to each layer.

 The sample 801 manufactured as described above was used.

Sample 802: Instead of the compound (30) of Sample 801, the compound (3
It was prepared in the same manner as Sample 801, except that 5) was added in an equimolar amount.

Sample 803: Prepared in the same manner as Sample 801, except that the comparative compound (b) was added in equimolar amount instead of the compound (30) of Sample 801.

Sample 804: A sample was prepared in the same manner as Sample 801, except that a comparative compound (G) was added in an equimolar amount instead of the compound (30) of Sample 801.

Compound used to prepare sample Sensitizing dye I: Anhydro-5,5'-dichloro-3,3 '
-Di- (γ-sulfopropyl) -9-ethyl-thiacarbocyanine hydroxide / pyridinium salt Sensitizing dye II: anhydro-9-ethyl-3 / 3'-di-
(Γ-Sulfopropyl) -4,5'4'5'-dibenzothiacarbocyanine hydroxide triethylamine salt Sensitizing dye III: anhydro-9-ethyl-5,5'dichloro-3,3'-di- ( γ-sulfopropyl) oxacarbocyanine sodium salt Sensitizing dye IV: anhydro-5,6,5 ', 6'-tetrachloro-1,1'-diethyl-3,3'-di- {β-
[Β- (γ-sulfopropoxy) ethoxy] ethylimidazolocarbocyanine hydroxide sodium salt The obtained Samples 801 to 804 were processed into a film having a size of 35 mm and subjected to wet exposure, and 600 m of each was subjected to the developing treatment shown below in two developer tanks.

1. Color development …… 3 minutes 15 seconds 2. Bleaching …… 6 minutes 30 seconds 3. Washing …… 3 minutes 15 seconds 4. Fixing …… 6 minutes 30 seconds 5. Washing …… 3 minutes 15 seconds 6. Stable… 3 minutes 15 seconds The composition of the treatment liquid used in each step is as follows.

Color developer Sodium nitrilotriacetate 1.0g Sodium sulfite 4.0g Sodium carbonate 30.0g Potassium bromide 1.4g Hydroxylamine sulfate 2.4g 4- (N-ethyl-N-β hydroxyethylamino)-
2-Methyl-aniline sulfate 4.5g Water added 1 Bleach Ammonium bromide 160.0g Ammonia water (28%) 25.0ml Ethylenediamine-tetraacetic acid sodium iron salt 130g Glacial acetic acid 14ml Water added 1 Fixer Tetra Sodium polyphosphate 2.0g Sodium sulfite 4.0g Ammonium thiosulfate (70%) 175.0ml Sodium bisulfite 4.6g Add water 1 Stabilizer Formalin 8.0ml Add water 1 Regenerate the developer overflow by the following method Processed and reused repeatedly.

The reproduction process was performed by the batch method. First, the overflow solution was placed in an electrodialysis tank, and electrodialysis was performed so that KBr was 0.7 g / or less.

Sodium nitrilotriacetate, sodium sulfite, sodium carbonate, potassium bromide, hydroxylamine sulfate, 4- (N-ethyl-
N-β hydroxyethylamino) -2-methyl-aniline sulfate was added to adjust the pH to 10.05 and reused as a replenisher. Table 1 shows that once every 1 minute overflow
It showed a decrease in sensitivity after 10 reuses.

From the results of Table 8, the samples 801 and 802 showed almost no decrease in sensitivity, while the samples 803 and 804 showed a large decrease in sensitivity. This is because the leaving groups of the compounds (30) and (35) are dispersed and decomposed into a photographically unaffected compound even if they flow out to the color developing solution, so that they are similar to other non-decomposable leaving groups. , Shows that it can be reused repeatedly without being accumulated in the developing solution.

Example 9 80 mol% silver chloride, 19.5 mol% silver bromide, and 0.5
A silver halide emulsion consisting of mol% silver iodide was prepared by gold sensitization and sulfur sensitization by a conventional method. The gelatin contained in this emulsion was 45% by weight based on silver halide. 5- [3- (8-sulfobutyl) -5 was added to this emulsion.
-Chloro-2-oxazolidylidene ethylidene] -1-
Hydroxyethoxyethyl-3- (2-pyridyl) -2
Thiohydanin potassium salt (sensitizing dye), sodium dodecylbenzene sulfonate (surfactant), polymer latex as described in Preparation Example Formula 3 of US Pat. No. 3,525,620, and then 1,2-bis ( Vinylsulfonylacetamido) ethane (a hardening agent) is added so as to be 2.6 wt% based on the total dry gelatin (that is, based on the total dry gelatin including the non-photosensitive upper layer described later), and the compound of the present invention is further added. The compounds shown in Table 9 were added as a methanol solution to prepare a photosensitive silver halide emulsion layer coating solution.

On the other hand, concurrently with this, sodium dodecylbenzenesulfonate (surfactant) and polymethylmethacrylate latex (matt agent) with an average particle size of 3.0 to 4.0μ were added to a 5% gelatin solution to prepare a non-photosensitive upper layer coating solution. Made.

Next, the coating solution for the photosensitive silver halide emulsion layer and the coating solution for the non-photosensitive upper layer were coated on a polyester terephthalate support by a two-layer simultaneous coating method. The amount of coated silver is 3.0g
/ m ² , the dry film thickness of the non-photosensitive upper layer is 1.0 μm. In this way, Samples 901 to 904 were prepared. 8 white tungsten light is applied to these samples through a step wedging with a step of 0.1.
Second exposure.

Halftone images were formed on these samples by the following method. That is, a commercially available negative gray contact screen (150 lines / inch) was brought into close contact with the sample, and white tungsten light was passed through the staircase wedge with a step difference of 0.1.
Exposure was for 0 seconds. Each sample was developed at
Development was carried out for 0 seconds, and fixing, washing with water and drying were carried out by a usual method.

Table 9 shows the results of evaluation of relative sensitivity, γ and dot quality.

The relative sensitivity is the relative value of the reciprocal of the exposure amount that gives a density of 1.5, and Sample 1 was set to 100.

The halftone dot quality is visually evaluated on a four-level scale, and is “A”.
Is the best quality, "B" is the practical quality, "C" is the quality below the practical limit, and "D" is the worst quality.

As is clear from Table 9, the compounds of the present invention have a high feeling, an extremely large film-hardening and curing, and a very good dot quality.

Example 10 80 mol% silver chloride, 19.5 mol% silver bromide, and 0.5
A silver halide emulsion consisting of mol% silver iodide was prepared by gold sensitization and sulfur sensitization by a conventional method. The gelatin contained in this emulsion was 45% by weight based on silver halide. To this emulsion was added 3-carboxymethyl-5- [2-
(3-Ethyl-thiazolinylidene) ethylidene] rhodamine (spectral sensitizer), 4-hydroxy-1,3,3a, 7-tetrazaindene (stabilizer), polyoxyethylene nonyl containing 50 ethylene oxide groups Phenyl ether, US Pat. No. 3,525,620, polymer latex as described in Recipe 3 of Preparation Example was added, followed by addition of 1,2-bis (vinylsulfonylacetamido) ethane (hardener) per total dry gelatin (ie, as described below). 2.6 wt% (based on the total dry gelatin including the non-photosensitive upper layer), and the compound of the present invention was added as a methanol solution as shown in Table 10 to obtain a photosensitive silver halide. A coating solution for emulsion layer was prepared.

On the other hand, concurrently with this, sodium dodecylbenzenesulfonate (surfactant) and polymethylmethacrylate latex (matt agent) with an average particle size of 3.0 to 4.0μ were added to a 5% gelatin solution to prepare a non-photosensitive upper layer coating solution. made.

Next, the photosensitive silver halide emulsion layer coating liquid and the non-photosensitive upper layer coating liquid cloth were coated on a polyester terephthalate support by a two-layer simultaneous coating method. The amount of coated silver is 3.0g
/ m ² , the dry film thickness of the non-photosensitive upper layer is 1.0 μm. In this way, samples 1001 to 1008 were prepared.

Halftone images were formed on these samples by the following method.
That is, a commercially available negative gray contact screen (150 lines / inch) was brought into close contact with the sample, and there was no step
After exposure to white tungsten light for 10 seconds through a 0.1 step wedge, each sample was exposed to 10 ° C at 27 ° C using the following developer.
Development was carried out for 0 seconds, and fixing, washing with water and drying were carried out by a usual method.

The following compounds were used as comparative compounds in Table 10.

(Comparative compound a) 1-Phenyl-5-methylcaptotetrazole (Comparative compound b) 5-Methylzotriazole (Comparative compound c) 2-Methylthio-5-mercapto-1,3,4-thiadiazole Halftone dot quality and mesh floor Table 10 shows the results of evaluation of the tones. The halftone dot quality is visually evaluated in four levels,
"A" is the best quality, "B" is the practical quality,
"C" represents quality below the practical limit, and "D" represents the worst quality. The halftone is the difference between the logarithmic values of the exposure amount that gives the blackened areas of halftone dots of 5% and 95%. The larger the difference, the softer the halftone.

As is clear from Table 10, the compound of the present invention is extremely hardened to soften the halftone gradation without degrading the halftone dot quality. That is, the comparative compound (a),
0.1% compared with the case where halftone gradation is not added using (b) and (c)
When the tone is softened as described above, the halftone dot quality becomes "D" rank, but when the compound of the present invention is used, the halftone gradation is greatly softened to 0.1 to 0.2 and the halftone dot quality is "A" as compared with the case of no addition. It was good with rank.

Example 11 Samples 1001, 1002, and 1003 of Example 10 were exposed and developed in the same manner as in Example 10. However, the development is 27 ℃ 90 seconds, 100
3 seconds of 110 seconds were performed. Table 11 shows the results of five-level evaluation of the halftone dot quality at that time. “5” is the best quality, “1” is the worst quality, and “5” to “3.5” is the practical range.

From Table 11, the halftone dot quality of the sample of the present invention is good in both 5% and 95% halftone dots as compared with the case of no addition, and even with a developing time shorter than the standard developing time (100 seconds), It can be seen that the halftone quality is good and the development latitude is wide even with a long development time.

Example 12 Samples 1001, 1002 and 1003 of Example 10 were overlaid on an original (A) containing a white line having a line width of 50 μ on a black background and an original (B) containing a black line having a line width of 50 μ on a white background. After exposure with white tungsten light for 10 seconds using a camera, each sample was developed in the same manner as in Example 10. The results are shown in Table 12.

It can be seen from Table 12 that the line width reproducibility of the fine line is good when the compound of the present invention is used. From this result, it can be understood that the exposure latitude is wide when an original in which Mincho characters and Gothic characters are mixed is used in the actual plate making process.

Example 13 1 × 10 5 consisting of 95 mol% silver chloride, 5 mol% silver bromide
^-4 mol / mol silver rhodium-containing silver halide emulsion hardener 2-hydroxy-4,6-dichloro-1,3,5-triazine sodium salt and polyoxy containing 30 ethylene oxide groups Ethylene nonylphenyl ether was added at 1 × 10 ^-4 mol / mol silver, and the compound of the present invention shown in Table 10 was further added as a methanol solution as shown in Table 10 to give 1 m on the polyethylene terephthalate film.
^It was applied so that the amount of silver per ² was 4.5 g.

The film sample thus prepared was used in US Pat.
After exposing it with a P-607 type printer manufactured by Dainippon Screen Co., Ltd. using a manuscript having the constitution shown in FIG. 1 of No. 2,882, development was carried out at 38 ° C. for 20 seconds using the following developing solution, and then by a usual method. It was fixed, washed with water and dried.

The results are shown in Table 13.

Here, the blank character image quality 5 in Table 13 is a US patent.
Using an original such as that shown in Fig. 1 of 4,452,882, the image quality that reproduces a character of 30 μm width when properly exposed so that a halftone dot area of 50% becomes a halftone dot area of 50% on a return photosensitive material. It is a very good character quality without blank characters. On the other hand, the blank character image quality 1 is an unexplained blank character quality that can reproduce only a character with a width of 150 μm or more when the same appropriate exposure is given, and it is between 4 and 2 in the sensory evaluation between 5 and 1. Rank is set. Two or more is a practical level.

As is apparent from Table 13, the compounds of the present invention show good blank character quality.

Claims (1)

(57) [Claims] 1. A silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer, containing at least one photographic reagent represented by the following general formula (I). Silver photographic light-sensitive material. General formula (I) (In the formula, X represents a hydrogen atom or a group capable of becoming a hydrogen atom by a hydrolysis reaction. Time represents a divalent linking group, t represents 0 or 1. PUG represents a photographically useful group. V is a carbonyl group, a sulfonyl group, a sulfoxy group, (R ₀ represents an alkoxy group or an aryloxy group.), An iminomethylene group, a thiocarbonyl group or (W represents an electron-withdrawing substituent). R represents a hydrogen atom, an aliphatic group, an aromatic group, or Represents