JPH07117724B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention is a novel compound which can be satisfactorily incorporated in a light-sensitive material layer and can be decolorized so as not to cause residual color contamination due to development processing. The present invention relates to a silver halide photographic light-sensitive material having at least one layer containing a light absorbing compound.

(Prior Art) Generally, in a silver halide photographic light-sensitive material, sensitivity adjustment, safelight safety improvement, light color temperature adjustment, halation prevention, static fog prevention, or sensitivity balance adjustment in a multilayer color light-sensitive material For the purpose of
It has been conventionally practiced to incorporate a light absorbing compound into a silver halide emulsion layer or other hydrophilic colloid layer in order to absorb light having a specific wavelength.

For example, a silver halide photographic light-sensitive material is formed by forming a hydrophilic colloid layer such as a light-sensitive silver halide emulsion layer on a support, and an image is recorded on the light-sensitive silver halide emulsion layer to form an image. In the case of similar exposure, it is necessary to control the spectral composition of light incident on the silver halide emulsion layer in order to improve photographic sensitivity. In such a case, a dye capable of absorbing light in a wavelength range unnecessary for the silver halide emulsion layer is usually added to the hydrophilic colloid layer present on the side farther from the support than the photosensitive silver halide emulsion layer. A method is used in which it is contained to form a filter layer and only light in a target wavelength range is transmitted.

In particular, the silver halide photographic light-sensitive material used in the photoengraving process, more specifically, the light-sensitive material for the bright room, contains a dye that absorbs UV light or visible light in the light-sensitive layer or the light source in order to enhance safety against safelight light. And in the layer between the photosensitive layer and the photosensitive layer.

Further, it is added to the hydrophilic colloid layer between the light-sensitive silver halide emulsion layer and the support to prevent halation.

The dye used for such a purpose is one that is decolorized during the photographic development process and is easily eluted from the silver halide photographic light-sensitive material to prevent substantial residual color contamination by the dye after the development process. It does not adversely affect the emulsion such as fogging and desensitization, does not diffuse from the colored layer to other layers, has good absorption spectrum characteristics according to the purpose of use, and further Alternatively, it must satisfy various conditions such as excellent stability over time and no deterioration in the silver halide photographic light-sensitive material.

Many efforts have been made to find dyes that meet these conditions. For example, pyrazolone oxonol dyes described in British Patent 506,385, U.S. Pat.
Oxonol dyes described in U.S. Pat. No. 2,390,707, azo dyes described in U.S. Pat.
Styryl dyes described in 2,255,077, British Patent No. 58
Hemioxonol dyes described in 4,609, merocyanine dyes described in U.S. Pat.No. 2,493,747, cyanine dyes described in U.S. Pat.No. 2,843,486, methylene benzylidene dyes described in U.S. Pat. can give.

When the layer containing the dye functions as a filter layer or an anti-halation layer, it is necessary that the layer be selectively colored so that the other layers are not substantially colored. This is because when the other layers are substantially colored, not only the harmful spectral effect is exerted on the other layers, but also the effects as the filter layer and the antihalation layer are eliminated. Further, if the dye added to a specific layer diffuses and the other layers are colored for the purpose of preventing irradiation, the same problem as described above occurs. Further, in the printing light-sensitive material, the diffusion of the dye into the light-sensitive silver halide emulsion layer causes a problem of impairing "tone variability".

In general, image conversion in printing can be said to be "a process of converting continuously changing light and shade into the size of a halftone dot area". However, this conversion is not always performed faithfully to the manuscript, and it is possible to intentionally soften the gradation or harden it because of the sensory requirements such as "to give a texture" and "to give a gloss". It is a daily practice to make changes. The gradation correction in the returning step is performed by increasing the exposure amount as compared with the standard exposure. The easiness of gradation change at this time is called tone variability. The modification is to increase the halftone dot having a halftone dot area of 50% at the standard exposure by 5 to 10%, that is, the halftone dot area of 55 to 60%. This correction is 3-5 of standard exposure
It is desirable that the exposure amount be doubled. If the tone changes with a very small change in the exposure amount, it is difficult to control, and if the exposure amount is too long, it takes too much working time.

As a method for solving this problem, conventionally known is a method in which a so-called acidic dye having a sulfo group or a carboxyl group is localized in a specific layer by using a mordant.

As such a mordant, an ethylenically unsaturated compound polymer having a dialkylaminoalkyl ester residue described in British Patent No. 685,475, a reaction product of a polyvinyl alkyl ketone and aminoguanidine described in No. 850,281, U.S. Pat. No. 2,548,564, No. 2,484,430, No.
Vinyl pyridine polymers and vinylpyridinium cationic polymers described in 3,148,061 and 3,756,814 are known, and secondary and tertiary amino groups are contained in the polymer so that the acid dye described above can be mordant effectively. ,
A cationic mordant containing a nitrogen-containing heterocyclic group and these quaternary cationic groups is used.

(Problems to be Solved by the Invention) However, these cationic mordants are gelatin which is often used as a hydrophilic colloid and a surfactant having an alcoholate group, a carboxylate group, a sulfonate group, and a sulfato group which are usually used as a coating aid. Electrostatic interaction may occur and the coating properties may deteriorate.

Further, in the color light-sensitive material, desilvering property may be deteriorated and the sensitivity of the adjacent emulsion layer may be lowered.

In such a mordant, the acid dye described above was often found to diffuse to other layers, and it was considered to use a large amount of the mordant to eliminate the diffusion, but it is not possible to completely eliminate the diffusion. However, the film thickness of the layer to be contained becomes large, which causes a defect that the sharpness is lowered.

Further, in the sensitizing material for printing plate making, a reduction operation using a reducing liquid is usually performed to adjust the concentration and gradation, and the reducing liquid contains water-soluble iron as a reducing agent. The complex is contained, and when the cationic mordant described above is used, it has the drawback that it is electrostatically bound to the iron complex and causes yellow contamination by the iron complex.

(Object of the Invention) Accordingly, the first object of the present invention is to provide a silver halide photograph which is dyed with a dye and has at least one layer in which diffusion of the dye to other layers is suppressed and which is decolorized during photographic development processing. It is an object of the present invention to provide a silver halide photographic light-sensitive material that does not elute from the light-sensitive material and causes substantially no stain after development processing.

A second object of the present invention is to provide a silver halide photographic material containing at least one layer colored with a dye having improved coating properties and suppressing interaction with gelatin and coating aids.

A third object of the present invention is to provide a silver halide photographic material having improved desilvering property and suppressing desensitization of an adjacent emulsion layer.

A fourth object of the present invention is to provide a photographic material that suppresses color contamination by the reducing solution during the reducing process.

(Means for Solving Problems) The above object of the present invention has at least one silver halide emulsion layer on a support, and the emulsion layer or other hydrophilic colloid layer has the general formula [II]. This is achieved by a silver halide photographic light-sensitive material containing a compound represented by and a hydrazine derivative as a contrast-increasing agent.

General formula (II) In the general formula [II], EAG represents a group that receives an electron from a reducing substance, and is bonded to a nitrogen atom.

(Time _t LA binds to at least one of R ¹ , R ^{2 and} EAG. (Time _t LA is released from the molecule represented by the general formula (II) when EAG receives an electron from a reducing substance.

Time is calculated from the numerator represented by general formula (II) (Time _t LA
Represents a group that releases LA as LA and then releases LA through a subsequent reaction.

t represents an integer of 0 or 1.

LA represents a dye group having a light absorption maximum at 310 nm or more.

X is a group containing an oxygen atom (-O-), a sulfur atom (-S-), and a nitrogen atom. Represents

R ¹ , R ² and R ³ represent a group other than a hydrogen atom or a simple bond. R ¹ , R ² and R ³ are bonded to each other to
An 8-membered ring may be formed.

EAG represents a group that receives an electron from a reducing substance, and is bonded to a nitrogen atom. As EAG, a group represented by the following general formula [A] or [B] is preferable.

General formula [A] General formula [B] In the general formula [A], Z ₁ is Alternatively Vn 'is Z _1, together with Z ₂ represents an atomic group necessary for forming a 3 to 8-membered ring and n' represents an integer of 3 to 8 V ₃ which represent _{-N; -Z 3 -, V 4} ; - _{Z 3 -Z 4 -, V 5} ; -Z 3 -Z 4 -Z 5,
Z ₆ ; -Z ₃ -Z ₄ -Z ₅ -Z _6- , Z ₇ ; -Z ₃ -Z ₄ -Z ₅ -Z
_{6 -Z 7 -, Z 8;} -Z 3 -Z 4 -Z 5 -Z 6 -Z 7 -Z 8 - a.

Z _{2 to} Z ₈ are -O -, - S-, or -SO ₂ - it represents, Sub represents a mere bond ([pi bond), a hydrogen atom or a substituent noted below. Subs may be the same or different, and may be bonded to each other to form a 3- to 8-membered saturated or unsaturated carbocycle or heterocycle. In the general formula [A], Sub is selected so that the sum of the Hammett substituent constants σp of the substituents is +0.09 or more, more preferably +0.3 or more, and most preferably +0.45 or more.

List examples when Sub is a substituent. (The number of carbon atoms is preferably 0 to 40, respectively) Substituted or unsubstituted alkyl group (eg, methyl group, ethyl group, sec-butyl group, t-octyl group, benzyl group, cyclohexyl group, chloromethyl group, dimethylaminomethyl group) , N-hexadecyl group, trifluoromethyl group, 3,3,3-trichloropropyl group, methoxycarbonylmethyl group, etc.) and substituted or unsubstituted alkenyl groups (eg vinyl group, 2-chlorovinyl group, 1-methylvinyl group) Group), a substituted or unsubstituted alkynyl group (eg, ethynyl group, 1-propynyl group, etc.), cyano group,
Nitro group, halogen atom (fluorine, chlorine, bromine, iodine), substituted or unsubstituted heterocyclic residue (2-pyridyl group, 1-imidazolyl group, benzothiazol-2-yl group, morpholino group, benzoxazole- 2-yl group, etc.), sulfo group, carboxyl group, substituted or unsubstituted aryloxycarbonyl or alkoxycarbonyl group (eg, methoxycarbonyl group, ethoxycarbonyl group, tetradecyloxycarbonyl group, 2-methoxyethylcarbonyl group, phenyl group). Enoxycarbonyl group, 4
-Cyanophenylcarbonyl group, 2-chlorophenoxycarbonyl group, etc.), a substituted or unsubstituted carbamoyl group (for example, a carbamoyl group, a methylcarbamoyl group,
Diethylcarbamoyl group, methylhexadecylcarbamoyl group, methyloctadecylcarbamoyl group, phenylcarbamoyl group, 2,4,6-trichlorophenylcarbamoyl group, N-ethyl-N-phenylcarbamoyl group, 3
-Hexadecylsulfamoylphenylcarbamoyl group), hydroxyl group, substituted or unsubstituted azo group (eg, phenylazo group, p-methoxyphenylazo group, 2-cyano-4-methanesulfonylphenylazo group, etc.) A substituted or unsubstituted aryloxy or alkoxy group (for example, methoxy group, ethoxy group, dodecyloxy group, benzyloxy group, phenoxy group, 4-methoxyphenoxy group, 3-acetylaminophenoxy group,
3-methoxycarbonylpropyloxy group, 2-trimethylammonioethoxy group, etc.), sulfino group, sulfeno group, mercapto group, substituted or unsubstituted acyl group (eg acetyl group, trifluoroacetyl group, n-
Butyroyl group, t-butyroyl group, benzoyl group, 2-
Carboxybenzoyl group, 3-nitrobenzoyl group, formyl group, etc.), substituted or unsubstituted aryl or alkylthio group (for example, methylthio group, ethylthio group,
t-octylthio group, hexadecylthio group, phenylthio group, 2,4,5-trichlorothio group, 2-methoxy-5-
t-octylphenylthio group, 2-acetylaminophenylthio group, etc.), a substituted or unsubstituted aryl group (eg, phenyl group, naphthyl group, 3-sulfophenyl group, 4-methoxyphenyl group, 3-lauroylamino group) A phenyl group), a substituted or unsubstituted sulfonyl group (eg, methylsulfonyl group, chloromethylsulfonyl group, n-octylsulfonyl group, n-hexadecylsulfonyl group, sec-octylsulfonyl group, p-toluenesulfonyl group, 4 -Chlorophenylsulfonyl group, 4-
Dodecylphenylsulfonyl group, 4-dodecyloxyphenylsulfonyl group, 4-nitrophenylsulfonyl group, etc.), substituted or unsubstituted sulfinyl group (for example, methylsulfinyl group, dodecylsulfinyl group, phenylsulfinyl group) Group, 4-nitrophenylsulfinyl group, etc.), a substituted or unsubstituted amino group (eg, methylamino group, diethylamino group, methyloctadecylamino group, phenylamino group, ethylphenylamino group, 3-tetradecylsulfinyl group). Amoylphenylamino group, acetylamino group, trifluoroacetylamino group, N-hexadecylacetylamino group, N-methylbenzoylamino group, methoxycarbonylamino group, phenoxycarbonylmethyl group, N-methoxyacetylamino group, Amidinoamino group Phenylaminocarbonylamino group, 4-cyanophenylaminocarbonylamino group, N-ethylethoxycarbonylamino group, N-methyldodecylsulfonylamino group, N- (2-cyanoethyl) -p-toluenesulfonylamino group, hexadecyl Sulfonylamino group, trimethylammonio group, etc.),
A substituted or unsubstituted sulfamoyl group (eg, dimethylsulfamoyl group, hexadecylsulfamoyl group,
Sulfamoyl group, methyloctadecylsulfamoyl group, methylhexadecylsulfamoyl group, 2-cyanoethylhexadecylsulfamoyl group, phenylsulfamoyl group, N- (3,4-dimethylphenyl) -N-octyl Sulfamoyl group, dibutylsulfamoyl group,
Dioctadecylsulfamoyl group, bis (2-methoxycarbonylethyl) sulfamoyl group, etc.), substituted or unsubstituted acyloxy group (eg acetoxy group, benzoyloxy group, desyloyloxy group, chloroacetoxy group etc.), substituted or unsubstituted And a sulfonyloxy group (for example, a methylsulfonyloxy group, a p-toluenesulfonyloxy group, a p-chlorophenylsulfonyloxy group, etc.).

In the general formula [B], n ″ represents an integer of 1 to 6, U ₁ ; -Y ₁ , U ₂ ; -Y ₁ -Y ₂ , U ₃ ; -Y ₁ -Y ₂ -Y ₃ , U ₄ ;
_{-Y 1 -Y 2 -Y 3 -Y 4} -, U 5; -Y 1 -Y 2 -Y 3 -Y 4 -
Y ₅ -, U _6; a _{Y 1 -Y 2 -Y 3 -Y 4} -Y 5 -Y 6.

Y _{1 to} Y ₆ are Or Represents

Sub ′ represents a simple bond (σ bond, π bond) or a substituent of Sub described in the general formula [A]. In the general formula [B], Sub 'is selected so that the total sum of the substituent hamet substituent constant σp is +0.09 or more, more preferably +0.3 or more, and most preferably +0.45 or more.

As a more specific example of EAG, an aryl group substituted with at least one electron-withdrawing group (eg, 4-nitrophenyl group, 2-nitro-4-N-methyl-N-octadecylsulfamoylphenyl group) , 2-N, N-dimethylsulfamoyl-4-nitrophenyl group, 2-cyano-
4-octadecylsulfonylphenyl group, 2,4-dinitrophenyl group, 2,4,6-tricyanophenyl group, 2-nitro-4-N-methyl-N-octadecylcarbamoylphenyl group, 2-nitro-5- Octylthiophenyl group, 2,4-dimethanesulfonylphenyl group, 3,5-dinitrophenyl group, 2-chloro-4-nitro-5-methylphenyl group, 2-nitro-3,5-dimethyl-4-tetra Decylsulfonylphenyl group, 2,4-dinitronaphthyl group, 2-ethylcarbamoyl-4-nitrophenyl group,
2,4-bis-dodecylsulfonyl-5-trifluoromethylphenyl group, 2,3,4,5,6-pentafluorophenyl group, 2-acetyl-4-nitrophenyl group, 2,4-diacetylphenyl group Group, 2-nitro-4-trifluoromethylphenyl group, etc.), substituted or unsubstituted heterocycle (eg, 2-pyridyl group, 2-pyrazyl group, 5-nitro-2-pyridyl group, 5
-N-hexadecylcarbamoyl-2-pyridyl group, 4
-Pyridyl group, 3,5-dicyano-2-pyridyl group, 5-
Dodecylsulfonyl-2-pyridyl group, 5-cyano-2
-Pyrazyl group, 4-nitrothiophen-2-yl group, 5
-Nitro-1,2-dimethylimidazol-4-yl group,
3,5-diacetyl-2-pyridyl group, 1-dodecyl-5
-Carbamoylpyridinium-2-yl group), substituted or unsubstituted quinones (e.g., 1,4-benzoquinone-2-yl group, 3,5,6-trimethyl-1,4-benzoquinone-2-yl group, 3-methyl-1,4-naphthoquinone-2-
Ile group, 3,6-dimethyl-5-hexadecylthio-1,4-
Benzoquinone-2-yl group, 5-pentadecyl-1,2-
Benzoquinon-4-yl group, etc.) or a nitroalkyl group (for example, 2-
Examples thereof include a nitro-2-propyl group), a nitroalkenyl group (eg, 2-nitroethenyl group), and a monovalent group of the α-diketo compound (eg, 2-oxopropanoyl group).

R ¹ , R ² and R ³ represent a group other than a hydrogen atom or a simple bond.

R ¹ and R ³ are preferably substituted or unsubstituted alkyl groups, aryl groups, heterocyclic residues, acyl groups, sulfonyl groups and the like.

R ² is preferably a substituted or unsubstituted acyl group or sulfonyl group. R ¹ , R ² and R ³ are bonded to each other and are 5 to 8
A member ring may be formed.

Further, among the compounds represented by the general formula [II], those represented by the general formula [III] are more preferable for achieving the object of the present invention.

General formula (III) To do.

(Time _t LA binds to at least one of R ⁴ and EAG.
For the portion corresponding to PWR in the general formula [III], Y is a divalent linking group, preferably Y Or -SO ₂ - it is. X is -O-, -S as described above.
-Or , But preferably an oxygen atom.

R ⁴ represents an atomic group which is bonded to X and Y to form a 5- to 8-membered monocyclic ring or a condensed heterocycle including a nitrogen atom.

less than A preferable example of the portion corresponding to the above will be described including the binding position of Time _t LA.

Time represents a group that releases LA through a reaction that follows the cleavage between N and X.

t represents an integer of 0 or 1, and when t = 0, Time represents a simple bond.

Examples of Time include those described as Time in JP-A-61-236549.

In the present invention, preferred examples of Time are specifically described below, but in the compound of the present invention, (*) is (*) on the PWR side.
(*) Means binding to the LA side.

LA represents a group having an absorption maximum at 310 nm or more and is a dye used in a silver halide photographic light-sensitive material, and examples thereof include arylidene dyes, styryl dyes, butadiene dyes, oxonol dyes, cyanine dyes, and merocyanine dyes. , Hemicyanine dyes, diarylmethane dyes, triarylmethane dyes, azomethine dyes, azo dyes, metal chelate dyes, anthraquinone dyes, stilbene dyes, chalcone dyes, and indophenol dyes.

Specific examples of the compound represented by the general formula [II] used in the present invention are shown below. However, the present invention is not limited to these.

Concrete example The compounds of the present invention release dyes which are released from U.S. Pat. No. 4,139,389.
No. 4,139,379, a method for synthesizing the compounds disclosed in JP-A-59-185333, US Pat. No. 4,232,107, JP-A-59-101649.
No. 61-88257 method of synthesizing the compound disclosed in U.S. Pat.Nos. 4,343,893, 4,619,884, the method of synthesizing the compounds disclosed in U.S. Pat.Nos. 4,450,223 and 4,609,610.
Reference is made to the synthetic methods of the compounds disclosed in Japanese Patent Application Nos. 60-244873 and 61-88625. It can be easily synthesized by binding to.

Next, synthetic examples of specific compounds are shown so that the synthetic method of the compounds of the present invention can be more easily understood.

Synthesis of compound 3 1- (1) 4-chloro-3-nitro-N-methyl-N
-Synthesis of octadecylbenzenesulfonamide 100 g of 4-chloro-3-nitrobenzenesulfonyl chloride was dissolved in 300 ml of chloroform and cooled to 0 ° C. A chloroform solution of 84.3 g of methyl octadecylamine was added dropwise thereto. Then, triethylamine 39.5g
Was added dropwise while maintaining 0 ° C to 10 ° C. After reacting for 1 hour after completion of dropping, chloroform was distilled off and 500 ml of methanol was added.
Was added, and the mixture was heated and dissolved, and when left to cool, crystals were precipitated.

Crystals were collected by vacuum filtration and dried. Yield 109g, yield 71.2
%, Melting point 86-87 ° C. 1- (2) 5-t-butyl-2- (4-N-methyl-
Synthesis of N-octadecylsfluamoyl-2-nitrophenyl) -3-isooxolone 4-chloro-3-nitro-N-methyl-N-octadecylbenzenesulfonamide 600 g, 5-t-butyl-3-
202 g of hydroxyisoxazole (see Japanese Patent Application No. 60-244,873, page 75), 200 g of potassium carbonate and dimethyl sulfoxide
1.8 l were mixed and reacted at 65 ° C. for 6 hours. Then, the reaction solution was poured into ice water, and the precipitated crystals were filtered under reduced pressure, washed with water and dried. Yield 709 g, yield 98.0%, melting point 68-69 ° C. 1- (3) 5-t-butyl-4-chloromethyl-2-
(4-N-methyl-N-octadecyl sulfamoyl-
Synthesis of 2-nitrophenyl) -3-isoxazolone 650 g of isoxazolone synthesized in 1- (2), zinc chloride
200 g, 200 g of paraformaldehyde, and 3 l of acetic acid were mixed, and the mixture was heated under reflux for 10 hours while bubbling hydrogen chloride gas. After cooling, the reaction solution was poured into water, the precipitated crystals were taken, and recrystallized from acetonitrile: methanol = 1: 4. Yield 579
g, yield 82.4%, melting point 55-56 ° C. 1- (4) 5-t-butyl-4- (4-formylphenoxy) methyl-2-{(2-nitro-4-N-methyl-N) -Octadecyl sulfamoyl) phenyl} -3-
Synthesis of Isooxolone 12.4 g of the chloride synthesized in 1- (3) was dissolved in 150 ml of acetone, and 2.7 g of 4-hydroxybenzaldehyde, 0.5 g of sodium iodide and 3 g of potassium carbonate were added thereto. After heating under reflux for 5 hours, inorganic substances were filtered off by absorption filtration, the filtrate was dried and the residue was recrystallized from methanol. Yield 10.2g, Yield 67.6%, mp.60-61 ° C 1- (5) Synthesis of Compound Example 3 7.5g of aldehyde synthesized in 1- (4) was added to 100m of methanol.
In addition to 1, 3.1 g of potassium 3-cyanoacetamidebenzenesulfonate and 1 g of ammonium acetate were added, and the mixture was heated under reflux for 6 hours. The solid dissolved as the reaction proceeded. After the reaction, the mixture was cooled and the solvent was distilled off under reduced pressure. The residue was purified by silica gel column chromatography with chloroform-methanol solvent system.

Yield 5.0 g, yield 49.3%, Synthesis Example 2 Synthesis of Compound 19 2- (1) 5-t-butyl-4- (4-formylphenoxy) methyl-2- (2-nitro-4-diethylsulfamoylphenyl) -3-iso Synthesis of Oxazolone 1- (1) in Synthesis Example 1 except that diethylamine was used in place of methyloctadecylamine
It was synthesized by the same method as (1) to 1- (4).

Melting point 144-145 ° C. 2- (2) Synthesis of compound example 19 13.0 g of aldehyde synthesized in 2- (1) was added to methanol 150
7.5 ml of (3-cyanoacetamide) benzenesulfonic acid potassium salt and 1 g of ammonium acetate were added to the mixture, and the mixture was heated under reflux for 8 hours. After completion of the reaction, the solvent was distilled off under atmospheric pressure, and the residue was purified by silica column chromatography with a solution of chloroform / methanol. Yield 13.0g, Yield 67.0%, Synthesis Example 3 Compound 20 3- (1) 5-t-butyl-4- {N-ethyl-N-
(4-Formyl-3-methylphenyl) aminoacetoxymethyl} -2-{(2-nitro-4-N-methyl-N
-Octadasylsulfamoyl) phenyl} -3-isoxazolone Synthesis 6.2 g of the chloride synthesized in Synthesis Example 1- (3) was dissolved in 70 ml of dimethylsulfoxide, and 4- (N-methyl-N) was added thereto.
-Carboxymethylamino) -2-methylbenzaldehyde 2.7 g, potassium carbonate 1.7 g, and sodium iodide 0.4 g were added, and the mixture was reacted at room temperature for 6 hours. Water was added to the reaction solution and extracted with ethyl acetate. The organic phase was washed twice with water and the solvent was distilled off under reduced pressure. The residue was crystallized from methanol and a little acetonitrile. Yield 7.2 g, 85.8% 3- (2) Synthesis of Compound Example 20 5.5 g of the aldehyde synthesized in 3- (1), 2.2 g of 3-cyanoacetamidobenzenesulfonic acid potassium salt, 0.7 g of ammonium acetate in 100 ml of methanol. Mix and heat to reflux for 3 hours. After the solvent was distilled off under reduced pressure, the residue was purified by silica gel column chromatography using a methanol / chloroform eluent. Yield 4.0g, yield 56.2%, The compound of the general formula [I] used in the present invention can be added in a necessary amount in the layer depending on the purpose, but it is preferably used in an optical density range of 0.05 to 3.0. The specific amount of dye will vary depending on the dye, but in general
^{10 -3 g / m 2 ~3.0g /} m 2, it is possible to find particular preferred amounts in the range of ^{10 -3 g / m 2 ~1.0g /} m 2.

The compound of the general formula [II] according to the present invention can be incorporated into the hydrophilic colloid layer by various known methods.

For example, these compounds are dissolved in a suitable solvent [e.g. alcohol (methanol, ethanol, propanol), acetone, methyl ethyl ketone, methyl cellosolve, dimethylformamide, cyclohexanone, ethyl acetate] and dissolved or dispersed in gelatin, or Alternatively, it may be dissolved in an oil having a higher boiling point and added in the form of a fine oil droplet emulsion dispersion. As the oil, known oils such as tricresyl phosphate, diethyl phthalate, dibutyl phthalate and triphenyl phosphate can be used.

Other dispersion methods include US Pat. No. 4,512,969 and JP-A-51-51.
59, 943, JP-B-51-39, 853, after dissolving the compound of the present invention in an organic solvent miscible with water, and then mixed with a polymer latex swellable in the organic solvent, By removing at least a part, a stable dispersion can be prepared and put to use.
Alternatively, it is also possible to prepare a dispersion of the compound of the present invention in water using an intermediary disperser such as a ball mill or a colloid mill, and mix it with an aqueous gelatin solution for use. At this time, it is effective to use various well-known surfactants as the dispersion aid. Examples of surfactants are
51-39,853 etc.

The compound of the general formula [II] according to the present invention can be contained in an intermediate layer, a photosensitive layer, a protective layer, an overcoat layer, or the like, but is preferably outside the photosensitive layer located farthest from the support. It may be contained in a certain non-sensitive hydrophilic colloid layer (for example, a surface protective layer) or a non-photosensitive hydrophilic colloid layer between the support and the photosensitive layer located closest to the support.

The layer containing the compound represented by the general formula [II] of the present invention, during development processing, is mainly decomposed and eluted by hydroquinone, sulfite, or alkali in a developing solution, so that a photographic image is colored, Does not cause pollution.

Gelatin is most preferable as the hydrophilic colloid, and various known gelatins can be used. For example, lime-processed gelatin, acid-processed gelatin and the like which are different in the method of producing gelatin, or gelatin obtained by chemically modifying these obtained gelatins such as phthalation and sulfonylation can be used. If necessary, it can be used after desalting.

The mixing ratio of the compound of the general formula [II] of the present invention and gelatin varies depending on the structure of the compound and the addition amount, but is 1/10 ³
A preferable ratio can be found in the range of 1/3.

The silver halide emulsion which can be used in the present invention may be any of silver chloride, silver bromide, silver chlorobromide, silver iodobromide and silver iodochlorobromide.

The silver halide grains in the photographic emulsion layer are cubic, octahedral,
It may have a regular (regular) crystal such as a tetradecahedron or a rhombodecahedral, or may have an irregular (irregular) crystal form such as a sphere or a plate, or one of these crystal forms. It may have a complex shape. It may consist of a mixture of particles of different crystal forms. Further, it may have an epitaxial structure.

The silver halide grains may have different phases in the inside and the surface layer, or may be composed of a uniform phase. Also, grains in which a latent image is mainly formed on the surface (eg negative emulsion).
Alternatively, it may be a grain that is mainly formed inside the grain (for example, an internal latent image type emulsion, a direct inversion type emulsion which has been fogged in advance).

The silver halide grain size is generally preferably in the range of 0.01 μ to 4.0 μ, and particularly, in the graphic quartz light-sensitive material, it is 0.02 μm.
~ 0.4μ, 0.2 for general photographic materials and X ray film
3.0μ is preferable.

The photographic emulsion used in the present invention is P. grafchides (P.
Glafkides), Chimie er Physique Photogroheque (Paul Montel, 1967), G. Duffin (G.
F.Duffin), Phtograpic Emulsion Chemistry (published by Foucal Press, 1966), Vu El Zelikmann (V.
L. Zelkman) et al., Making and Coating Photographs
ting Photographic Emulsion) (Published by Focal Press,
1964) and the like.

In the process of silver halide grain formation or physical ripening,
Cadmium salt, zinc salt, thallium salt, iridium salt or complex salt thereof, rhodium salt or complex salt thereof, iron salt or iron complex salt may be allowed to coexist.

The silver halide emulsion may or may not be chemically sensitized. For chemical sensitization, for example, H. Friesel (H. Frie
ed), Die Grundlagen def Photographischen Prozesse (Die Grundlagen def Photographischen Prozesse)
mit Silberhalogeniden) (Akademitsushie Ferurugus Gezerujiakt 1968) pages 675-734 can be used.

That is, a sulfur sensitization method using a compound containing sulfur capable of reacting with active gelatin or silver (for example, thiosulfate, thioureas, mercapto compounds, rhodanines); a reducing substance (for example, first tin salt, Reduction sensitization using amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (eg, gold complex salts, complex salts of Group VIII metals such as Pt, Ir, Pd) The noble metal sensitizing method to be used 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, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds), heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as Oxazoline thiones; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfonic acids; benzene It can be added a number of compounds known to the antifoggants or stabilizers such as; Nsurufuin acid; hydroquinone and derivatives thereof.

The silver halide photographic emulsion of the present invention is a color coupler such as a cyan coupler, a magenta coupler and a yellow coupler.
A coupler and a compound that disperses the coupler may be included.

That is, it may contain a compound capable of forming a color by oxidative coupling with an aromatic primary amine developing agent (for example, a phenylenediamine derivative, an aminophenol derivative or the like) in the color development processing. For example, magenta couplers include 5-pyrazolone couplers, pyrazolone benzimidazole couplers, cyanoacetylcoumarone couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include acylacetamide couplers (for example, benzoylacetanilides, pivaloylacetanilides), And 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. The coupler may be either 4-equivalent or 2-equivalent with respect to silver ion. Further, a colored coupler having a color correction effect, or a coupler releasing a development inhibitor upon development (so-called DI
R coupler).

In addition to the DIR coupler, a non-colored DIR coupling compound which is colorless in the coupling reaction product and releases a development inhibitor may be contained.

In the photographic emulsion of the present invention, for the purpose of increasing sensitivity, increasing contrast or accelerating development, for example, polyalkylene oxide or its derivative such as ether, ester, amine, thioether compound, thiomorpholine, quaternary ammonium salt compound, urethane derivative, urea. Derivatives, imidazole derivatives, 3-pyrazolidones and the like may be included.

In the silver halide photographic emulsion of the present invention, known water-soluble dyes other than the dyes disclosed in the present invention (for example, oxonol dyes; hemioxonol dyes and merocyanine dyes) are used as a filter dye or for various purposes such as prevention of irradiation. Benzylidene dye). The spectral sensitizer may be used in combination with a known cyanine dye, merocyanine dye or hemicyanine dye other than the dyes shown in the present invention.

Further, regarding the light-sensitive material of the present invention, with respect to anti-fading agent, anti-fogging agent, ultraviolet absorber, protective colloid such as gelatin, and various additives, specifically, Research Disclosure Vol. 176 (1978, XII) RD-17643 and the like.

Further, in the case of a super-hard tone negative photosensitive material used in Grafic Arts, U.S. Patent Nos. 4,224,401, 4,168,977, 4,4,
166,742, 4,311,781, 4,272,606, 4,211,857,
A hydrazine derivative can be included as shown in 4,243,739.

A particularly preferred hydrazine derivative is represented by the following general formula.

In the formula, A represents an aliphatic group or an aromatic group, B represents a formyl group, an acyl group, an alkyl or aryl sulfonyl group, an alkyl or aryl sulfinyl group, a carbamoyl group, an alkoxy or aryloxycarbonyl group, a sulfinamoyl group. , An alkoxysulfonyl group, a thioacyl group, a thiocarbamoyl group, a sulfaniyl group or a heterocyclic group, wherein X and Y are both hydrogen atoms or one is a hydrogen atom and the other is a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted Represents an arylsulfonyl group or a substituted or unsubstituted acyl group.

Further, in Graphite Quartz, especially in a light-sensitive photographic light-sensitive material, an organic desensitizer may be contained. Particularly preferred organic desensitizers are those having at least one water-soluble group or alkali-labile group.

A specific example is described in Japanese Patent Application No. 61-205603.

Further, in the case of a light-sensitive material using a hydrazine derivative as described above, as a development accelerator, JP-A-53-77,616 and JP-A-54-37,7
32, 53-137,133, 60-140,340, 60-14,959, and Japanese Patent Application No. 61-205603 are preferably used.

The photographic light-sensitive material of the present invention is disclosed in JP-A-60-76743 and 60-873.
22. Nitron and its derivatives described in JP-A No.
A mercapto compound described in JP-A-0839, JP-A-57-16473.
The heterocyclic compound and the complex salt of a heterocyclic compound and silver (for example, 1-phenyl-5-mercaptotetrazole silver) described in JP-A-5 can be preferably used.

For a photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material produced by using the present invention, a coating aid, an antistatic agent, an improvement in slipperiness, an emulsion dispersion, an adhesion prevention and an improvement in photographic characteristics (for example,
Various surfactants may be included for various purposes such as development acceleration, contrast enhancement, and sensitization.

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 oxide adducts of silicones), sugar alkyl esters Nonionic surfactants such as; alkyl sulfonates, alkyl benzene sulfonates, alkyl naphthalene sulfonates, alkyl sulfates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl Anionic surfactants such as polyoxyethylene alkyl phenyl ethers; amphoteric surfactants such as alkyl betaines and alkyl sulfobetaines; fats Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, pyridinium salts and imidazolium salts can be used.

Among them, saponin, dodecylbenzene sulfonic acid Na salt,
Di-2-ethylhexyl α-sulfosuccinic acid Na salt, p-
Octylphenoxyethoxyethoxyethanesulfonic acid
Na salt, sodium dodecyl sulfate, triisopropyl naphthalene sulfonic acid Na salt, N-methyl-oleoyl taurine Na
Anions such as salts, dodecyltrimethylammonium chloride, cations such as N-oleoyl-N ', N', N'-trimethylammoniodiaminopropane bromide, dodecylpyridinium chloride, N-dodecyl-N, N
-Dimethylcarboxybetaine, N-oleyl-N, N-
Betaines such as dimethylsulfobutyl betaine, poly (average degree of polymerization n = 10) oxyethylene cetyl ether,
Nonionics such as poly (n = 25) oxyethylene p-nonylphenol ether and bis (1-poly (n = 15) oxyethylene-oxy-2,4-di-t-pentylphenyl) ethane are particularly preferably used. You can

Perfluorooctane sulphonic acid K as an antistatic agent
Salt, N-propyl-N-perfluorooctanesulfonylglycine Na salt, N-propyl-N-perfluorooctanesulfonylaminoethyloxypoly (n = 3) oxyethylenebutanesulfonic acid Na salt, N-perfluorooctanesulfonyl- Fluorine-containing surfactants such as N ', N', N'-trimethylammophodiaminopropane chloride and N-perfluorodecanoylaminopropyl-N, N'-dimethyl-N'-carboxybetaine, JP-A-60- -8
0848, 61-112144, Japanese Patent Application No. 61-13398, 61-1605
Nonionic surfactants such as those described in No. 6, alkali metal nitrates, conductive tin oxides, zinc oxides, vanadium pentoxide, or composite oxides obtained by doping these with antimony or the like can be preferably used.

In the surface layer of the photographic light-sensitive material of the present invention as a slip agent U.S. Pat.No. 3,489,576, silicone compounds described in 4,047,958 and the like, in addition to colloidal silica described in Japanese Patent Publication No. 56-23139, Paraffin wax, Higher fatty acid ester,
Denden powder derivatives and the like can be used.

Polyols such as trimethylolpropane, pentanediol, butanediol, ethylene glycol and glycerin can be used as a plasticizer in the hydrophilic colloid layer of the photographic light-sensitive material of the present invention. Furthermore, the hydrophilic colloid layer of the photographic light-sensitive material of the present invention preferably contains a polymer latex for the purpose of improving pressure resistance. As the polymer, a homopolymer of an alkyl ester of acrylic acid, a copolymer with acrylic acid, a styrene-butadiene copolymer, or a polymer or copolymer comprising a monomer having an active methylene group can be preferably used.

The photographic emulsion and the non-photosensitive hydrophilic colloid of the present invention may contain an inorganic or organic hardener. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-
s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc., active halogen compounds (2,4-dichloro-6-hydroxy-s-triazine, etc.) ), Mucohalogen acids (mucochloric acid, etc.), N-carbamoylpyridinium salts ((1-mololi, carbonyl-3-pyridinio) methanesulfonate, etc.), haloamidinium salts (1- (1-chloro-1-pyridinomethylene)) Pyrrolidinium, 2-naphthalene sulfonate, etc.) can be used alone or in combination. Among them, JP-A-53-41220, 53-57257, 59-162546,
Active vinyl compounds described in the same 60-80846 and US Patent 3,
The active halides described in 325,287 are preferred. In addition, JP-A-56-66,841, British patent 1,322,971 and US patent 3,
The polymeric hardeners described in 671,256 may be used.

The finished emulsion is coated on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, other plastic bases or glass plates.

The silver halide photographic light-sensitive material of the present invention includes a color positive film, a color paper, a color negative film, a color reversal film (which may or may not contain a coupler), and a plate-making photographic light-sensitive material (for example, a lith film or a lithographic film). (Up film, etc.), photosensitive materials for cathode ray tube displays (eg, emulsion X-ray recording photosensitive materials, direct and indirect imaging materials using screens), silver salt diffusion transfer process photosensitive materials, color Light-sensitive material for diffusion transfer process, emulsion used in silver dye bleaching method, light-sensitive material for heat development (for details, U.S. Pat. No. 4,500,626, JP-A-60-133449, JP-A-59-218443 or JP-A-60-79709). No.), etc.

The exposure for obtaining a photographic image may be performed using a usual method. That is, any of various known light sources such as natural light (sunlight), a halogen lamp, a tungsten lamp, a fluorescent lamp, a mercury lamp, a xenon arc lamp, a carbon arc lamp, a xenon flash lamp, and a cathode ray tube flying spot can be used. Exposure time is 1/1000 that is usually used in cameras
Exposure time from 1 second to 1 second, as well as exposure shorter than 1/1000 second, for example, 1/10 ⁴ using a xenon flashlight or cathode ray tube.
Exposures of up to 1/10 ⁶ seconds can be used or exposures longer than 1 second can be used. If necessary, the spectral composition of the light used for exposure can be adjusted with a color filter. Laser light can also be used for the exposure. Further, the exposure may be carried out by the light emitted from the phosphor excited by the electron beam, X-ray, γ-ray, α-ray or the like.

Photographic processing of a light-sensitive material produced by using the present invention includes, for example, Research Disclosur (Research Disclosur).
e) Any known method and known processing solution as described in No. 176, pages 28 to 30 (December 1978) can be applied. This photographic processing may be either photographic processing for forming a silver image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. The pH of the developing solution cannot be unconditionally specified depending on the difference between the black and white developing solution and the color developing solution, the type of developing agent, the type of photosensitive material to be processed, etc., but it is usually in the range of pH 9 to 12.5. The treatment temperature is usually chosen between 18 and 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C.

(Effect of the Invention) In the silver halide photographic light-sensitive material of the present invention, the light-absorbing compound represented by the general formula [I] of the present invention selectively dyes a layer containing the light-absorbing compound, and the other layers are substantially dyed. It provides an excellent silver halide photographic light-sensitive material, which has the excellent effect of not diffusing into light, the effect of filtering light, the effect of adjusting sensitivity, the effect of improving safelight safety, and the effect of preventing light fogging due to static electricity.

Since the layer containing the compound of the present invention is easily decolorized and eluted by photographic processing, there is no fear of adversely affecting photographic performance.

In the present invention, since the interaction with the binder such as gelatin and the coating aid is small, the coating property can be improved.

Further, even if the treatment with the reducing liquid is performed, the adverse effect such as stain is not exerted.

Further, the silver halide photographic light-sensitive material of the present invention gives an image with improved sharpness. Further, a photograph obtained from the silver halide photographic light-sensitive material of the present invention does not cause stain, is stable even for long-term storage, and does not deteriorate in photographic performance.

(Example) Next, the present invention will be described in more detail based on examples.

Example 1 (Preparation of Emulsion A) An aqueous solution of silver nitrate and an aqueous solution of sodium chloride containing 2.5 × 10 ⁻⁵ mol of ammonium hexachlororhodium (III) chloride per mol of silver were adjusted to pH in a gelatin solution at 35 ° C. by the double jet method. Mix while controlling to 2.3
A monodisperse silver chloride emulsion with an average grain size of 0.1 micron was made.

After the particles are formed, soluble salts are removed by a flocculation method well known in the art, and 4-hydroxy-6-methyl-1,3,3a, 7-tetraazaindene and 1-phenyl are used as stabilizers. -5-Mercaptotetrazole was added. Gelatin contained in 1 kg of emulsion is 55 g, and silver is 10
It was 5g. (Emulsion A) (Preparation of light-sensitive material) The emulsion A containing 20 mg / g of silver as a nucleating agent represented by the following formula:
Add 2 mg / silver 1 g of organic desensitizer, Further, as a hardener, 2,4-dichloro-6-hydroxy-1,
It was added 3,5-triazine sodium salt, 1 m ² per 3.
A silver halide emulsion layer was coated on a polyethylene terephthalate transparent support so that the amount of silver was 5 g, and gelatin (1.3 g / m ² ) was added to the layer above the compound 19 of the present invention (0.1 g / m ² ).
A protective layer containing m ² ) was applied and dried (Sample 1).

Compound 19 was prepared as a gelatin dispersion and applied by the following procedure; a solution prepared by dissolving 194.9 g of compound in 39 ml of methyl ethyl ketone was stirred at 45 ° C. in 260 g of 5.0% (by weight) aqueous gelatin solution. While mixing, a slightly emulsified dispersion was obtained.

Comparative Example-1 1) A sample was prepared by removing the compound 19 in Example 1 (Sample A) 2) The following water-soluble ultraviolet absorbing dye (0.05 g / m ² ) was used in place of the compound 19 in Example 1. A comparative sample B was prepared in the same manner except that it was used. Compound 19 was added after being dissolved in water.

(Evaluation of Performance) (1) The above three samples were exposed through an optical wedge with a bright room printer P-607 manufactured by Dainippon Screen Co., Ltd., and developed with the following developing solution at 38 ° C. for 20 seconds to obtain a normal It was fixed by the method, washed with water and dried. Sample B and Sample 1 have the same low UV optical density in the highlight area as Sample A ,
It was completely decolorized.

Basic formulation of developer Hydroquinone 35.0g N-methyl-p-aminophenol 1/2 sulfate 0.8g Sodium hydroxide 13.0g Sodium triphosphate 74.0g Potassium sulfite 90.0g Ethylenediaminetetraacetic acid tetrasodium salt 1.0g Potassium bromide 4.0 g 5-methylbenzotriazole 0.6 g 3- diethylamino 1,2-propanediol 15.0g water to make 1 (pH = 11.5) sensitivity, relative to Comparative sample a, Comparative sample B is lo
The gE value was 0.4, and Sample 1 of the present invention could be lowered by 0.5. Practically, the sensitivities of Sample B and Sample 1 were in the proper range.

(2) Safelight safety test The above 3 samples were tested for safe time under 400 lux with Safelight UV cut fluorescent lamp [Toshiba Corp. FLR-40SW-DLX-NU / M]. . The comparative sample A is 10 minutes, the comparative sample B is 20 minutes, and the inventive sample 1 is 25 minutes.
Showed the safety of minutes.

From the above test results of (1) and (2), it is understood that the compound 1 of the present invention more effectively reduces the sensitivity to the proper range and enhances the safelight safety.

(3) Tone variability test The above three samples were exposed with a printer as described above through a screen screen, and otherwise developed as in the test (1). After determining the exposure time for which the halftone dot area can be returned to 1: 1 for each sample, perform the exposure time twice or four times as long as the exposure time to determine how much the halftone dot area is. I checked to see if it would expand. The larger the magnification, the better the tone variability. The results are shown in Table-1. As can be seen from Table-1, the comparative sample B has a markedly lowered tone variability, whereas the sample 1 of the present invention has a high tone variability. This is because the dye used in Comparative Sample B is water-soluble and diffusible, so that the dye is evenly diffused from the added layer to the photosensitive emulsion layer. This is because the prevention effect suppressed the expansion of the halftone dot area. On the other hand, the compound 19 of the present invention, which is fixed in the added layer, shows high tone variability.

(4) Evaluation of Contamination (Stain) by Reducer Solution The strip of Sample 1 of the present invention obtained by treatment in (3) above was immersed in the following Farmer reducer solution at 20 ° C. for 60 seconds, washed with water and dried. did. As a result, 50% of the dot area is 33%
It was also reduced to 0, and the occurrence of stain was also confirmed.

Farmer reducer When using, mix 1st liquid: 2nd: liquid water = 100 parts: 5 parts: 100 parts.

Example 2 Instead of the compound 19 of Example 1, compounds 3 , 5 , 21 23 , 4
Samples 2a, 2b, 2c, 2d, 2e, 2f, 2g and 2h were prepared by using 0 , 41 , 50 and 51 , respectively, at 1.26 × 10 ⁻⁴ mol / m ² and evaluated in the same manner as in Example 1. .

As a result, as in the case of Sample 1 of Example 1, the sensitivity was effectively lowered to the proper range, the safelight safety was enhanced, and a large tone variability was exhibited. No stain was generated by the reduction process.

Example 3 A compound that absorbs ultraviolet light instead of the compound 19 of Example 1
Sample 3 of the present invention was prepared in the same manner as in Example 1 except that 0.1 g / m ^{2 of} 41 was used in combination with 0.15 g / m ² of the yellow compound 59 . Compound 41 was used as an ultraviolet light absorber to reduce the sensitivity to the appropriate level, and compound 59 was 430 nm.
It has a maximum absorption in and was used as a dye to prevent fogging due to safelight light.

Comparative Example 2 A comparative sample C was prepared in the same manner except that the following conventionally known water-soluble safelight dye was used in place of the compound 59 of Example 3 in an amount of 0.1 g / m ² .

(Evaluation of Sample 3 of the Present Invention and Comparative Sample C) Each item 1) to 4) was tested in the same manner as in Example 1. All were completely decolorized by the development process. The safelight safety was greatly improved by 50 minutes for the comparative sample and 60 minutes for the sample 3 of the present invention. Sample 3 was more effective. As shown in Table 2, the test result of the tone variability was significantly small in the comparative sample C, while the sample 3 of the present invention showed a large tone variability.

As can be seen from the above results, in the sample of the present invention, the compounds 41 and 59 are well localized in the added layer and effectively block the light to reduce the sensitivity, and the safelight safety. In addition, since it does not substantially diffuse into other layers, it does not cause harm to the tone variability.

Also, no contamination with the reducing liquid occurred.

Example 4 Compound 3 was dissolved in an oil and a cosolvent as follows, and an emulsified dispersion in gelatin was prepared using a homogenizer. After emulsifying and dispersing, it was made into a Nuder shape and washed with water, and finally water was added to make 300 g.

Gelatin (10 wt% aqueous solution) 100 g Sodium nonylphenylsulfonate 0.5 g Compound 3 5.8 g Tricresyl phosphate 5.8 g Cyclohexane 26 ml Ethyl acetate 26 ml Water was added up to 300 g The emulsified dispersion thus obtained was prepared in Example 1 Example 9 was carried out in the same manner as in Example 1 except that Compound 19 of Example 1 was used instead of Compound 19 .

As a result, good results were obtained as in Sample 1.

Preferred embodiments of the present invention are as follows.

1) A compound represented by the general formula [I] is represented by the general formula [II]
The photosensitive material according to the claims, characterized in that

2) The compound of the general formula [II] is a compound of the general formula [II
The photosensitive material according to the claims, characterized in that it is represented by I].

3) A photosensitive material according to claim 1 or 2 above, wherein X is an oxygen atom in the general formula [I], [II] or [III].

4) The light-sensitive material according to claim 1, wherein the compound represented by the general formula [I] is contained in the non-light-sensitive layer located outside the light-sensitive layer farthest from the support.

5) The light-sensitive material according to claim 1, wherein the compound represented by the general formula [I] is contained in a non-photosensitive layer located between the support and the light-sensitive layer closest to the support.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Masahiro Okada, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture, Fuji Photo Film Co., Ltd. (72) Kazunobu Kato, 210, Nakanuma, Minami Ashigara City, Kanagawa Prefecture, Fukatsu, Examiner, Fuji Photo Film Co., Ltd. Hiroshi (56) Reference JP 61-236549 (JP, A) JP 62-215270 (JP, A) JP 62-287247 (JP, A)

Claims (1)

[Claims] 1. A compound having at least one silver halide emulsion layer on a support, wherein the emulsion layer or another hydrophilic colloid layer is represented by the general formula [II] and a hydrazine derivative as a contrast-increasing agent. A silver halide photographic light-sensitive material containing. General formula (II) In the general formula [II], EAG represents a group that receives an electron from a reducing substance, and is bonded to a nitrogen atom. (Time _t LA binds to at least one of R ¹ , R ^{2 and} EAG. (Time _t LA is released from the molecule represented by the general formula (II) when EAG receives an electron from a reducing substance. From the numerator represented by general formula (II) (Time _t LA
Represents a group that releases LA as LA and then releases LA through a subsequent reaction. t represents an integer of 0 or 1. LA represents a dye group having a light absorption maximum at 310 nm or more. X is a group containing an oxygen atom (-O-), a sulfur atom (-S-), and a nitrogen atom. Represents R ¹ , R ² and R ³ represent a group other than a hydrogen atom or a simple bond. R ¹ , R ² and R ³ are bonded to each other to
An 8-membered ring may be formed.