JPH0693095B2 - Silver halide photographic light-sensitive material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial field of application) The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer of the present invention, which is photographic-chemically inert and is easily decolorized in the course of photographic processing. And / or a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a dye to be eluted.

(Prior Art) In a silver halide photographic light-sensitive material, a photographic emulsion layer or other layers are often colored for the purpose of absorbing light in a specific wavelength range. When it is necessary to control the spectral composition of light to be incident on the photographic emulsion layer, a coloring layer is provided on the side of the photographic light-sensitive material farther from the support than the photographic emulsion layer. Such a colored layer is called a filter layer. When there are a plurality of photographic emulsion layers as in a multi-layer color light-sensitive material, the filter layer may be located between them.

Light scattered during or after passing through the photographic emulsion layer may be reflected again at the interface between the emulsion layer and the support or on the surface of the light-sensitive material on the side opposite to the emulsion layer and enter the photographic emulsion layer again. Between the photographic emulsion layer and the support for the purpose of preventing blurring of the image, that is, halation.
Alternatively, a coloring layer is provided on the side of the support opposite to the photographic emulsion layer. Such a colored layer is called an antihalation layer. In the case of multi-layer color light-sensitive material,
An antihalation layer may be placed between the layers.

Decrease in image sharpness due to light scattering in photographic emulsion layer (this phenomenon is generally called irradiation)
Coloring of the photographic emulsion layer is also carried out in order to prevent the above phenomenon.

These layers to be colored are often composed of hydrophilic colloids and therefore for their coloring usually water-soluble dyes are included in the layers. This dye is required to satisfy the following conditions.

(1) It has a proper spectral absorption according to the purpose of use.

(2) Photochemically inactive. That is, it should not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as reduction in sensitivity, latent image regression, or fog.

(3) It should not be decolorized or dissolved and removed in the course of photographic processing to leave no harmful coloring on the photographic light-sensitive material after processing.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and the dyes listed below are known. For example, British Patent Nos. 506,385, 1,177,429, and
1,311,884, 1,338,799, 1,385,371, 1,46
7,214, 1,433,102, 1,553,516, JP-A-48-8
5,130, 49-114,420, 55-161,233, 59-111,
640, U.S. Pat.Nos. 3,247,127, 3,469,985, and 4,0
Oxonol dyes having a pyrazolone nucleus and a barbituric acid nucleus described in 78,933 etc., U.S. Pat.No. 2,533,472
No. 3,379,533, other oxonol dyes described in British Patent No. 1,278,621, British Patent No. 575,691.
No., 680,631, 599,623, 786,907, 907,1
25, 1,045,609, U.S. Pat.
Azo dyes described in 59-211,043 and the like, JP-A-50-100,1
No. 16, No. 54-118,247, British Patent No. 2,014,598, No. 75
Azomethine dyes described in U.S. Pat.
Anthraquinone dyes described in 65,752, U.S. Pat.
2,538,009, 2,688,541, 2,538,008, British Patents 584,609, 1,210,252, JP-A-50-40,625,
51-3,623, 51-10,927, 54-118,247, Japanese Patent Publications 48-3,286, 59-37,303, 62-106,455, 62-
Arylidene dyes described in No. 133,453, etc.
3,082, 44-16,594, 59-28,898 and the like styryl dyes, British Patent No. 446,583, 1,335,422
No. 1, the triarylmethane dyes described in JP-A-59-228,250, etc., British Patent Nos. 1,075,653, 1,153,341, and
1,284,730, 1,475,228, 1,542,807 and other merocyanine dyes, U.S. Pat.No. 2,843,486,
Cyanine dyes described in 3,294,539 and the like can be mentioned.

Of these, the arylidene dyes having a pyrazolone nucleus have the property of being decolorized in a developer containing a sulfite, and have little adverse effect on photographic emulsions and are used as useful dyes for dyeing photographic materials.

For example, JP-A-59-206,829, 59-211,035 and 59-21.
1,041, 59-208,548, 59-211,042, etc. However, some of these dyes remain after the processing due to the speeding up of the developing processing which has been performed in recent years. In order to solve this, it has been proposed to use a dye having a high reactivity with sulfite ion, but in this case, the stability in the photographic film is not sufficient, and the density decreases with time, It has the drawback that the desired photographic effect cannot be obtained.

(Problems to be Solved by the Invention) The object of the present invention is, firstly, a silver halide in which a hydrophilic colloid layer is dyed with a novel water-soluble dye which does not adversely affect the photographic characteristics of the silver halide emulsion layer. It is to provide a photographic light-sensitive material.

Secondly, an object of the present invention is to provide a silver halide photographic light-sensitive material in which a hydrophilic colloid layer is dyed with a novel water-soluble dye which is excellent in decolorization by processing.

The third object of the present invention is to provide a silver halide photographic light-sensitive material in which the dyed hydrophilic colloid layer contains a novel water-soluble dye which is stable over time.

Fourthly, an object of the present invention is to provide a silver halide photographic light-sensitive material which is excellent in a filter effect, an antihalation effect, or a sensitivity adjusting effect of a photosensitive emulsion.

(Means for Solving Problems) These objects of the present invention have been investigated by the present inventors in Japanese Patent Laid-Open No. 51-362.
As a result of further investigations based on the dyes described in 3, it was achieved by a silver halide photographic light-sensitive material containing at least one dye compound represented by formula (I).

General formula (I) In the formula, R ₁ is an aryl group, a cyano group, —COOH, or —COO.
_{R 7, -CONH 2, -CONHR 7} , -COR 8, -SO 2 R 8, -SOR 8, -
SO ₂ NR ₈ R ₉ or —OR ₇ (wherein R ₇ represents an aryl group, R ₈ and R ₉ represent an alkyl group or an aryl group, and R ₈ and R 9
₉ may combine to form a 5- or 6-membered ring. ) And R ₂ represents a hydrogen atom or an alkyl group. Q represents an aryl group, X represents a bond or a divalent linking group, Y represents a sulfo group or a carboxyl group, and L ₁ , L ₂ ,
L ₃ each represents a methine group. n represents 0 or 1, m represents 1 or 2, p represents 0, 1, 2, 3 or 4, and q represents 1, 2 or 3. R ₃ and R ₄ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, a substituted amino group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group or a sulfo group. .

R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group or a sulfonyl group, and at least one of R ₅ and R ₆ is a sulfo group as a substituent. Have.

The dye represented by formula (I) will be described in more detail.

The aryl group represented by R ₁ , R ₇ , R ₈ and R ₉ is preferably a phenyl group or a naphthyl group, a substituent (for example, a halogen atom such as fluorine, chlorine or bromine, a sulfo group, a carboxyl group, a hydroxyl group, cyano). Group, an alkyl group having 1 to 4 carbon atoms (eg methyl, ethyl, n-propyl), an alkoxy group (eg methoxy, ethoxy), an aryloxy group (eg phenoxy)].

The alkyl group represented by R ₈ and R ₉ has 1 to 8 carbon atoms.
An alkyl group of (for example, methyl, ethyl, n-propyl,
Isopropyl, n-butyl, isobutyl, t-butyl,
n-amyl, n-hexyl, n-octyl, isoamyl) is preferable, and a substituent [for example, halogen atom such as fluorine, chlorine, bromine, phenyl group, hydroxyl group, cyano group, alkoxy group (for example, methoxy, ethoxy, hydroxyethoxy)] , Aryloxy group (eg phenoxy, p-methoxyphenoxy), carboxyl group, sulfo group, amino group, substituted amino group (eg dimethylamino, diethylamino)].

The alkyl group represented by R ₂ is preferably an alkyl group having 4 or less carbon atoms (eg, methyl, ethyl, n-propyl).

The aryl group represented by Q is preferably a phenyl group or a naphthyl group, and a substituent other than a sulfo group or a carboxyl group [eg, an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethyl), an alkoxy group (eg, methoxy, ethoxy). A halogen atom (eg fluorine, chlorine, bromine), carbamoyl (eg methylcarbamoyl, ethylcarbamoyl), sulfamoyl (eg ethylsulfamoyl), cyano group, nitro group, alkylsulfonyl group (eg methanesulfonyl) arylsulfonyl group (eg Benzenesulfonyl), an amino group (eg dimethylamino, diethylamino), an acylamino group (eg acetylamino), a sulfonamide group (eg methanesulfonamide), a hydroxyl group].

As the divalent linking group represented by X, for example, -O-,
_{-NR 10 -, - NR 10 CO} -, - SO 2 -, - NR 10 SO 2 - can be exemplified, R ₁₀ is a hydrogen atom, alkyl group having 5 or less carbon atoms (e.g. methyl, ethyl, n- propyl , N-butyl, n-amyl, isobutyl) or a substituted alkyl group having 5 or less carbon atoms [as a substituent, an alkoxy group having 3 or less carbon atoms (eg, methoxy, ethoxy), a sulfo group, a carboxyl group, a cyano group, a hydroxyl group , An amino group (eg dimethylamino, diethylamino), a carbamoyl group (eg hydroxyethylaminocarbonyl, ethylaminocarbonyl) or a sulfamoyl group (eg ethylaminosulfonyl)].

Examples of the 5- or 6-membered ring formed by connecting R ₈ and R ₉ include a piperidine ring, a morpholine ring, a pyrrolidine ring and a pyrrolidone ring.

The methine group represented by L ₁ , L ₂ and L ₃ may have a substituent (for example, methyl, ethyl, cyano, phenyl, chlorine atom, sulfoethyl).

R ₃ and R ₄ are a hydrogen atom, a halogen atom (eg chlorine, bromine), an alkyl group (an optionally substituted alkyl group having preferably 5 or less carbon atoms, eg, methyl, ethyl), an alkoxy group (substituted) Optionally substituted alkoxy group having 5 or less carbon atoms, for example, methoxy, ethoxy, 2-
Chloroethoxy), a hydroxy group, a carboxyl group, a substituted amino group (for example, acetylamino, methylamino, diethylamino, methanesulfonylamino), a carbamoyl group (an optionally substituted carbamoyl group, for example, methylcarbamoyl), a sulfamoyl group ( It is an optionally substituted sulfamoyl group and represents, for example, ethylsulfamoyl), an alkoxycarbonyl group (eg, methoxycarbonyl), and a sulfo group.

R ₅ and R ₆ are a hydrogen atom, an alkyl group (an optionally substituted alkyl group, preferably having 8 or less carbon atoms, such as methyl, ethyl, propyl and butyl, and the substituents are a sulfo group, Carboxyl group, halogen atom, hydroxy group, cyano group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, acyloxy group, acylamino group, carbamoyl group, sulfamoyl group, alkylamino group, dialkylamino group, alkoxycarbonyl group, aryloxycarbonyl group Group, alkylsulfonyl group, arylsulfonyl group, sulfonylamino group, ureido group, aryl and the like), alkenyl group (alkenyl group which may be substituted, for example, 3
-Hexenyl), an aryl group (the aryl group is preferably a phenyl group, and may have the substituent described in the item of the aryl group of Q), an acyl group (for example, acetyl,
Benzoyl) and a sulfonyl group (for example, methanesulfonyl, phenylsulfonyl), and at least one of R ₅ and R ₆ has a sulfo group as a substituent.

In the above general formula (I), the sulfo group and the carboxyl group each have a free form or a salt form (for example, Na salt, K salt, (C ₂ H ₅ ) ₃ NH salt,
(Pyridinium salt, ammonium salt) may be formed.

Preferred in the general formula (I) is that R ₁ is an aryl group, a cyano group, —COOH, —COOR ₇ , —CONH ₂ , or —CONH.
_{R 7, -COR 8, -SO 2} R 8, -SOR 8, -SO 2 NR 8 R 9 -, - OR
₇ (R ₇ , R ₈ and R ₉ are as defined above.)
R ₂ represents a hydrogen atom or a methyl group, and Q is a phenyl group or a substituted phenyl group [as a substituent, an alkyl group having 4 or less carbon atoms, an alkoxy group having 4 or less carbon atoms, a halogen atom (eg, fluorine, chlorine, bromine) A dialkylamino group having 6 or less carbon atoms and a hydroxyl group are preferable. X is a bond or —O— or —NR ₁₀ — (R ₁₀ is as defined above). More preferably, under the above conditions, m = 1 and n = 1.

Next, specific examples of the compound represented by formula (I) used in the present invention are shown below, but the present invention is not limited thereto.

The exemplified compounds 8, 9, 10 and 13 are reference compounds.

(Exemplified compound) The synthesis of the compound represented by formula (I) is described in JP-A-51-3.
No. 623, as described in JP-A-59-211,041 and the like,
It can be easily carried out by condensation of a pyrazolone ring and benzaldehydes. Hereinafter, a specific synthesis example will be shown.

Synthesis Example 1. (Synthesis of Exemplified Compound 11.) 1- (2-Sulfobenzyl) -3-carboxypyrazolone monosodium salt 32.0 g (0.1 mol), 2-methyl-4
29.3 g (0.1 mol) of-{N-ethyl-N- (2-sulfoethyl) amino} benzaldehyde sodium salt was stirred in 250 ml of methanol, 2 ml of acetic acid was added, and the mixture was heated under reflux for 1.5 hours. After filtering the dust, 12.3 g of sodium acetate
A methanol solution of (0.15 mol) was added, and 600 ml of isopropyl alcohol was added to precipitate crystals. The crystals were collected by filtration and washed with isopropyl alcohol.

Synthesis Example 2 (Synthesis of Exemplified Compound 12.) 1- (2-Sulfobenzyl) -3-phenoxycarbonylpyrazolone sodium salt 19.8 g (0.05 mol), 2-methyl-4- {N-ethyl-N- (2- 14.7 g (0.05 mol) of sulfoethyl) amino} benzaldehyde sodium salt was stirred in 125 ml of methanol, 1 ml of acetic acid was added, and the mixture was heated under reflux for 1 hour. After removing dust and filtering, 300 ml of isopropyl alcohol was added to precipitate crystals. The crystals were collected by filtration and washed with isopropyl alcohol.

Other exemplified compounds can be easily synthesized by the same method.

When the dye represented by formula (I) is used as a filter dye, an anti-irradiation dye or an antihalation dye, any effective amount can be used,
It is preferably used so that the optical density is in the range of 0.05 to 3.0. The addition time may be any step before coating.

The dye according to the present invention can be dispersed in a hydrophilic colloid layer such as an emulsion layer (intermediate layer, protective layer, antihalation layer, filter layer, etc.) by various known methods.

A method of directly dissolving or dispersing the dye of the present invention in an emulsion layer or a hydrophilic colloid layer, or a method of dissolving or dispersing it in an aqueous solution or a solvent and then using it in the emulsion layer or the hydrophilic colloid layer. Suitable solvents such as methyl alcohol, ethyl alcohol, propyl alcohol, methyl cellosolve, halogenated alcohols described in JP-A-48-9715 and U.S. Pat. No. 3,756,830, acetone, water, pyridine, etc., or a mixture thereof. It may be dissolved in a solvent or the like and added to the emulsion in the form of a solution.

A method in which a hydrophilic polymer having a charge opposite to that of a dye ion coexists in a layer as a mordant, and the dye is localized in a specific layer by interacting with the dye molecule.

The polymer mordant is a polymer having secondary and tertiary amino groups, a polymer having a nitrogen-containing heterocyclic portion, and a polymer having a quaternary cation group. Those having a molecular weight of 5000 or more are particularly preferably 10,000 or more. .

For example, vinyl pyridine polymer and vinyl pyridinium cation polymer described in US Pat. No. 2,548,564; vinyl imidazolium cation polymer disclosed in US Pat. No. 4,124,386; US Pat. Polymer mordant capable of cross-linking with existing gelatin; US Pat. No. 3,958,995, JP-A-5
Aqueous sol type mordants disclosed in 4-115228, etc .; Water-insoluble mordants disclosed in U.S. Pat. No. 3,898,088; Can be covalently bound to the dyes disclosed in U.S. Pat. No. 4,168,976. Reactive mordant; British patent
Polymers derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described in 685,475; products obtained by reaction of polyvinyl alkyl ketone with aminoguanidine as described in British Patent 850,281. Polymers derived from 2-methyl-1-vinylimidazole as described in U.S. Pat. No. 3,445,231 can be mentioned.

A method of dissolving a compound using a surfactant.

The useful surfactant may be an oligomer or a polymer.

Details of this polymer are described on pages 19 to 27 of the specification of JP-A-60-158437 (filed by Fuji Photo Film Co., Ltd. on January 26, 1984).

Further, a hydrosol of a lipophilic polymer described in JP-B-51-39835 may be added to the hydrophilic colloid dispersion obtained above.

Gelatin is a typical hydrophilic colloid, but any of those conventionally known as those usable for photography can be used.

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

The silver halide grains that can be used in the present invention have a regular crystal form such as a cube or an octahedron,
Those having an irregular (irregular) crystal form such as a sphere or a plate, or a compound form of these crystal forms. It is also possible to use a mixture of grains having various crystal forms, but it is preferable to use a regular crystal form.

The silver halide grains used in the present invention may have different phases in the inside and the surface layer, or may be composed of a uniform phase. The grains may be such that a latent image is mainly formed on the surface (for example, a negative emulsion), and the grains are mainly formed inside the grains (for example, an internal latent image type emulsion, a pre-fogged direct reversal emulsion). It may be. Preferably,
The particles are such that a latent image is formed mainly on the surface.

The silver halide emulsion used in the present invention has a thickness of 0.5 micron or less, preferably 0.3 micron or less and a diameter of preferably 0.6 micron or more, and grains having an average aspect ratio of 5 or more account for 50% or more of the total projected area. Or a monodisperse emulsion having a statistical coefficient of variation (standard deviation S when the projected area is approximated to a circle, divided by the diameter s /) of 20% or less is preferred. Further, two or more kinds of tabular grain emulsions and monodisperse emulsions may be mixed.

The photographic emulsions used in the present invention are pea, graph kiddes (P.
Glafkides), Chimie er Physique Photographeque (Paul Montel, 1967), GFDuffin, Photographic Emulsion Chemistry
(Published by Focal Press, 1966) by VLZelikman et al., Making and Coating Photographic Emulsion (Making
and Coating Photographic Emulsion) (published by Focal Press, 1964) and the like.

Further, in order to control the growth of grains during the formation of the silver halide grains, as a silver halide solvent, for example, ammonia rhodan potassium, rhodan ammonium, and a thioether compound (for example, U.S. Pat.Nos. 3,271,157 and 3,574,628).
No. 3, No. 3,704, 130, No. 4,297, 439, No. 4,276, 37
No. 4, etc.), thione compounds (for example, JP-A-53-144319,
53-82408, 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) and the like can be used.

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.

Silver halide emulsions are usually chemically sensitized. For chemical sensitization, for example, H. Frieser edited by Die Grundlagen del Photography Shen Protese Mitt Gilber Halden (Die Gr)
undlagen der Photographischen Prozesse mit Silberh
alogeniden) (Academiche Philragus Gesellschact 1968) pp. 675-734.

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 method using amines, hydrazine derivatives, formamidinesulfinic acid, silane compounds); using noble metal compounds (eg, gold complex salts, complex salts of metals of Group VIII of the Periodic Table such as Pt, Ir, Pd) The noble metal sensitization method and the like can be used alone or in combination.

The silver halide photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, storage or photographic processing, or stabilizing photographic performance. it can. 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, mercaptotetrazole compounds (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; carboxyl groups and sulfone groups, etc. Heterocyclic mercapto compounds having a water-soluble group; thioketo compounds such as oxazillinthione; azaindenes such as tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzene Many compounds known to be antifoggants or stabilizers such as thiosulfonic acids; benzenesulfines; and the like can be added.

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 or an aminophenol derivative) in the color development processing. For example, magenta couplers include 5-pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylchroman couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, and the like, and yellow couplers include:
There are 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. The coupler is 4 equivalent or 2 with respect to silver ion.
Either equivalence may be used. Further, it may be a colored coupler having a color correcting effect, or a coupler releasing a development inhibitor with development (so-called DIR coupler).

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

The photographic emulsions of the present invention include, for example, polyalkylene oxide or its derivatives such as ethers, esters and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds and urethane derivatives for the purpose of increasing sensitivity, increasing contrast or promoting development. , Urea derivatives, imidazole derivatives, 3-pyrazolidones and the like.

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, benzylidene dye, oxonol dye; hemioxanol dye) are used as filter dyes or for various purposes such as prevention of irradiation. And a merocyanine dye). Further, as a spectral sensitizer, it may be used in combination with a known cyanine dye, merocyanine dye or heminanine dye other than the dyes shown in the present invention.

The photographic emulsion of the present invention contains various surfactants for various purposes such as coating aid, antistatic property, sliding property improvement, emulsion dispersion, adhesion prevention and photographic property improvement (for example, development acceleration, hardening, sensitization). But it's okay.

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

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), a plate-making photographic light-sensitive material (for example, lith film, lithdeny). Film), photosensitive materials for cathode ray tube displays (for example, emulsion X-ray recording photosensitive materials, direct and indirect imaging materials using screens), silver salt diffusion transfer process photosensitive materials, and color diffusion. Photosensitive material for transfer process, imbibition transfer process
Light-sensitive material, light-sensitive material used in silver dye bleaching method, light-sensitive material for recording printout image, photo-developing printout (Direct
Print image) Photosensitive materials, photothermographic materials, physical development photosensitive materials, and the like.

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), tungsten lamp, fluorescent lamp, mercury lamp, xenon arc lamp, carbon arc lamp, xenon flash lamp, and cathode ray tube flying spot can be used. The exposure time is usually 1/1000 second to 30 seconds, but 1/10
An exposure shorter than 00 seconds, for example, a 1/10 ⁴ to 1/10 ⁶ second exposure using a xenon flash lamp or a cathode ray tube can be used, or an exposure longer than 30 seconds can be used. The spectral composition of the light used for exposure can be adjusted with a color filter as needed. Laser light can also be used for the exposure. It may also be exposed by light emitted from a phosphor excited by an electron beam, X-ray, γ-ray, α-ray or the like.

For photographic processing of a light-sensitive material produced by using the present invention, for example, Research Disclosur
e) Any known method and known processing solution as described in No. 176, pp. 28-30 (RD-17643) can be applied. This photographic processing may be either photographic processing for forming a recorded image (black and white photographic processing) or photographic processing for forming a dye image (color photographic processing) depending on the purpose. The treatment temperature is usually chosen between 18 and 50 ° C, but it may be lower than 18 ° C or higher than 50 ° C.

(Effects of the Invention) According to the present invention, it is possible to obtain a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a novel water-soluble dye that has appropriate spectral absorption and does not adversely affect photographic characteristics. it can.

Further, according to the present invention, a silver halide photographic light-sensitive material having a hydrophilic colloid layer containing a novel water-soluble dye that is decolorized in photographic processing can be obtained.

Furthermore, according to the present invention, a silver halide photographic light-sensitive material excellent in stability over time can be obtained.

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

Example 1 An aqueous silver nitrate solution (a) and an aqueous solution (b) in which sodium chloride, potassium bromide, and rhodium (III) hexachloride symmonium salt were dissolved were prepared, and a gelatin aqueous solution (gelatin concentration was adjusted to pH 2.3 with phosphoric acid was prepared. 1.8%) 1 in the double jet method for 15 minutes.

The temperature of the gelatin aqueous solution was controlled so as to be maintained at 40 ° C. After forming the particles, the temperature was lowered to 30 ° C., and soluble salts were removed by a flocculation method well known in the art. After that, 40 g of gelatin was added and chemical ripening was not carried out. 4-hydroxy-6-methyl-1,3,3a, 7- was used as a stabilizer.
3 × 10 ⁻³ mol of tetrazaindene and 4 × 10 ⁻⁴ mol of 1-phenyl-5-mercaptotetrazole were added.

Thus, a monodisperse silver chlorobromide emulsion having an average grain size of 0.18μ was prepared. The yield of the obtained emulsion was 950 g.

The emulsion was divided into 100 g portions, each containing 0.2 g of the dye compound shown in Table I.
(The amount added in the photosensitive material is 53 mg / m ² ) and 0.4 g
(The amount added in the light-sensitive material is 106 mg / m ² ). Further as a polymer latex U.S. Pat.
1.5 g of the latex described in Production Example Formulation 3 of No. 620 was added,
0.4 g of saponin as a surfactant and 0.3 g of 1,3-divinylsulfonyl-2-propanol as a hardening agent were added to the mixture to prepare a final amount of 150 cc.

Thus the emulsion made by coating onto a polyethylene terephthalate transparent support so that the coating amount of 40cc per 1 m ² (thickness 100 microns), made of gelatin 1 m ² per 1.2g as a protective layer further thereon A protective layer was applied to prepare light-sensitive materials of sample numbers (1) to (9). The silver amount of each sample was 3.0 g per 1 m ² .

After coating, each sample of (1) to (9) was stored under the temperature and humidity conditions of the following (A) and (B) after application and then passed through an optical wedge to make a P-617DQ type printer (light source 100 manufactured by Dainippon Screen Co., Ltd.).
V, 1kw Quartz halogen lamp) and exposed to 38 with Fuji Photo Film Co., Ltd. automatic processor, FG-680A.
Development was carried out at 20 ° C for 20 seconds. The developing solution was GR-D1 developing solution manufactured by Fuji Photo Film Co., Ltd., and the fixing solution was GR-F1 developing solution.

Storage condition with time (A) Temperature 25 ° C, humidity 60%, 3 days (B) Temperature 50 ° C, humidity 70%, 3 days Separately, sample numbers (1) to (9) (A)
(B) Samples stored under each condition were left for 0 to 40 minutes under the light of 200lux of Toshiba anti-fading fluorescent lamp (FLR40SW-DL-X NU / M), and then evaluated with the above-mentioned photographic performance. The development processing was performed under the same conditions and the safety of safelight was evaluated.

The density of each developed sample is measured, and the relative value of the exposure dose that gives a density of 1.5 is calculated to calculate the relative sensitivity of each sample.In the safelight light irradiation test, the irradiation time for which the fog density remains within 0.02 is calculated. Therefore, the longer this time is, the higher the safelight safety is evaluated.

Also, visually observe the tint of the unexposed area and set the residual color level to A
The evaluation was made on a scale of 5 to E. A has almost no residual color, and B
Is a level at which a residual color is slightly recognized, C is a residual color at an allowable limit level, and D and E are notable because the residual color is noticeable.

The above evaluation results are shown in Table-1.

The following compounds were used as the comparative compounds (a) and (b) in Table-1.

Exemplified compound (a) Exemplified compound (b) The light-sensitive materials of sample numbers (2), (3), (4) and (5) according to the present invention are more sensitive than the light-sensitive materials of Comparative Examples (8) and (9) in terms of sensitivity, safelight safety and residual color. It has excellent performance, and it can be seen that the samples under the storage condition (B) with time have excellent residual color, as compared with the light-sensitive materials (6) and (7) of Comparative Example.

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Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one dye compound represented by the following general formula (I). General formula (I) (In the formula, R ₁ is an aryl group, a cyano group, —COOH, or —COOR.
_{7, -CONH 2, -CONHR 7,} -COR 8, -SO 2 R 8, -SOR 8, -S
O ₂ NR ₈ R ₉ or -OR ₇ (wherein R ₇ represents an aryl group,
R _8, R ₉ represents an alkyl group or an aryl group, R ₈ and R ₉ may form a 5- or 6-membered ring. ), And R ₂
Represents a hydrogen atom or an alkyl group. Q represents an aryl group, X represents a bond or a divalent linking group, Y represents a sulfo group or a carboxyl group, and L ₁ , L ₂ and L ₃ each represent a methine group. n represents 0 or 1, m represents 1 or 2, p represents 0, 1, 2, 3 or 4, and q represents 1, 2 or 3. R ₃ and R ₄ may be the same or different, and are a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, a substituted amino group, a carbamoyl group,
It represents a sulfamoyl group, an alkoxycarbonyl group or a sulfo group. R ₅ and R ₆ may be the same or different and each represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group or a sulfonyl group, and at least one of R ₅ and R ₆ is a sulfo group as a substituent. Have.