JPS59208548A - Photographic sensitive material basing on silver halide - Google Patents

Abstract

PURPOSE:To obtain a photosensitive material which is completely decolored during development remaining only slight contamination due to residual color after treatment by providing a hydrophilic colloidal layer contg. a specified compd. on the base material. CONSTITUTION:A compd. expressed by the formula is added, if necessary, to a silver halide emulsion contg. a chemical sensitizer, a sensitizing pigment, color coupler, wetting agent, etc. wherein in the formula, R1 is a univalent group having <=-0.20 sigmaP of Hammet's substituent constant; R1 is an aryl having >=1 sulpho group; R3 is a univalent group; X, Y are H or alkyl; X and Y may form a 5 or 6 membered ring by connecting with each other interposing a substituent having >=-4.70 value of SIGMApi which is time sum of the hydrophobic substituent constant pi's of substituents if said alkyl group contains substituents; L is a methine group; m is 1-5; n is 1-2). Then, the silver halide emulsion is coated on the base material so as to distribute said compd. to 1-800mg/m<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention can be utilized in photographic technology, particularly in manufacturing technology for photographic light-sensitive materials.

The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material having a hydrophilic colloid layer colored with a novel light-absorbing dye and having improved residual color staining after processing. .

Prior Art Generally, in silver halide photographic materials (hereinafter referred to as "photosensitive materials"), light of a specific wavelength is used for the purpose of light absorption filters, antihalation, antiirradiation, or sensitivity adjustment of photosensitive emulsions. It is well known that dyes are included in constituent layers of photosensitive materials for absorption, and therefore, it has been conventionally practiced to color hydrophilic colloid layers with the dyes.

Among the constituent layers of the above-mentioned light-sensitive material, one filter layer is usually located above a light-sensitive emulsion layer or between this emulsion layer and another emulsion layer, and converts incident light reaching the emulsion layer into light having a preferable spectral composition. Regarding the antihalation layer, which plays the role of changing the image, an antihalation layer is provided between the light-sensitive emulsion layer and the support, or on the back side of the support, for the purpose of improving the sharpness of the image. Therefore, the interface between the emulsion layer and the support and the support absorb harmful radiation, thereby reducing the sharpness of the image.

Furthermore, it is possible to color the I-beam emulsion layer using a dye to completely absorb harmful reflected light and scattered light to the silver halide grains, thereby preventing irradiation. (4) Improving sharpness Not only does it have good absorption spectral characteristics depending on the purpose of use, but it can also be completely decolored during photo-processing, and easily removed from photosensitive forest materials during photo-processing. It does not cause residual color staining due to dyes after processing, and does not have any adverse effects such as capri or desensitization on light-sensitive emulsions, resulting in a faded color. It must satisfy all conditions, such as not diffusing from layer to pond layer, having excellent stability over time in photosensitive forest materials or aqueous solutions, and not causing discoloration or fading. .

To date, numerous studies have been conducted with the aim of developing dyes that satisfy the above conditions, such as U.S. Pat. No. 3,540,887, U.S. Pat.
No. 3,560.214, Special Publication Show 3] -1057
Benzylidene dyes were proposed in British Patent No. 506,385 and Japanese Patent Publication No. 39-22069, and merocyanine dyes were proposed in U.S. Patent No. 2,493,747. Dyes such as styryl dyes have been proposed in US Pat. No. 1,845,404.

However, the present situation is that a dye that satisfies the above conditions has not yet been found.

Purpose of the Invention Therefore, the purpose of the present invention is to have optimal absorption spectrum characteristics, completely decolorize during development processing, have extremely little residual color contamination after processing, prevent diffusion to other layers, and be photosensitive. An object of the present invention is to provide a dye having excellent stability over time in an emulsion or an aqueous solution, and a silver halide photographic material containing such a dye.

Structure of the Invention As a result of repeated studies, the present inventors have determined that the above object can be achieved by a silver halide photographic material containing a compound represented by the following general formula (I). I found it.

General formula (I) 2 In the formula, R5 represents a monovalent group having a Hammett moiety smaller than -0,20, R and fl represent an aryl group having at least one sulfo group, and R8 represents a monovalent group having at least one sulfo group. represents,X
and Y represent a hydrogen atom or an alkyl group, respectively, and when the alkyl group has a substituent, the sum of the hydrophobic substituent constant π values of this substituent is -4,70
In the case of a larger substituent, X and Y may be bonded to each other to form a 5- or 6-membered ring. Further, L represents a methine group, and m is 1 to 5.
, represents n digit 1 dimension 2.

Hereinafter, the present invention will be explained in detail.

In the present invention, the dye contained in the light forest material can be represented by the general formula (T), and the dye can be represented by the general formula (T).
r), Hammett's great value represented by R1 is -0,2
Monovalent groups smaller than 0 include hydroxy groups, alkoxy groups (e.g. methoxy, ethoxy, butoxy, 2-methoxyethoxy, 2-hydroxyethoxy), amine groups (e.g. amino, methylamino, dimethylamino, ethylamine, diethylamino, anilino), ureido group (
For example, ureido, methylureido, ethylureide) and the like are preferably mentioned.

Next, the aryl group having at least one sulfo group represented by R2 is, for example, an alkyl group, a hydroxy group,
From mercapto group, alkoxy group, alkylthio group, alkylsulfonyl group, arylthio group, arylsulfonyl group, carboxyl group, alkoxycarbonyl group, cyan group, nitro group, amino group, acylamino group, sulfonamide group, carbamoyl group, sulfamoyl group, etc. Preferably, it is substituted with a selected group.

The preferred aryl group having at least one sulfo group represented by R2 above is represented by the following general formula (TII).

General formula (1) (Z)v In the formula, M represents a water bulk atom or a cation, a two-digit alkyl group (e.g. methyl group, ethyl group), a hydroxy group,
Alkoxy groups (e.g. methoxy group, ethoxy group), mercapto group, alkylthio group (e.g. methylthio group, ethylthio group), alkylsulfonyl group (e.g. methanesulfonyl group, ethanesulfonyl group), arylthio group (e.g. phenylthio group, tolylthio group), Arylsulfonyl A (benzenesulfonyl group, toluenesulfonyl group), carboxyl group, alkoxycarbonyl group (e.g. ethoxycarbonyl group, methoxycarbonyl group), cyano group, nitro group, amine group (e.g. amine, methyl ε), dimethylamino, anilino), acylamino groups (e.g. acetylamino, benzoylamino, sulfamide & (fall methanesulfonamide, benzenesulfonamide)), carbamoyl groups (e.g. carbamoyl, methylcarbamoyl, phenylcarbamoyl), and 6u representing a sulfamoyl group (e.g. sulfamoyl, methylsulfamoyl, phenylsulfamoyl), etc. represents an integer of 1 to 3;
represents an integer from O to 4. However, 1≦u −)−v≦5
It is. Specific examples of the group represented by the above general formula (II) include 3-sulfophenyl group, 4-sulfophenyl group, 2-methyl-4-sulfophenyl group, 2-methoxy-4-sulfophenyl group, -Hydroxy-4-sulfophenyl group, 2,6-dimethyl-4-sulfophenyl group, 3-9-carboxy-2-hydroquino-5-sulfophenyl group,
2.5-disulfophenyl group, 3*5-disulfophenyl group, 3.6-disulfo-2-naphthyl group, 8-hydroxy-3,6-disulfo-2-naphthyl group, 5-hydroxy-7- Examples include sulfo-β-naphthyl group and 6,8-disulfo-β-naphthyl group.

Next, the monovalent group represented by R3 has 1 to 4 carbon atoms.
Alkyl groups (e.g. methyl group, ethyl group, n-butyl group), halogen atoms (e.g. fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxy group (e.g. methoxy group, ethoxy group), nitro group, amino group (e.g. amino, ethylamino, dimethylamino, anilino), acylamino groups (acetylamino group, benzoylamino group),
Sulfonamide group, (e.g. methylsulfonamide) carboxyl group, cyan group, sulfo group, alkoxycarbonyl group (methoxycarbonyl group, propoxycarbonyl & etc.), alkylsulfonyl group (methylsulfonyl group, ethylsulfonyl Jl), 10-carbamoyl group (e.g. carbamoyl, methylcarbamoyl 1. ethylcarbamoyl), sulfamoy/L4 (
For example, sulfamoyl and methylsulfa are produced.

In the general formula (I), the alkyl group represented by X and Y is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, and the like. When this alkyl group has a substituent, examples of the substituent include substituents where the sum of the hydrophobic substituent constants π and Σπ is greater than -4.70. Examples of these substituted alkyl groups include is cyanoalkyl, hydroxyalkyl, halogenoalkyl, carboxyalkyl, alkoxycarbonylalkyl, (e.g. methoxycarbonylalkyl), acylalkyl (e.g. acetylalkyl), acyloxyalkyl (e.g. acetyloxyalkyl), alkoxyalkyl (e.g. methoxyalkyl, phenoxy alkyl group), dialkylaminoalkyl (e.g. dimethylaminoargyl)
, phenylaminoalkyl, acylaminoalkyl (e.g. acetylaminoalkyl), alkylsulfonylaminoalkyl (e.g. methylsulfonylaminoalkyl), alkylsulfonylalkyl (e.g. evamethylsulfonylalkyl), alkylthioalkyl (e.g. methylthioalkyl), aminoalkyl Examples include methylaminoalkyl, aralkyl (eg, benzyl), and the like. Further, X and Y may be different from each other or may be the same. Furthermore, examples of the 5-membered group or 6-membered group formed by X and Y bonding to each other include a pyrrolidino group, a piperidino group, a morpholino group, and the like.

In the present invention, the substituent of the alkyl group having the substituents represented by X and Y is, as described above, a substituent whose sum of the values of the hydrophobic substituent constant π is larger than -4.70. characterized by being, namely X and/-
! or when Y is represented as -R-X' and/or -R-Y' (where Rfi represents an alkylene group, and Y' and Y' each represent a substituent), Y', Y
The substituents X' and Y' are selected such that Σπ is greater than -4 and 70, respectively. The value of this hydrophobic substituent constant π is described on the same page of the above-mentioned publication, and the substituent can be selected based on the description in this table.

In the general formula (I), the methine group represented by L may be substituted with an alkyl group having 1 to 4 carbon atoms (e.g., methyl group, ethyl group, n-butyl group) or an aryl group (e.g., phenyl group). dance.

The dye according to the present invention represented by the general formula (I) can be synthesized by condensing an aldehyde compound represented by the following general formula (m) and a pyrazolone compound represented by the following general formula (TV). can.

13- General formula (IV) ■(.

In the formula, R1, R1, R3, X1Y, L and m each represent groups or several groups having the same meaning as those in the above general formula (I). p and q are integers of 1 or 2. However, between n and V in the general formula (I), n=p+q-
Since there is a relationship of 1, p and q cannot be 2 at the same time.

The above reaction is carried out in the presence of a basic condensing agent such as pyridine, piperidine, triethylamine, etc.
) and (Iv) by heating the mixture. Further, the above reaction is carried out in the presence or absence of the above basic condensing agent, using an inorganic compound such as methanol, ethanol, ethylene glycol, methyl cellosolve, acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, dioxane, 14-acetic acid, or water. It can also be carried out in an active medium.

The aldehyde compound represented by the above general formula (m) is
It can be manufactured by a known method. For example, the general formula (I
In II), the aldehyde compound with P=1 is dimethylformamide as a formyl additive? Bilsmeyer and Hack's reaction (Berichte, Vol. 60, 1] 9)
p., 1927) from the corresponding substituted anilines.

-10,000, P-2 aldehyde is prepared using N-methylanilinopropane(1)-al(3) and appropriate aniline.
Erichte, Vol. 91, p. 850 (1958), it can be produced in the same manner as the Vilsmeier reaction. Berlchte, Vol. 61, 20
It can also be obtained from the reaction of the corresponding substituted aminobenizaldehyde with valaldehyde as described on page 74 (1928).

Pyrazolone compounds of the general formula (IV) with q=l can be prepared by condensing various sulfoarylhydrazines with appropriate substituted esters by vertical methods practiced in dye chemistry.

The intermediate represented by q-2 of the general formula (TV) can be superior to the intermediate represented by q-2 of the general formula (TV) by condensation of the product represented by q-1 of the general formula (IV) with a dialkyl ketone, an alkylaryl ketone, or an aliphatic alkyl ketone. can.

The pyrazolone compound represented by the general formula ([V)] can be prepared, for example, by the method described in Organic 5 Syntheses, Vol. 28, 87 Sada (1948), J. Am.
chem, Sac, vol. 66, p. 1849 (1
94, 4) method described in J.

Am, Ohem, Eloc, Volume 65, 52
-m (1943) method 1, J, Am,
It can be obtained by using the method described by Sada (1942), Chem, Soc, Vol. 64, 2136. Typical specific examples of the dyes according to the present invention are described below.

(Exemplary compound Th1 (1) (2) S○, Na (3) o3Na (4) 17- (5) (6) (7) 03Na J8- (8) (9) l0sNa (10) (11) (12 ) NaO8S (13) So, Na (1・1) o3Na (15) (16) 2l- (17) NaO8S (18) (19) So, H・ (C,H,)3N 22- (20) KO, 5 (21) (22) (23) ■ 03Na (24) (25) (26) (27) (28) ``In 03, next, synthesis examples of the method for synthesizing the dye according to the present invention are shown. Explain in detail.

Synthesis Example 1 (Synthesis of Exemplary Dye ()) In methanol JQ ml, 3.061/ml of 3-ethoxy-1-(4-sulfophenyl)-2-pyrazoline-
Add 5-one sodium salt and 1.571 il' of 4-dimethylaminobenzaldehyde and add pyridine 1
．． 61! was added and reacted for 2 hours under heating under reflux. Thereafter, 0.8211 mL of acetic anhydride dissolved in 10 ml of distilled water was added, and reflux was continued for 5 minutes. The reaction solution was cooled, all precipitated crystals were collected by filtration, thoroughly washed with methanol, and dried to obtain the above-mentioned exemplified dye 4.22.9. The λmax of the aqueous solution of this dye was 477 nm.

Synthesis Example 2 (Synthesis of Exemplary Dye (7)) In 40 m/m of methanol, 2.56.9 g of 3-hydroxy-1-(4-sulfophenyl)-2-pyrazolin-5-one and 1.64 g of 4 -Dimethylaminobenzaldehyde was added, and then 1.58.9' of pyridine was added, and the mixture was reacted under heating under reflux for 2.5 hours. Then 26- 1.6 anhydrous sodium acetate dissolved in 1 o ml of distilled water
4 g was added and reflux was continued for 5 minutes. The reaction solution was cooled, and the precipitated crystals were collected by filtration, thoroughly washed with methanol, and then dried to obtain the exemplified dye 3.35.9. The λmax of the aqueous solution of this dye was 488 nm.

The dye according to the present invention produced as described above has R at the 3-position of the pyrazolone ring, as shown by the general formula (I).
8 has a monovalent group having a Hammett's 4 value of less than 20, and has at least one sulfo group as R2 in the 1st position, and further has an aryl group which may have a substituent. Therefore, the dye according to the present invention has significantly improved storage stability in an aqueous solution (acidic aqueous solution) compared to the conventionally known dye 1, and can be used in a treatment bath. It has excellent decolorization properties and very little residual color staining.

Furthermore, in the dye according to the present invention, the substituted alkylamino group of the benzylidene group is substituted with a substituent having a hydrophobic substituent constant π value sufficient to prevent the dye from diffusing as described above. , there was less diffusion to other layers, which also improved the reduction in sensitivity.

In the light-sensitive material of the present invention, the oxonol dye represented by the above general formula can be incorporated into the silver emulsion and used as an irradiation prevention agent. It can also be incorporated into a colloid layer and used as a filter dye or antihalation dye.

Depending on the purpose of use, two or more dyes may be used in combination with R-silk, or they may be used in combination with IL dye once a month. In order to incorporate it into the hydrophilic colloid layer, it can be easily carried out by a conventional method.In general, dyes are dissolved or organic/inorganic alkali salts of dyes are dissolved in water. However, the dye can be incorporated into the photosensitive material by preparing a dye hydroxyl solution with an appropriate concentration, adding it to a coating solution, and coating it by a known method.
Although it varies depending on the purpose of use, it is generally applied in an amount of 1 to 800 m 9 per 1 m 8 of area on the photographic forest material.

Supports in the photosensitive material of the present invention include cellulose acetate, cellulose nitrate, polyester films such as polyethylene terephthalate, polyolefin films such as polyethylene, polystyrene films, polyamide films, polycarbonate films, baryta paper, polyolefin-covered paper, and polypropylene. synthetic paper,
There are glass plates, metals, etc., and these supports are appropriately selected depending on the intended use of the photosensitive material.

Hydrophilic colloids in the photosensitive material of the present invention include gelatin, derivative gelatin such as phthalated gelatin and benzenesulfonylated gelatin, water-soluble natural polymers such as agar, casein, and alginic acid, and synthetic resins such as polyvinyl alcohol and polyvinylpyrrolidone. , cellulose derivatives such as carboxymethyl cellulose, etc., and these can be used alone or in combination.

The silver halide emulsion in the light-sensitive material of the present invention includes:
Any of those commonly used in silver halide emulsions, such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, and silver chloroiodobromide, is included.

The silver halide emulsion used in the light-sensitive material of the present invention can be prepared by all conventional manufacturing methods, as well as by divine manufacturing methods, such as the
6-7772, or the method described in U.S. Pat. No. 2,592,250, in which at least a portion of A method for producing a so-called conversion emulsion, such as forming an emulsion of silver salt grains made of silver salt, and then converting at least a part of the grains to silver bromide salt or silver iodobromide salt, or an average grain size of 0.1 μm or less It can be prepared by any manufacturing method such as the manufacturing method of Knoppmann emulsion consisting of silver halide (fine grains having a diameter) or silver halide. This silver chloride emulsion is
Chemical sensitizers, such as thiosulfate, allylthiocarbamide, thiourea, allyl isothiocyanate, sulfur sensitizers such as cystine, active or inactive selenium sensitizers, potassium chloroaurate, auric trichloride, Gold compounds such as potassium auric thiocyanate, 2-aurothiabenzthiazole methyl chloride, etc.
? 11 - Noble metal sensitizers like ammonium chlorovaladate, sodium chloropalladite and other palladium compounds, potassium chloroplatinate and other platinium compounds, ruthenium compounds, etc.! l:fr: can be sensitized using such sensitizer combinations. Moreover, this emulsion can be reduced sensitized with a reducing agent other than Ich-sensitized, such as triazoles, imidazoles, asaindenes, benzthiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or It can be stabilized with a mixture of these, and a thioether type, quaternary ammonium salt type, or polyalkylene oxide type sensitizing compound can be contained.

The silver halide emulsion used in the light-sensitive material of the present invention may be spectrally sensitized with a sensitizing dye according to the need for peace of mind.6 Sensitizing dyes include cyanine dyes, merocyanine dyes, complex cyanine dyes, oxonol dyes, and hemioxonol dyes. Colorful dyes such as nol dyes, styryl dyes, merostyryl dyes, and streptocyanin colors can be used, and one sensitizing dye or a combination of two or more of them can be used.

In the photosensitive material VC of the present invention, the emulsion layer and its [11
(In the aqueous colloid layer, glycerin, 1.5-
Dihydroxy alkanes such as bentanediol, esters of ethylene bisglycolic acid, bisethyl diethylene glycol saccharide, wetting agents such as water-dispersible fine particulate monomolecular compounds obtained by emulsion polymerization, plasticizers, film property improvers, etc. All of the aldehyde compounds, N.

N-methylol compounds such as N'-dimethylol urea, mucohalogen acids, divinyl sulfones, active halogen compounds such as 2゜4-dichloro-6-hydroxy-8-triazine, dioxane derivatives, divinyl ketones, isocyanates, carbodiimides Hardening agents such as saponin, polyalkylene glycol, polyalkylene glycol ether, alkyl sulfonic acid P! Contains surfactants such as alkylbenzene sulfone, argylnaphthalene sulfonate, and photographic additives such as fluorescent brighteners, antistatic agents, antistain agents, ultraviolet absorbers, and stabilizers. I can do things.

In the light-sensitive material of the present invention, a color coupler may be contained in the emulsion layer, and the coupler may be either a 4-fold or 2-fold coupler, and a colored coupler for masking or a color suppressor may be released. It may be a coupler that As yellow-forming couplers, open-chain ketomethylene compounds such as acylacetamides are preferred; as magenta-forming couplers, pyrazolone-based compounds; as cyanide-forming couplers, phenol-based or naphthol-based compounds are usually advantageous. It is used in

Furthermore, the photosensitive material of the present invention can have any layer structure that can be used in conventional photosensitive materials.

Next, the present invention will be specifically explained with reference to Examples, but the present invention is not limited thereto.

Example 1 Add 5 m/g of glacial acetic acid to 2°OX 10-" mol/l 33- water@liquid of exemplary dye (1) according to the present invention and stir 1~
The decomposition rate measuring solution (pH 2.8 to 2.9) was adjusted.

Spectrophotometer I was used to measure the decrease in the absorbance of this solution at its maximum absorption wavelength over time (every 10 minutes at 1 o'clock!i, ?l l
The initial decomposition rate was determined. Similarly, exemplary dyes (8), (131, (19), and (2)
1) as well as the following specific v dyes (A), (Bl,
(0) , (T)) OJ: hi(]'Th1 KTsumo was also measured.The results obtained are shown in Table 1.

Comparative dye (A) So, Na Comparative dye (C) Comparative dye (D) Comparative dye (K) Table 1 As is clear from Table 1, the dyes according to the present invention are Comparative dyes (A) to (Dl Compared to dyes having a monovalent group with a Hammett Q value larger than -0.20 at the 3-position of the pyrazolone ring, the stability in aqueous solutions is significantly improved. In addition, when the 1st position of the pyrazolone ring is substituted with an alkyl group like the comparative dye (E), a monovalent compound with a /% concentration value of less than -0.20 is substituted at the 3rd position. group (-oc2n in the case of comparative sample (E), the value of -
It was also understood that the storage stability as described above was not improved even if the composition had 0.0, 24).

Example 2 3.5.9 ml of gelatin was added to 35 ml of distilled water and stirred, and 2.OX 1. 0-'
Add 5 ml of an aqueous solution containing mol, and then add 1.25 mA' of a 10% saponin aqueous solution and 0.75 mA of a 1% formalin m solution.
m1? Add water and make a total volume of 50 ml. This dye solution was coated on an acetyl cellulose film support, dried, and the samples [1], [2] and [3]
And so. -! Comparative samples 37- Comparative dye (F) o3Na Comparative dye (G) Each of these samples was prepared in the same manner using the following comparative dyes (F) and (G) instead of the dye according to the present invention. was immersed in Genzuka solution having the following composition at 5° C. for 1 minute, washed with water for a second, and then dried.

(Composition of current bride solution) −A　− water? In addition, it is set to 11.

The optical spectrum of each sample was measured before and after immersion in the liquid, and the decolorization rate was determined from the difference in absorbance at the thickest wavelength (VC). The results are shown in Table 2 below.

1 (A is the absorbance before being immersed in the liquid, and E is the absorbance after being immersed in the liquid.) As is clear from Table 2, the present invention It was found that the dyes related to the above showed superior decolorizing properties compared to the comparative dyes39-61.However, in the samples containing the comparative dyes (F and G), the processing solution was slightly reduced due to the dyes releasing H. However, with the dye according to the present invention, such coloring and staining was observed. It consists of 0.57 ruti of silver oxide, and the semi-average grain size of the particles is 0.32.
A 1' silver gelatin emulsion with a uniform odor of μ was added to the adrenal gland. This gelatin I'L agent] kg (contains 75 g of silver 4811 gelatin), 2,4-dichloro-6-hydroxy-
1゜3.5-) riazine sodium salt (1゜aqueous solution) 3
5 ml and Zabonin (10 ml water heart fj)! '101nA
! After addition of y, the undercoat-treated Bo 1) was coated on an ethylene terephthalate film support so that 5Q + 119 silver per 100 cnt was impregnated and dried □ Furthermore, the present invention was applied on top of this quenching agent 11- Exemplary dyes related to (
A protective layer having the following composition containing 2) was applied so that the dry film thickness was 2/Am. (Sample 6) (Collection layer 1 composition) Similarly, in j-, instead of the exemplary dye (2) according to the present invention,
All samples containing the exemplary dyes (9) and (16) according to the present invention and the comparative dyes (Fl and (G) used in Example 2) were prepared, and samples 7, 8.9 and 1 were prepared, respectively.
It was set to 0.

Each of these samples was cut into small pieces and exposed to photographic light P2! It was then processed using a developing solution and a fixing solution having the following compositions. Development was carried out for 1.5 minutes at a heated temperature, and fixation was carried out at 2 (1'
After washing with water at (a) C for 5 minutes, it was dried.

(Composition of Gentsuka solution) 4l-- (j], t, composition of No.H solution) Ten of each of the treated samples were stacked one on top of the other, and the presence or absence of colored contamination on the samples was examined. The disappointing results are shown in Table M3 below.

42- Table 3 In the samples using comparative dyes, colored stains were observed in the samples, but with the dyes according to the present invention, there was no colored staining due to excellent run-off and decolorizing properties.

Example 4 A putrid-smelling silver gelatin emulsion containing 70 moles of 1M silver and 30 moles of silver bromide and having an average grain size of 0.3 μm was prepared. After adding 20 ml of formalin (1% aqueous solution) and 5 Qml of saponin (10% aqueous solution) per 1 kg of this gelatin emulsion (containing 48 I silver and 75 ml gelatin), subbing-treated polyethylene was added. The emulsion layer was coated on a terephthalate film support, and a protective layer having the following composition was further coated on the emulsion layer.

(Protective layer composition) On the back side of the support coated with the emulsion layer and the toughening layer, one coat of gelatin containing all the dyes of the same composition was coated so that the dry film thickness was 3 μm (sample 6). 11) (Gelatin-free composition) Similarly, instead of the exemplary dye (2) according to the present invention,
Exemplary dye (28) according to the present invention and the following dye [H
]'e were used to prepare samples and designated as samples (12 and (13)).

Comparative sample (H) Developed in the same manner as in Example 3 above, and each sample 10
The sheets were stacked one on top of the other and colored contamination was evaluated. The results obtained are shown in Table 4 below.

Table 4 As shown in the above table, colored stains were observed in the samples using the comparative dyes, but not a single colored stain was observed with the dyes according to the present invention. However, it has been found that the dye according to the present invention can produce a photosensitive material having an effect of preventing immersion in Halley's 45-joules without causing any adverse effects such as capri or desensitization on photographic emulsions. .

Example 5 A gelatin solution having a composition of F'gr: containing %-F'gr in the dye was coated as a first layer on a polyethylene V-terephthalate support to a film thickness of 2 μm after drying.

(Gelatin liquid composition) Next, 1 kg of gelatin %'L was added to a silver iodine gelatin emulsion consisting of 96 mol of tin bromide and 4 mol of silver iodide and having an average grain size of 0.8 μm. [Su2,4-dichloro-6-hydroxy-+,3.5-) riazine sodium ji (1% solution in water) 20 m, l and sodium dodecylbenzenesulfonate (1% water solution W l 20 m
Add 1-1 and apply the second layer so that the dry thickness is 5 itm.

Further, on top of this emulsion layer, a gelatin solution prepared as shown below was coated as a protective layer to a dry film thickness of 2 μm, and sample (14) was prepared as follows.

(Gelatin solution set I7!1:) In a similar manner, instead of the 47-exemplified dye (6) according to the invention in the first layer, exemplified dye (8) and ao
Nara IJ K T Fi own his own troubles (I), (1)
Create a trial visit using Oyohi (K) 1~. At the same time, a sample containing no dye at all was also prepared by the same 1≦1 strain. One song of these samples (C samples (15), (16), (17),
(18), (yen) and (nige)) Toshi/ζ.

Ratio 111! Samples (I) Each of these samples was cut into small pieces, exposed through a photographic light wedge, and processed using the developing solution and fixing solution used in Example 2 having the following composition. Development was carried out at 5°C for 2 minutes, fixing was carried out at 25°C for 2 minutes, water washing was carried out at 5°C for 5 minutes, and then dried.

(Composition of dark solution) After development, sensitometry was performed to obtain a photographic characteristic curve, and the relative sensitivity was determined with the sensitivity of sample (20) containing no dye being set as 100. The results obtained are shown in Table 5.

49-Table 5 Samples containing dyes according to the present invention show less decrease in sensitivity than samples containing all comparative dyes, that is, the dyes according to the present invention have less diffusion from the mordanted layer to the curved layer. It turns out that there are few. On the other hand, the hydrophobic 1a substituent constant π of the substituent of the substituted alkyl group of the substituted alkylaminobenzylidene group at the 4-position of the pyrazolone ring is smaller than −4.70, such as comparative dyes (11 to (K)). (Sample (1), (
J) For P and (K, ), the π1 directness of SOl is -4,761
, it was found that the sensitivity of samples containing these conditions was greatly reduced.

- Regarding - Effects of the Invention In the photosensitive forest material containing the dye of the present invention as represented by the general formula (T), the σ retention stability of the dye in acidic water resistance is significantly improved. It also has excellent run-off properties and decolorization properties in the processing bath, so there is no risk of residual color contamination. Since the shredded VC is also prevented from diffusing from the mordanted layer, it does not cause a decrease in sensitivity.

Agent Yoshimi Kuwahara 51- Procedural Amendments Showa Edict November 4 II 1978 + I Special d'1 Application No. 83684 Li2 Name of the invention Silver halide photographic light-sensitive material: 1 Supplementary statement: Small A'1 Relationship Patent applicant I 1 Location Nishi-a, Shinjuku-ku, Tokyo "Shuku +"'1126 2
Name (+27) Konishi Rokugeshin 1-Gyo Co., Ltd. 15
Clause 11 of the Supplement 11" Order, Vol. 6, "Detailed Description of the Invention" column 7 of the specification subject to amendment, Contents of the Amendment (1) The detailed description of the invention is amended as follows.

2-

Claims (1)

[Claims] (1) A silver halide photographic light-sensitive material characterized by containing (!-) a compound represented by the following general formula (T). represents a monovalent group having a value smaller than -0.20, R7 represents an aryl group having at least one sulfo group, R3 represents a monovalent group, X and Y are a hydrogen atom, a sulfo group, respectively; represents an alkyl group, and when the alkyl group has a substituent, the sum of the hydrophobic substituent constant π values of the substituents Σπ is -
It is a substituent larger than 4,70, and X and Y may be bonded to each other to form a 5-membered or hexacyclic ring. Further, L represents a methine group, m represents an integer of 1 to 5, and n represents an integer of 1 or 2. ] (2) The aryl group having at least one sulfo group f represented by R2 above is an alkyl group, a hydroxy group, a mercapto group, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an arylthio group, an arylsulfonyl group, a carboxyl group, Claim (1) characterized in that the substance is substituted with a group selected from an alkoxycarbonyl group, a cyano group, a nitro group, an amino group, an acylamino group, a sulfonamide group, a carbamoyl group, and a sulfamoyl group. silver halide photographic material.