JPH01193735A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain a hydrophilic colloid layer by a novel water soluble dye which does not exert harmful influence on photographic characteristics by incorporating at least one kind of specific dye compds. into said layer. CONSTITUTION:At least one kind of the dye compds. expressed by the formula I is incorporated into the above-mentioned layer. In the formula I, R1 denotes an aryl group, cyano group, etc.; R2 denotes a hydrogen atom or alkyl group; Q denotes an aryl group; X denotes a bond or bivalent combination group; Y denotes a sulfo group or carboxyl group; L1-L3 denote a methine group; n denotes 0 or 1; m denotes 1 or 2; p denotes 0-4; q denotes 1-3; R3, R4 may be the same or different and denote a hydrogen atom, halogen atom, alkyl group, sulfo group, etc.; R5, R6 may be the same or different and denote a hydrogen atom, alkyl group, sulfonyl group, etc.; at least either of R5, R6 has a sulfo group as a substituent. The hydrophilic colloid layer contg. the novel water soluble dye which does not exert the harmful influence on the photographic characteristics is thereby obtd.

Description

Detailed Description of the Invention (Industrial Application Field) The silver halide photographic light-sensitive material of the present invention having a dyed hydrophilic colloid layer is photochemically inert and easily decolorized during photographic processing. The present invention relates to a silver halide photographic material having a hydrophilic colloid layer containing a dye to be eluted and/or a hydrophilic colloid layer.

(Prior Art) In silver halide photographic materials, photographic emulsion layers 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 incident on the photographic emulsion layer, a colored layer is provided on the photographic light-sensitive material on the side 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, such as in a multilayer color light-sensitive material, a filter layer may be located between them.

Light scattered during or after passing through the photographic emulsion layer may be reflected at the interface between the emulsion layer and the support, or at the surface of the light-sensitive material opposite to the emulsion layer, and enter the photographic emulsion layer again. Between the photographic emulsion layer and the support, in order to prevent blurring of images, that is, halation,
Alternatively, a colored layer may be provided on the opposite side of the support from the photographic emulsion layer. In the case of a zero-layer color photosensitive material, such a colored layer is called an antihalation layer.
An antihalation layer may be placed between each layer.

Image sharpness decreases due to light scattering in the photographic emulsion layer (this phenomenon is generally called irradiation)
In order to prevent this, the photographic emulsion layer is also colored.

These layers to be colored are often composed of wood-philic colloids, and therefore, for coloring them, a water-soluble dye is usually incorporated into the layer. This dye must satisfy the following conditions.

fil Must have appropriate spectral absorption according to the purpose of use.

(2) It is photochemically inert, that is, it does not adversely affect the performance of the silver halide photographic emulsion layer in a chemical sense, such as a decrease in sensitivity, latent image regression, or fog.

(3) No harmful coloring will remain on the photographic material after processing by being bleached or dissolved away during the photographic processing process.

Many efforts have been made by those skilled in the art to find dyes that meet these conditions, and the following dyes are known, for example British Patent Nos. 506°385 and 1,17.
7.429, 1,31). No. 884, 1,338
, No. 799, No. 1゜385.371, No. 1,467.
No. 214, No. 1.433.102, No. 1,553.5
No. 16, JP-A-48-85, 130, JP-A No. 49-1) 4
゜No. 420, No. 55-161, 233, No. 59-1)
No. 1.640, U.S. Patent No. 3,247.127, No. 3
, 469,985, 4,078°933, etc., oxonol dyes having a pyrazolone nucleus or barbyl scattering, U.S. Pat. No. 2,533,472, 3,
No. 379,533, other oxonol dyes described in British Patent No. 1,278,621, etc., British Patent No. 5
75°691, 680,631, 599,62
No. 3, No. 786.907, No. 907,125, No. 1
, 045,609, U.S. Pat. )8.
247, British Patent No. 2゜014.598, British Patent No. 750
azomethine dyes described in U.S. Pat. No. 2,865.752, U.S. Pat. No. 2.538.009, U.S. Pat. 688.
No. 541, No. 2,538,008, British Patent No. 58
No. 4.609, No. 1,210,252, Japanese Unexamined Patent Publication No. 1973-
No. 40.625, No. 51-3,623, No. 51-10
, No. 927, No. 54-1) No. 8.247, Special Publication No. 1973-
No. 3,286, No. 59-37゜303, No. 62-10
Arylidene dyes described in No. 6.455, No. 62-133.453, etc., Japanese Patent Publication No. 2B-3,082, No. 4
Styryl dyes described in British Patent No. 4-16゜594, British Patent No. 59-28,898, etc., described in British Patent No. 446,583, British Patent No. 1,335,422, JP-A-59-228゜250, etc. First British patent for triarylmethane dye
, No. 075,653, No. 1,153゜341, No. 1,
284.730, 1,475.228, 1,5
Examples include merocyanine dyes described in U.S. Pat. No. 42.807, and cyanine dyes described in U.S. Pat.

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

For example, JP-A-59-206,829, JP-A-59-21
), 035, 59-21), 041, 59-20
No. 8,548, No. 59-21), No. 042, etc. However, some of these dyes remain after processing due to the rapid development processing that has been carried out in recent years. In order to solve this problem, it has been proposed to use dyes that are highly reactive with sulfite ions, but in this case, the stability in the photographic film is insufficient, and the concentration may decrease over time. It has the disadvantage that the desired photographic effect cannot be obtained.

(Problems to be Solved by the Invention) The object of the present invention is, firstly, to obtain a silver halide emulsion layer dyed with a hydrophilic colloid layer by a novel water-soluble dye that does not have a detrimental effect on the photographic properties of the silver halide emulsion layer. An object of the present invention is to provide photographic materials.

A second object of the present invention is to provide a silver halide photographic light-sensitive material in which the rough aqueous colloid layer is dyed with a novel water-soluble dye having excellent decolorizing properties through processing.

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

A fourth object of the present invention is to provide a silver halide photographic material which is excellent in filter effect, antihalation effect, or sensitivity adjustment effect of a light-sensitive emulsion.

(Means for Solving the Problems) These objects of the present invention have been achieved by the present inventors in
As a result of further investigation based on the dyes described in No. 3623, at least one of the dye compounds represented by the general formula (r)
This was achieved using a silver halide photographic material containing seeds.

General formula (1) % formula %) In the formula, RI is an aryl group, a cyano group, C0OH, C0
0Ry, -CONHz, CONHRw, C0NR
tRs, -CORe, -3OiRs, 5ORs
, 5OzNRsR*, -OR,, -NHCORl, ~
N Rs COR1, N HCON HRv, N R
t CON HRt, -NHCONRtRs, -NR
tSOzRw, -NH3OtRs, -NHR, or -N Rq Rs (where R1 represents an aryl group, R3 and R droplets represent an alkyl group or an aryl group, and R
8 and R9 may be linked to form a 5- to 6-membered ring, R1 represents a hydrogen atom or an alkyl group, Q represents an aryl group, and X represents a bond or a divalent linking group. , Y represents a sulfo group or a carboxyl group, and L
+, Lx, Ls each represent a methine group, n is O or 1, m is l or 2, p is 0, 1.2.3 or 4, q is l, 2 or 3* R,, R4 may be the same or different and represent 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, and a sulfo group.

Rs and R4 may be the same or different and represent a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group, or a sulfonyl group, and at least one of R1 and R4 has a sulfo group as a substituent.

The dye represented by general formula (1) will be explained in more detail.

The aryl group represented by Rt, Rt, Re and R9 is preferably a phenyl group or a naphthyl group, and a substituent [for example, a halogen atom such as fluorine, chlorine, or bromine, a sulfo group, a carboxyl group, a hydroxyl group, a cyano group, a carbon number 1-4
an alkyl group (e.g. methyl, ethyl, n-propyl)
, an alkoxy group (eg, methoxy, ethoxy), or an aryloxy group (eg, phenoxy)].

The alkyl group represented by R8 and R9 has 1 carbon number
~8 alkyl groups (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, n-amyl, n-hexyl, n-octyl, isoamyl) are preferred, and substituents (e.g. fluorine, Halogen atoms such as chlorine and bromine, phenyl groups, hydroxyl groups, cyano groups, alkoxy groups (e.g. methoxy, ethoxy, hydroxyethoxy), aryloxy groups (e.g. phenoxy, p-
methoxyphenoxy), carboxyl group, sulfo group, amino group, substituted amino group (eg dimethylamino, diethylamino)].

The alkyl group represented by R2 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 [e.g. , halogen atoms (e.g. fluorine, chlorine, bromine), carbamoyl (e.g. methylcarbamoyl, ethylcarbamoyl), sulfamoyl (e.g. ethylsulfamoyl)
, cyano group, nitro group, alkylsulfonyl M (91
It has an arylsulfonyl group (e.g., methanesulfonyl), an amino group (if ignited, dimethylamino, diethylamino), an acylamino group (e.g., acetylamino), a sulfonamide group (e.g., methanesulfonamide), and a hydroxyl group. Also good.

The divalent linking group represented by X is, for example, -0-1
”-N R1o-1-N R+.C0-2S Oz-1
-NR1,5Ot-, where R1° is a hydrogen atom, an alkyl group having up to 5 carbon atoms (e.g. methyl, ethyl, n-propyl, n-butyl, n-amyl, isobutyl), or an alkyl group having up to 5 carbon atoms. Substituted alkyl groups (substituents include alkoxy groups having 3 or less carbon atoms (e.g. methoxy, ethoxy), sulfo groups, carboxyl groups, cyano groups, hydroxyl groups, amino groups (e.g. dimethylamino, diethylamino), carbamoyl groups (e.g. hydroxyethyl) aminocarbonyl, ethylaminocarbonyl) or sulfamoyl group (eg, ethylaminosulfonyl)].

Examples of the 5- or 6-membered ring formed by connecting Rs and R9 include a piperidine ring, a morpholine ring, a pyrrolidine ring,
Mention may be made of the pyrrolidone ring.

The methine group represented by L+ and Lx 1Ls may have a substituent (eg, methyl, ethyl, cyano, phenyl, chlorine atom, sulfoethyl).

R3 and R4 are hydrogen atoms, halogen atoms (e.g. chlorine, bromine), alkyl groups (optionally substituted alkyl groups preferably having 5 or less carbon atoms, e.g. methyl, ethyl)
, alkoxy group (optionally substituted alkoxy group preferably having 5 or less carbon atoms, such as methoxy, ethoxy,
2-chloroethoxy), hydroxy group, carboxyl group, substituted amino group (e.g. acetylamino, methylamino, diethylamino, methanesulfonylamino), carbamoyl group (optionally substituted carbamoyl group, e.g. methylcarbamoyl), sulfamoyl represents a sulfamoyl group (which may be substituted, such as ethylsulfamoyl), an alkoxycarbonyl group (such as methoxycarbonyl), or a sulfo group.

Rs and R4 are a hydrogen atom or an alkyl group which may be substituted with an alkyl group, and preferably have 8 or less carbon atoms;
For example, methyl, ethyl, propyl, butyl, and substituents include sulfo group, carboxyl group, halogen atom, hydroxy group, cyano group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, acyloxy group,
Acylamino group, carbamoyl group, sulfamoyl group,
Examples include an alkylamino group, a dialkylamino group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonylamino group, a ureido group, and an aryl group. )
, an alkenyl group (an optionally substituted alkenyl group, for example, 3-hexenyl), an aryl group (a phenyl group is preferred as the aryl group, and even if it has the substituent described in the section of the aryl group in Q. R,
At least one of R has a sulfo group as a substituent.

In the above general formula (I), the sulfo group and the carboxyl group may be in free form or in salt form (e.g. Na salt, K salt, (CJs)).
3NH salt, pyridinium salt, ammonium salt).

In the above general formula (1), R is preferably an aryl group, a cyano group, or -COOH.

-COOR,, -〇〇NH,, -CONHR,,C0R
5,5OxRe 1-3ORe, -3O,NR,R,,
-OR, , (Rff, R1, and Rq are as defined above), and R8 represents a hydrogen atom or a methyl group, and Q represents a phenyl group or a substituted phenyl group [having 4 or less carbon atoms as a substituent] an alkyl group, an alkoxy group having up to 4 carbon atoms, a halogen atom (e.g. fluorine, chlorine, bromine), a dialkylamino group having up to 6 carbon atoms, and a hydroxyl group are preferred, and X is a bond or 10- or -NR
,. -(Rlo is as defined above.

). More preferably, m=1 and n-1 under the above conditions.

Next, specific examples of the compound represented by the general formula (1) used in the present invention are shown below, but the present invention is not limited thereto.

(Exemplary compound) 1゜ C.I.

dawn H2 SO, Na " CH3C)1 0 Ja 4゜ CH. CH2 CH. C.I.

" CH.

SO, Na 8゜ CH.

" o3K C1)゜ C1)□ 10° C8゜ ■ 1)゜ CH.

12° " CI(.

13° CH.

Shizuku 5O1Na 14° 15° CH.

The synthesis of the compound represented by the general formula (1) was disclosed in Japanese Unexamined Patent Publication No. 51
This can be easily carried out by condensing a pyrazolone ring with a henzaldehyde, as described in Japanese Patent Application Laid-open No. 59-3623, JP-A-59-21), 041, and the like. A specific synthesis example will be shown below.

Enter 1. (Just a person 1). ) l-(2-sulfobenzyl)-3-carboxypyrazolone monosodium salt 32.0 g (0,1+mol), 2-methyl-
4-(N-ethyl-N-(2-sulfoethyl)amino)
Henzaldehyde sodium salt 29.3g (0.1m
ol) was stirred in 250 mj of methanol, acetic acid 2- was added, and the mixture was heated under reflux for 1.5 hours. After removing dust and filtering,
Add a methanol solution of 12.3 g (0.15 mol) of sodium acetate, and add 600% of isopropyl alcohol.
When added, crystals precipitated. The crystals were collected by filtration and washed with isopropyl alcohol.

19.8 g (0.05 mol), 2-methyl-4 -(N-ethyl-N-(2-sulfoethyl)amino)benzaldehyde sodium salt 14.7 g (
0.05+*ol) was stirred in methanol 125-,
Acetic acid 1- was added and the mixture was heated under reflux for 1 hour. After filtering to remove dust, 300% of isopropyl alcohol was added to precipitate crystals. The crystals were collected by filtration and washed with isopropyl alcohol.

aX mO ε 5.08 X 10' ax Other exemplified compounds can also be easily synthesized by a similar method.

-i When using the dye represented by formula (1) as a filter dye, anti-irradiation dye or antihalation dye, any effective amount can be used;
It is preferable to use it 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 dyes according to the invention can be dispersed in emulsion layers and other hydrophilic colloid layers (interlayers, retention layers, antihalation layers, filter layers, 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 solvent and then using it in an emulsion layer or a hydrophilic colloid layer, an appropriate solvent, etc. Eva, methyl alcohol, ethyl alcohol, propyl alcohol, methyl alcoholf, JP-A-48-9715, U.S. Patent No. 3,75
It can also be added to the emulsion in the form of a solution dissolved in a halogenated alcohol, acetone, water, lysine, etc., or a mixed solvent thereof, as described in No. 6.830.

■ A method in which a hydrophilic polymer with a charge opposite to that of the dye ions is made to coexist in the layer as a mordant, and this interacts with the dye molecules to localize the dye in a specific layer.

The polymer mordant is a polymer containing a secondary and tertiary amino group, a polymer having a nitrogen-containing heterocyclic moiety, a polymer containing a quaternary cation group, etc., and a molecular weight of 5,000 or more, particularly preferably 10,000 or more. .

For example, vinylpyridine polymers and vinylpyridinium cationic polymers described in US Pat. No. 2,548.564 and the like; US Pat. No. 4. .

Vinylimidazolium cationic polymers disclosed in U.S. Pat. No. 124.386 and others; U.S. Pat.
Polymer mordant crosslinkable with gelatin etc. disclosed in US Pat. No. 3,958.995, JP-A No. 5
4-1) Aqueous sol type mordant disclosed in US Pat. No. 5228, etc.; water-insoluble mordant disclosed in US Pat. No. 3,898.088; US Pat. No. 4,168,97
Reactive mordants capable of forming covalent bonds with the dyes disclosed in Patent No. 6, etc.; derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues as described in British Patent No. 685.475 Polymers; products obtained by the reaction of polyvinyl alkyl ketones with aminoguanidine as described in British Patent No. 850.281; 2-methyl-1- as described in U.S. Pat. No. 3,445.231 Examples include polymers derived from vinylimidazole.

■ A method of dissolving a compound using a surfactant.

Useful surfactants may be oligomers or polymers.

For details of this polymer, please refer to JP-A-60-15843.
It is described on pages 19 to 27 of the specification of No. 7 (published by Fuji Photo Film, published on January 26, 1980, II).

Further, in the hydrophilic colloid dispersion obtained above, for example, hydrosyl, a lipophilic polymer described in Japanese Patent Publication No. 51-39835, may be added.

Gelatin is a typical hydrophilic colloid, but any other conventionally known colloid used 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 include those having a regular crystal shape such as a cubic ζ octahedron, and those having an irregular crystal shape such as a spherical shape and a plate shape.
gular), or polymerized forms of these crystal forms. It is also possible to use particles consisting of 1n combinations of particles of various crystal forms, but it is preferable to use regular crystal forms.

The silver halide emulsion used in the present invention may have different phases inside and on the surface, or may consist of a uniform phase. Also, particles whose latent image is mainly formed on the surface (
(e.g., a negative-tone emulsion) or a grain in which the latent image is formed mainly inside the grain (e.g., an internal latent image type emulsion, a pre-fogged direct reversal emulsion). Preferably, the latent image is mainly formed on the surface. Such particles are formed.

The silver halide emulsion used in the present invention has a thickness of 0.5
It is a tabular grain emulsion in which grains having a diameter of 0.6 microns or less, preferably 0.3 microns or less, and an average aspect ratio of 5 or more occupy 50% or more of the total projected area. Coefficient of variation above (value s/1 obtained by dividing the standard deviation S by the diameter J when the projected area is approximated as a circle)
A monodisperse emulsion in which the emulsion is 20% or less is preferred, and two or more types of tabular grain emulsions and monodisperse emulsions may be mixed.

The photographic emulsion used in the present invention is P.
, Glafkides), Chi+wie er Physique Photography Inc.
photographeque) (Ballmontel, 1967), G.F. Duffin (
Photography Ink Emulsion Chemistry (Photography, G.F., Duffin)
c E++ulsion Chemistry) (Focal Press, 1966), Making and Coating Photographic Ink Emulsion (V, L, Zelik+5an) et al.
photographic emulsion) (Focal Press, 1964).

Further, during the formation of silver halide grains, silver halide solvents such as ammonia rhodankali, rhodanammonium, and thioether compounds (for example, U.S. Pat. Nos. 3,271,157 and 3,574) are used as silver halide solvents to control grain growth. No. 628, No. 3,704.130, No. 4.297.439, No. 4,276.374, etc.), thione compounds (e.g., JP-A No. 144319/1983)
No. 53-82408, No. 55-77737, etc.), amine compounds (for example, JP-A-54-100717, etc.) can be used.

In the process of silver halide grain formation or physical ripening,
A cadmium salt, a zinc salt, a thallium salt, an iridium salt or a complex salt thereof, a rhodium salt or a complex salt thereof, an iron salt or an iron complex salt, etc. may be present together.

Silver halide emulsions are usually chemically sensitized.

For chemical sensitization, for example H, Friesel (H.

Fr1eser)! , Die Grundlagen der Fotografisien Prozesse Mituto Zilberhalogenden
rPhotographischen Prozeas
e sit Silberhalogeniden) (
Akademische Verlagsgesellschacht 1968
) The method described on pages 675 to 734 can be used.

That is, a sulfur sensitization method using a sulfur-containing compound that can react with active gelatin or silver (e.g., thiosulfate, thioureas, mercapto compounds, rhodanine); , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts,
A noble metal sensitization method using complex salts of metals of group 1 of the periodic table such as pt, Ir, and Pd 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, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. can. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; The above-mentioned heterocyclic mercapto compounds having a water-soluble group; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindene (particularly 4-hydroxy substituted (1°3.3a
+ "I) Tetraazaindenes); benzenethiosulfone e1)1)1; benzenesulfinic acid; and many other compounds known as antifoggants or stabilizers can be added.

The silver halide photographic emulsion of the present invention can contain color pigments such as cyan coupler, magenta coupler, yellow coupler, etc.
Couplers and compounds that disperse couplers can be included.

That is, it may contain a compound that can develop color by oxidative coupling with an aromatic primary amine developer (eg, phenylene diamine derivative, aminophenol derivative, etc.) in color development treatment. For example, magenta couplers include 5-virazolone couplers, virazolobenzimidazole couplers, cyano 7-cetyl coumaron couplers, virazolotriazole couplers, open-chain azilacetonitrile couplers, etc., and yellow couplers include acylacetamide couplers (e.g., henzoyl Examples of cyan couplers include naphthol couplers and phenol couplers.

These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either 4-equivalent or 2-equivalent to silver ions.

It may also be a colored coupler that has a color correction effect or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to the DIR coupler, the coupling reaction product may contain a colorless DIR camping compound which is colorless and releases a development inhibitor.

For the purpose of increasing sensitivity, increasing contrast, or accelerating development, the photographic emulsion of the present invention contains, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, naoether compounds, thiomorpholines, quaternary ammonium salt compounds, and urethane. It may also include derivatives, urea derivatives, imidazole derivatives, 3-virazolidones, and the like.

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

The photographic emulsion of the present invention may contain various surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, accelerating development, increasing contrast, and sensitizing). But that's fine.

Further, regarding the photosensitive material of the present invention, anti-fading agents, hardening agents, anti-color fogging agents, ultraviolet absorbers, protective colloids such as gelatin, and various additives, specifically, Research Disclosure Vol. l 7 6 (1978, XI
) RD-17643, etc.

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

The halogenated photosensitive materials of the present invention include color positive films, color papers, color negative films, color reversals (which may or may not contain couplers), photosensitive materials for plate making (for example, lithium film, lithium (denip film, etc.), photosensitive materials for cathode ray tube displays (e.g., photosensitive materials for emulsion X-ray recording, materials for direct and indirect photography using screens), silver salt diffusion transfer process (e.g.
photosensitive material for color diffusion transfer process, photosensitive material for color diffusion transfer process, imbibition transfer pr
photosensitive material used in silver dye bleaching method, photosensitive material for recording printout images. Examples include optical materials, photodevelopable direct print image photoreceptive materials, photosensitive materials for thermal development, photoreceptive materials for physical development, and the like.

Exposure to obtain a photographic image may be carried out using a conventional method. That is, any of a wide variety of known light sources can be used, such as natural light (sunlight), tungsten electric lamps, fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, and shadow-wound tube flying spots. The exposure time is usually 1/1000 second to 30 seconds, but exposure shorter than 1/1000 second, for example, 1/10' to 1/10' second exposure using a xenon flash lamp or cathode ray tube may be used. or exposures longer than 30 seconds can be used. If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. Also, electron beams, X-rays,
Exposure may be performed by light emitted from a phosphor excited by gamma rays, alpha rays, or the like.

Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Disclosure) No. 176, pp. 28-30 (
RD-17643), any of the known methods and known treatment liquids 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 processing temperature is usually chosen between 18 and 50°C, but 18°C
Lower temperatures or temperatures above 50°C may also be used.

(Effects of the Invention) According to the present invention, a silver halide photographic material having a wood-philic colloid layer containing a novel water-soluble dye that has appropriate spectral absorption and does not adversely affect photographic properties is obtained. be able to.

Further, 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 is decolorized during photographic processing.

Further, according to the present invention, a silver halide photographic material having excellent stability over time can be obtained.

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

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

The temperature of the gelatin aqueous solution was controlled to be maintained at 40°C. After particle formation, the temperature was lowered to 30° C. and soluble salts were removed by the flocculagecon method well known in the art. After that, 40g of gelatin was added without chemical ripening, and 4-hydroxy-6-methyl-1,3 was added as a stabilizer.
.

In this way, a monodisperse silver chlorobromide emulsion with an average grain size of 0.18 μm was prepared. The yield of the resulting emulsion was 950 g.

Divide the emulsion into 100 g portions and add 0.2 g of the dye compounds shown in Table I (the amount added in the light-sensitive material is 53 μ/d).
and 0.4 g (the amount added in the light-sensitive material is 10 6 /i). Furthermore, 1.5 g of the latex described in the manufacturer's prescription 3 of U.S. Patent No. 3,525,620 was added as a polymer latex, 0.4 g of saponin was added as a surfactant, and 1.3-divinylsulfonyl-2- was used as a hardening agent. 150c each with 0.3g of Propatool added
The finished amount was prepared as c.

The emulsion thus prepared was coated on a polyethylene terephthalate transparent support (thickness: 100 μm) so that the amount of tofu was 40 cc per coat, and then 1.2 g of gelatin per coat was added as a protective layer on top. A protective layer consisting of the following was coated to prepare photosensitive materials of sample numbers +1) to (9). The amount of silver in each sample was 3.0 g per rrt.

After coating, each sample from fil to (9) was stored over time under the temperature and humidity conditions of After exposure with a halogen lamp), an automatic processor manufactured by Fuji Photo Film Co., Ltd.
Development was performed at -680A at 38°C for 20 seconds. The developer used was GR-DI developer manufactured by Fuji Photo Film Co., Ltd., and the same GR-Fl developer was used as the fixer.

Temperature storage conditions (A) Temperature 25°C, humidity 60%, 3 days (B) Temperature 50°C, humidity 70%, 3 days
) Samples stored under each condition were treated with a Toshiba anti-fade fluorescent light (
FLR40SW-DL-X NU/M) 200 l
After being left for 0 to 40 minutes under the brightness of UX, development was performed under the same conditions as in the photographic performance evaluation described above to evaluate safelight safety.

Measure the density of each developed sample, calculate the relative sensitivity of each sample by finding the relative value of the exposure amount that gives a density of 1.5,
In the safelight irradiation test, the fog density was 0.02.
The longer the irradiation time, the higher the safelight safety.

Also, visually observe the color of the unexposed area and check the remaining color level at A.
Evaluation was made on a five-point scale of -E. A has almost no residual color, B
In C, the residual color was at the permissible limit level, and in D and E, the residual color was quite noticeable and was outside the permissible level.

The above evaluation results are shown in Table-1.

In addition, the following compounds were used as comparative compounds (a) and d) in Table-1.

Exemplary compound (a) CH2 SO, Na Exemplary compound (b) ■ CH! The light-sensitive material of sample number (21 (31 + 41 + 51) according to the present invention is compared with the light-sensitive material of (81 (91) of the comparative example.
It has excellent performance in terms of sensitivity, safelight safety, and residual color, and is superior in terms of residual color in the sample under storage conditions (B) compared to the photosensitive material of Comparative Example 71. You can see that

Patent applicant: Fuji Photo Film Co., Ltd. Date of March 17, 1961

Claims (2)

[Claims] (1) A silver halide photographic material containing at least one dye compound represented by the following general formula (I). General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the formula, R_1 is an aryl group, a cyano group, -COOH, -COOR_7, -CONH_2, -CO
NHR_7, -CONR_7R_8, -COR_8, -
SO_2R_8, -SOR_8, -SO_2NR_8R
_9, -OR_7, -NHCOR_7, -NR_8CO
R_7, -NHCONHR_7, -NR_8CONHR
_7, -NHCONR_7R_8, -NR_8SO_2
R_9, -NHSO_2R_8, -NHR_7, or -
NR_7R_8 (here, 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 may be linked to form a 5- to 6-membered ring), and R_2 is hydrogen. Represents an 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, L_1, L_2, L_3 each represent a methine group, n is 0 or 1, m is 1 or 2, p is 0, 1, 2, 3
or 4, q represents 1, 2 or 3; R_3 and R_4 may be the same or different and represent 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 represent 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 has a sulfo group as a substituent. (2) General formula (I) described in claim (1)
In, R_1 is an aryl group, a cyano group, -COOH
, -COOR_7, -CONH_2, -CONHR_
7, -COR_8, -SO_2R_8, -SOR_8,
A silver halide photographic material containing at least one dye compound of -SO_2NR_8R_9 and -OR_7.