JPH01191136A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To realize the silver halide photographic sensitive material having a suitable spectral absorption and a dyed hydrophilic colloidal layer which has not harmful effect upon photographic characteristics by incorporating a specified oxonol dyestuff and a specified allylidene dyestuff together with each other in the sensitive material in a prescribed ratio. CONSTITUTION:At least one kind of a dyestuff compd. shown by formula I and at least one kind of a dyestuff compd. shown by formula II are incorporated in the sensitive material. In formula I, R1 and R2 are each alkyl or aryl group, etc., R3 and R4 are each hydrogen atom or alkyl group, Q1 and Q2 are each aryl group, X1 and X2 are each boning or a divalent linking group, L1, L2 and L3 are each methine group, (n) is 0, 1 or 2, (m1) and (m2) are each 1 or 2, (p1) and (p2) are each 0, 1, 2, 3 or 4, (q1) and (q2) are each 1, 2 or 3. In formula II, X and Y are each an electron attractive group, R11 and R12 are each hydrogen or halogen atom or alkyl group, etc., R13 and R14 are each hydrogen atom or alkyl group, etc., L11, L12 and L13 are each methine group, (k) is 0 or 1. Thus, the silver halide photographic sensitive material which has not the harmful effect upon the photographic characteristics is realized.

Description

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

(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. Such a colored layer is called an antihalation layer. In the case of multilayer color photosensitive materials,
An antihalation layer may be placed between each layer.

Image sharpness decreases due to scattering of p-light in the photographic emulsion layer (this phenomenon is generally called irradiation)
Coloring of the photographic emulsion layer is also used to prevent T-.

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

(1) Must have appropriate spectral absorption according to the purpose of use.

(2) Photochemically inert. In other words, it has an adverse effect on the performance of the silver halide photographic emulsion layer in a chemical sense.
For example, it should not cause low sensitivity, latent image regression, or fog.

(3) No harmful coloration remains 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 dyes listed below are known. For example, British Patent No. 506585, 1.177
．． No. 429, 1,311. ．． No. 884, 1.53 &
No. 799, No. 1.38 No. 371, No. 1.467.2
No. 14, No. 1.45A102, No. 1゜55A516, No. 130 to JP-A-48-8, No. 49-114.42Q
No. 55-161,253, No. 59-111,64
No. 0, U.S. Patent No. A 247.127, &469
．． No. 985, U.S. Pat. No. 4,078,955, etc., oquinol dyes having a pyrazolone nucleus or barbylic acid nucleus;
No. 53, other oquinol dyes described in British Patent No. 1゜27a621, etc., British Patent No. 575,691
No. 680゜631, No. 599.623, No. 7B
&9G7 No. 907.125, No. 1,04 609
No. 4.25, U.S. Patent No. 4.25-326, JP-A-59-21
Azo dyes described in No. 1.045 etc., JP-A-1983-1
Azomethine dyes described in British Patent No. 0111.116, British Patent No. 54-11 A247, British Patent No. 2,014,598, British Patent No. 750,031, etc., U.S. Patent No. 2.865.7
Anthraquinone dyes described in US Pat. No. 52, U.S. Pat.
．． 53a009, 2.68 & 541, 253
&008, British Patent No. 584.609, 1.21
CL252, JP-A-50-4 No. 625, JP-A No. 51-!
No. 11623, No. 51-1 No. 927, No. 54-11
& No. 247, Special Publication No. 1986-5286, No. 59-37:
No. 303, No. 62-10 & No. 455, No. 62-1544
Ally J7 den dye described in No. 55 etc., Special Publication No. 1973
-AO No. 82, No. 44-16.594, No. 59-21
Styryl dye described in L898 etc., British patent m4
No. 46.585, No. 1.35 422, JP-A-59-
22 & 250 etc., British Patent Nos. 1.075.655 and 1.15434.
Merocyanine dyes described in U.S. Pat. No. 1, U.S. Pat. No. 1, 284.750, U.S. Pat.
Examples include cyanine dyes described in No. 9 and the like.

Among these, arylideso dye has the property of being decolorized in a developer containing tetrasulfite, and is used as a useful dye for dyeing photographic materials as it has little adverse effect on photographic emulsions.

Oquinol dye, which has two pyrazolone nuclei, also has the property of being decolorized in developing solutions containing sulfites, and has been used as a useful dye for dyeing photographic materials as it has little negative effect on photographic emulsions. .

For example, pyrazolone having a sulfoaryl grave at the 1st position is Japanese Patent Publication No. 39-22069, No. 51-46607, No. 55-10061, No. 60-55304, No. 5
1-1419 etc., pyrazolone having a sulfoalkyl group at the 1st position is disclosed in JP-A-9-996.
No. 20, Japanese Patent Publication No. 55-10059, etc. However, although dyes belonging to these families have little effect on the photographic emulsion itself, they have a negative effect on the spectrally sensitized emulsion.
It has the disadvantage of causing a decrease in sensitivity, which is thought to be due to spectrally sensitized areas or the desorption of sensitizing dyes in unnecessary areas.

Furthermore, due to the speeding up of development processing that has become popular in recent years, some residual particles may remain after processing. 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 degree of oxidation decreases over time. However, it has the disadvantage that the desired photographic effect cannot be obtained.

On the other hand, those having a sulfoaralkyl group at the 1st position of the pyrazolone and a specific substituent at the 3rd position of the pyrazolone are disclosed in JP-A-5O-t45125, JP-A-50-147712,
Although it is described in No. 52-20830, etc., it had a similar drawback that the decolorizing performance was somewhat insufficient.

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

A second object of the present invention is to provide a silver halide photographic material in which a hydrophilic colloid layer is dyed with a water-soluble dye having excellent decolorization 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 water-soluble dye that is stable over time.

A fourth object of the present invention is to provide a silver halide photographic material that has excellent filter effects, antihalation effects, or sensitivity adjustment effects of light-sensitive emulsions by using dyes with different basic skeletons in combination. be.

(Means for Solving the Problems) The objects of the present invention are to contain at least one dye compound represented by general formula (1), and to contain at least one dye compound represented by general formula (1). This was achieved using a halogenated photographic material containing seeds.

General formula (1) General formula (II) In general formula (1), R1 and R are each an alkyl group.

Aryl group, cyan group, -QOOR@t -0O
NRgR4t-C! OR,, -8o, R,, -13OR
,,-80,NR,R,.

-0kN, , -NR,R,, -NR@OOR,,
-NRI○OMR, bird or -N R6S O,R, (where R1t Rs is a hydrogen atom.

represents an alkyl group or an aryl group, R1 represents an alkyl group or an aryl group, R1 and R6 or R1 and R, I
Ii, they may be connected to form a 5- to 6-membered ring. ), and tR, u, and ri each represent a hydrogen atom or an alkyl group. Q+ -Qt each represent a Ryl group.

X...! , represents a bond or Fi, a divalent linking group.

Yl and Y each represent a sulfo group or a carboxyl group, and #''l #IJ and lIJS each represent a methine group.

n is 0.1 or 2. m,, town is 1 or 2e ptpp,
is 0, 1, 2, 3 or 'tqtp (it is 1, 2 or #:
l: represents 3.

In the general formula (■), X and Y may be the same or different, represent an electron-withdrawing group, and X and Y may be connected to form a term.

R11, R1, rj or may be different, and is represented as a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, a hydroxy group, a carboxyl group, a substituted amine group, a carbamoyl group, a sulfamoyl group, an alkoxycarbonyl group, or a sulfo group.

Ro and Rla 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 RIM and RIM may be connected to form a 5- to 6-membered mound. .

Also, R11 and Rla % R1! and Rt4 may be respectively connected to form a 5- to 6-membered oak.

At least one of the above X%"1%RH%R11, Fttm, and 1Rta has a sulfo group or a carboxyl group as a substituent.

"11, LL11'L1. each represents a methine group.k
represents 0 or 1.

Next, the dye represented by general formula (1) will be explained in detail.

Rle Rt e Re * The alkyl group represented by Re and R1 includes an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, n-propyl, inglovir, n
-butyl, inbutyl, t-butyl, n-amyl, n-
hexyl, n-octyl, inamyl), and substituents [e.g. fluorine, chlorine.

Halogen atoms such as 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 amine group (
For example, dimethylamino, diethylamino)].

The alkyl group represented by R,, R, is an alkyl group having 4 or less carbon atoms (for example, methyl, ethyl, etc.).

n-propyl) is preferred.

The aryl group represented by Rla R1p Re # Re and R1 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, or a hydroxyl group.

Cyano group, alkyl group having 1 to 4 carbon atoms (e.g. methyl,
ethyl, n-7'lopyl), alkoxy groups (eg, methoxy, ethoxy), oryloxy groups (eg, phenoxy).

The aryl group represented by Qx-Qt is preferably a phenyl group or a 7-tyl group, and a substituent other than a sulfo group or a carboxyl group [for example, a C1-C4(2) furkyl group (
methyl, ethyl), alkoxy groups (e.g. methoxy, ethoxy, halogen atoms (e.g. fluorine, chlorine, bromine), carbamoyl 111, t hamethylcarbamoyl,
ethylcarbamoyl), sulfamoyl 114. t-ethylsulfamoyl), cyano group, nitro group, alkylsulfonyl group 11J, tba#Isulfonyl)arylsulfonyl group (N, t-benzenesulfonyl), amine group (e.g. dimethylamino, diethylamino), acylamino group (for example, acetylamino), a sulfonamide group (for example, methanesulfonamide), or a hydroxyl group].

! , ,X, are examples of divalent linking groups such as -○-, -11R@-e -NR@00-e -
BOI-t-NR,BO,- can be mentioned,
R is a hydrogen atom.

Alkyl groups having 5 or less carbon atoms (e.g. methyl, ethyl, n
-propyl, n-butyl, n-amyl, inbutyl) or a substituted alkyl group with 5 or less carbon atoms [Substituted groups include alkoxy groups with 5 or less carbon atoms (e.g. methoxy, ethoxy), sulfo group, carboxyl group, cyan group , hydroxyl group, amino group (e.g. dimethylamino, diethylamino), carbamoyl group (e.g. hydroxyethylaminocarbonyl, ethylaminocarbonyl) or sulfamoyl group (
91 e.g. ethylaminosulfonyl)]e[was.

The 5- or 6-membered ring formed by connecting R, and Ro or R6 and R1 includes, for example, a piperidine ring, 2 morpholine rings,
Examples include a pyrrolidine term and a pyrrolidone ring.

The methine group represented by Ls s ′Lt e ”h is a substituent (eg, methyl, ethyl, cyan, phenyl.

chlorine atom, sulfoethyl).

In the above general formula (2), the sulfo group, carboxyl group, and enol moiety of the hipyrazolone term may be in the free form or in the salt form (eg, Na salt, Ni salt, (○, H,), NII salt.

pyridinium salt, ammonium salt).

In the above general formula (1), preferable ones are R1゜R6
represents a hydrogen atom or a methyl group, and Ql e Qt represents a phenyl group or a substituted phenyl group [with 4 carbon atoms as a substituent]
The following alkyl groups, alkoxy groups having 4 or less carbon atoms, halogen atoms (e.g. fluorine, chlorine).

bromine), a dialkylamino group having 6 or less carbon atoms, and a hydroxyl group. ]&: N me, X, , ! , can be a bond or 10- or -hx, - (where Rs is defined above). ). Preferably, m = mt = 1 under the above conditions,
Particularly preferred <DII'im, = m, = 1, 6C, and R3゜R3 is an alkyl group, an aryl group, or a cyano group.

-GOOR,, -0011R,R@, -〇〇current,
-80,R,.

-80, M R, R@ or -NRa80tRy (
Rs # Els * R? is defined above. ).

Next, the dye represented by the general formula (■) will be explained in detail.

The electron-withdrawing group represented by X and Y includes a cyan group,
carboxyl group, alkylcarbonyl group [preferably 7 or less carbon atoms, for example acetyl, globionyl, which may have a substituent (e.g. halogen atom such as chlorine)], arylcarbonyl group [aryl group includes phenyl The group is preferably a naphthyl group, and may have a substituent. Substituents include sulfo group, carboxyl group,
Hydroxy group, halogen atom (e.g. chlorine, bromine),
Cyano group, alkyl group (for example, methyl, ethyl), alkoxy group (for example, fP4, ethoxy, ethoxy), carbamoyl group (IHJ, t, methylcarbamoyl), sulfamoyl group (for example, ethylsulfamoyl), nitro group, alkyl Sulfonyl group (e.g. methanesulfonyl)
, arylsulfonyl group (e.g. benzenesulfonyl)
, amino groups (e.g. dimethylamino), acylamino groups (e.g. acetylamino, trichloroacetylamine)
, sulfonamide group (e.g. methanesulfonamide)], alkoxycarbonyl group (
an optionally substituted alkoxycarbonyl group,
The number of carbon atoms is preferably 7 or less, for example, ethoxycarbonyl, methoxyethoxycarbonyl), aryloxycarbonyl group (the aryl group is preferably a phenyl group or a naphthyl group, and has a substituent as explained in the section of the arylcarbonyl group). carbamoyl group (optionally substituted carbamoyl group, preferably 7 or less carbon atoms, mJ, t, methylcarbamoyl, phenylcarbamoyl, 3-sulfophenylcarbamoyl),
Alkylsulfonyl group (F-substituted and fast alkylsulfonyl group, such as methanesulfonyl), arylsulfonyl group (optionally substituted -lsulfonyl group, examples include phenylsulfonyl group) to)
, To! with a sulfamoyl group which may be ct-substituted with a sulfamoyl group. ri, IQeha, methylsulfamoyl,
4-chlorophenylsulfamoyl).

In addition, if X and Y are connected, a pyrazolone ring,
A pyrazolotriazole ring, an oxindole ring, an inoxacilone ring, a barbylic acid ring, a thiobarbyl ring, or an indandione 3Jl) may be formed. A preferable ring is a pyrazolone ring, and the ring shown below is a monochrome ring (
III).

- Pattern hole (2) In general formula (11), Rto, R@, Qm, X
,,Yl,p,,q,respectively, -R at the hole (1), ,RQt,"t, Yl% Ps, qt
omm, which is synonymous with , represents 0.1 or ri2.

R□, horse! is a hydrogen atom, a halogen atom (for example, chlorine, bromine), an alkyl group (an optionally substituted alkyl group, preferably having 5 or less carbon atoms, such as 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 amine group (e.g. acetylamino, methylamino, diethylamino, methanesulfonylamine), carbamoyl group (optionally substituted carbamoyl group, e.g. methylcarbamoyl), Examples include sulfamoyl groups (optionally substituted sulfamoyl groups, such as ethylsulfamoyl), alkoxycarbonyl groups (such as methoxycarbonyl), and sulfo groups.

R11, R is a hydrogen atom, an alkyl group (an alkyl group that may be substituted, preferably having 8 or less carbon atoms,
Examples are methyl, ethyl, propyl, and butyl, and examples of substituents include sulfo group, carboxyl group, halogen atom, hydroxy group, cyan group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, acyloxy group,
Acylamide 7 groups, 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 aryol group.

), alkenyl group (3-hexenyl as an optionally substituted alkenyl group), aryl group (7enyl group is preferable as the aryl group, as described in the section of the arylcarbonyl group of x%Y) ), acyl group (acetyl, benzoyl), sulfonyl group (%J
, tb, )l sulfonyl, phenylsulfonyl), and may form a 5- to 6-membered heterocycle (eg, piperidine ring, morpholine ring, etc.) with Itis%R14.

Furthermore, R□ and Rlj, and R□ and R4 may be linked to each other to form a 5- to 6-membered heterocycle.

The above X! , "11', R1!%its, R14 has a sulfo group or a carboxyl group. Sulfo groups and carboxyl groups can be used in free form or in salt form (e.g. Na salt, K salt e (a !nJ@mH salt, pyridinium salt, ammonium salt).

The methine group represented by "Jtt t Ilt* e" 1M is a substituent (IFII, thamether, ethyl, cyano, phenyl.

chlorine atom, sulfoethyl).

k#'i represents 0 or 1.

Specific examples of the compounds represented by the general formula (1) and -Momona (1) used in the present invention are shown below, but the present invention is not limited thereto.

! -1 801M5L #3o, na ! -5 Summer-9 ni-10 l-12 ■-14 Lid-15 ! -16 1-170H.

■ 80BNa 5osNa! −
18 80, Na 80. Na801Na
80. Na1-220H.

! -23 80, Ma E? O,Na 803Ma 501Na! -25 do, K 80. K SO, Ma 8031Ja Summer-29 0C! H, OOH.

80, lJa 5olsaI-52 ! -33 ! -54 1-560H.

80BIA a 803N a8
0, Na 801Nal-42 C1ll.

! -45 801Na Sun 01Ma80, N
a801Na! -48! -50! -51 ■-52! -53 I-54 00 horses OH! 80. K OCR, OH
, So, 1-56 OH.

■-58 80, K 80. K1-(S.

■-2 U It-<S S　OjN　a ■-8 ■-10 (CEri.

80, N a (OH,).

So, to ■-12 It-13 B　O＠　M　a ■-14 on.

130, K l-15 80, K 301Na 80. K t-18 001(,0H180,K ...-20 011,01111801Na Uho 3 -2S .

80, the dye represented by the pattern hole (1) is disclosed in JP-A-50-1451.
No. 25, No. 50-147712, No. 59-11164
No. 0, No. 62-275527, Patent Application No. 62-7948
No. 3, No. 62-110515, or can be synthesized by a similar method.

The dye represented by the general formula (I) is disclosed in JP-A-51-562.
It can be easily synthesized by the method described in No. 3, etc.

Dye #4t of general formulas (1) and (...) - When used as a filter dye, anti-irradiation dye or antihalation dye, any effective amount can be used, but the optical IIk degree is 105 It is preferable to use it within a range of 50 to 50. 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, protective layers, antihalation layers, filter layers, etc.) by various known methods.

(2) A method in which the dye of the present invention is directly dissolved or dispersed in an emulsion layer or a hydrophilic colloid layer, or a method in which an aqueous solution is dissolved or dispersed in a solvent and then used in an emulsion layer or a hydrophilic colloid layer. Suitable solvents, N, t, ethyl alcohol, ethyl alcohol, flobyl alcohol, Metersernluff, JP-A-48-9715, U.S. Pat. No. 475
4830, halogenated alcohol, acetone,
It can also be added to the emulsion in the form of a solution dissolved in water, pyridine, etc. or a mixed solvent thereof.

■ 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, vinyl pyridine polymers and vinyl pyridinium cation polymers disclosed in U.S. Pat. No. 2,548,564, etc.; vinyl imidazolium cationic polymers disclosed in U.S. Pat. Polymer mordants capable of crosslinking with gelatin etc. disclosed in US Pat. No. 694, etc.; US Pat. No. 4
95 is also an aqueous sol-type mordant disclosed in No. 995, JP-A-54-115228, etc.; U.S. Patent No. 4891
A water-insoluble mordant disclosed in No. 11,088 Mei J4HFK; a reactive mordant capable of forming a covalent bond with the dye disclosed in U.S. Pat. Polymers derived from ethylenically unsaturated compounds having dialkylaminoalkyl ester residues such as; products obtained by reaction of polyvinyl alkyl ketones with aminoguanidine as described in British Patent No. 85 (L281); U.S. Pat. No. 4,445,231 Examples include polymers derived from 2-methyl-1-vinylimidazole as described in No.

■ A method of dissolving a compound using a surfactant.

Useful surfactants may also be oligomers or polymers.

For details of this polymer, please refer to Japanese Patent Application Laid-Open No. 1584/1960.
No. 57 (Fuji Photo Film, January 26, 1981)
No. 1, filed on page 19 to 27 of the specification.

Furthermore, hydrosil, a lipophilic polymer described in Japanese Patent Publication No. 51-39ASS, for example, may be added to the hydrophilic colloid dispersion obtained above.

Gelatin is a typical hydrophilic colloid, but any other conventionally known hydrophilic colloids that can be 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 regular crystal shapes such as cubic and octahedral, and those having irregular crystal shapes such as spherical and plate shapes.
gular) or a compound of these crystal forms. It is also possible to use a mixture of particles of various crystal forms, but it is preferable to use regular crystal forms.

The silver halide grains used in the present invention may have different phases inside and on the surface, or may have a uniform phase. Also, particles whose latent image is mainly formed on the surface (
For example, the emulsion may be a negative type emulsion), or it may be a grain mainly formed inside the grain (for example, an internal layer image type emulsion, a direct reversal emulsion that has been fogged in advance). Preferably 1,
These are particles on which a latent image is formed primarily on the surface.

The silver halide emulsion used in the present invention has a thickness of (15
microns or less, preferably [L3 microns or less in diameter, preferably d (16 microns or more, and a tabular grain emulsion in which grains with an average aspect ratio of 5 or more account for more than SOS of the total projected area, or statistically A monodisperse emulsion is preferred, which is the variation coefficient (the standard when the projected area is approximated as a circle).Furthermore, a tabular grain emulsion and a monodisperse emulsion of t-2 or more may be mixed.

The photographic emulsion used in the present invention is P.
, Glafkides), Chimia er Phys Photographic (Chimia er Phys Photographic)
(Photographeque) (Ballmontel, 1967), Photographic Emulsion Chemistry (Photograp), by G. Duffin (Ballmontel, 1967)
hic Emulsion Ohemiatry) (
Focal Press, 1966), V. L. Zelikman et al.
Making and Coating Photographic-Emma 7tz:! y (Making and
CoatingPhoto-graphic Iimu
Laion) (Focal Press, 1964).

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (U.S. Pat. No. 5,271,157, No.
．． No. 574.628, No. A704,130, No. 4 @4
, No. 297,439, No. 4.276.574, etc.)
, thione compounds (for example, JP-A-55-144519,
53-82408, 55-77737, etc.),
Amine compounds (for example, JP-A No. 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, line H, 7! J-Zel (Ii.

Die Grundlagen der Fotografisien Prozesse Mituto Zilpe At/' Clgendy (Die Grundl)
agen derPhotographiachen
Prowesss mit 811berhaloge
The method described in Akademissie Verlags Gesellschacht 19(58) pp. 675-734 can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanines); , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts,
A noble metal sensitization method using PT, PT, P (complex salts of metals of group 1 of the periodic table such as L) can be used alone or in combination.

The silver halide photographic emulsion used in the present invention contains various compounds for the purpose of preventing fog during the manufacturing process of the light-sensitive material, during storage, or during photographic processing, or to stabilize photographic performance. be able to. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted);
Heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, mesicabutobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptovirimidines; carboxyl groups and sulfones the above-mentioned heteromercaguto compounds having a water-soluble group such as a
, 7) tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; anti-capri agents and stabilizers, and many other compounds can be added thereto.

The silver halide photographic emulsion lines of the present invention include color rays such as cyan coupler, magenta coupler, yellow coupler, etc.
It can include a coupler and a compound that disperses the coupler.

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-pyrazolone couplers, birazolopenzimidazole couplers, cyanoacetylcoumarone couplers, pyrazolotriazole couplers, open-chain acylacetonitrile couplers, etc., and yellow couplers include:
Acylacetamide couplers (e.g. benzoylacetanilides, piparoylacetanilides) etc. are 6J)
Examples of cyan couplers include naphthol couplers and phenol couplers.

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

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 include a colorless DIR coupling 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 may contain, for example, polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium salt compounds, and urethane derivatives. , urea derivatives, imidazole derivatives, 5-pyrazolidones, and the like.

The silver halide photographic emulsion of the present invention contains known water-soluble dyes other than the dyes disclosed in the present invention (9.
For example, it may be used in combination with benzylidene dyes, oquinol dyes; hemioquinol dyes 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 contains various surfactants for various purposes such as coating aids, antistatic properties, improving slipperiness, dispersing emulsions, preventing adhesion, and improving photographic properties (for example, to accelerate development, increase contrast, and sensitize). May include.

In addition, the photosensitive material of the present invention contains antifading agents, hardening agents, antifogging agents, ultraviolet absorbers, protective colloids such as gelatin, and various additives. 197B,Xl)RD
-17645 etc.

The finished emulsion is prepared on a suitable support,
For example, baryta paper, resin-coated paper, synthetic paper, triacetate film, polyethylene terephthalate film, and other plastic-based materials are coated onto glass plates.

Examples of the silver halide photographic material of the present invention include color positive film, paper, color negative film, color reversal film (which may or may not contain a coupler), photographic material for plate making (for example, lithium film, Lisdenip film, etc.), photosensitive materials for cathode ray tube displays (e.g. 91 emulsion xyli recording photosensitive materials, materials for direct and indirect photography using screens), silver salt diffusion transfer process (811ver 8alt diffusion)
transf@r Proc@ss) photosensitive materials,
Photosensitive materials for color diffusion transfer process, die transfer process (imbibition transfer process)
photosensitive materials for use in silver dye bleaching methods, photosensitive materials for recording printout images, photodevelopment type printing materials
(age) photosensitive materials, photosensitive materials for thermal development, photosensitive materials for physical development, etc.

Exposure to obtain a photographic image may be carried out using a conventional method. i.e. natural light (sunlight), tungsten electric light,
Any of a variety of known light sources can be used, such as fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, and cathode ray tube flying spots. The exposure time is usually 171,000 seconds to 30 seconds, but exposures shorter than 1/1000 seconds, such as 1/10' to 1/10' seconds exposure using a xenon flash lamp or cathode ray tube, may also be used. Yes, 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 beam, Xm
, r-rays, α-rays, etc., and emitted from a phosphor.

For photographic processing of light-sensitive materials made using the present invention, for example, Research Disclosure (Re5earch)
Any of the known methods and known treatment liquids, such as those described in Disclosure No. 176, pages 28-30 (RD-17645), 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 18
The temperature may be lower than 50°C or higher than 50°C.

(Effects of the Invention) According to the present invention, appropriate spectral absorption can be achieved by using a novel oquinol dye represented by the general formula (1) and an arylidene dye represented by the general formula (ff) in an arbitrary ratio. It is possible to obtain a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer that does not have a detrimental effect on photographic properties.

Furthermore, 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.

(Implementation row) Next, the present invention will be explained in more detail based on examples of implementation.

Example 1 [Preparation of emulsion] A mixed aqueous solution of potassium iodide and potassium bromide, 1 kt of an aqueous solution of silver nitrate, and an aqueous gelatin solution containing 8-dihydroxy-46-cythiaoctane were vigorously stirred, and 1 kt was added at 75°C.
It was added while controlling the PAg to be 17 for 5 minutes, containing 6 mol of silver iodide, and having an average grain size (L28μ).
Monodispersed cubic silver iodobromide was obtained. Using this silver iodobromide emulsion as a core, the PA of the solution was
While controlling so that g is 7.4,
A potassium bromide aqueous solution containing 04 and (liBa)mRh04 and a silver nitrate aqueous solution were added, and finally, K,
Engineering rC1゜ and (nu, ), Rha4 is silver halide 1
The average particle size containing 10-7 moles each is (
A monodisperse cubic core/shell silver iodobromide emulsion (average silver iodide content t5 molar) with L45μ was obtained. After washing with water and desalting, sodium thiosulfate in an amount of b5q per mole of silver and 4 molar amounts of chloroauric acid were added to the emulsion, heated at 65°C for 70 minutes, and chemically sensitized, and 4-hydroxy- 6 methyl-1.45a, 1% solution of 7-chitrazaindene 1 to 3
0 mg was added.

The above emulsion was added with 45'-di(3-sulfopropyl)-4s'-cyclo9ethyltheacarbocyanine sodium salt and Is'-di(3-sulfopropyl)-9ethylna7) as a spectral sensitizing dye. , 2-d] Sodium thiacarbocyanine was added to each mole of silver halide, and the general formula [l] was obtained.

A compound belonging to CID and a compound represented by [mu] as a comparative compound were added in the types and amounts shown in Table 1. In addition, 1-phenyl-5-mercagutotetrazole was added as an antifoggant at 50 capes per mole of silver, and as a plasticizer, polyethyl acrylate latex was added at 1 F per mole of silver.
60 q of 2-bis(vinylsulfonylacetamido)ethane (per mole of silver) was added as a hardening agent, and the above emulsion was coated on a subbed polyethylene terephthalate support at a silver density of 4.5 f/m. and 4.7 tons of gelatin.
/W13 together with a protective layer.

The sample thus obtained was wedge-exposed with light emitting diode light having an emission maximum at 660 n1EI, and a developer-1 having the following composition and a fixer for 7Gillis automatic processor - IF-308 were used as a fixer. (manufactured by Fuji Photo Film Co., Ltd.) using Fuji Seihan/Print Grocer PG-360.
30 at 35℃ on 1F (manufactured by Fuji Photo Film Co., Ltd.)
It was developed for seconds, fixed, washed with water, dried, and evaluated for sensitivity and color staining after processing. In addition, an unexposed sample of light emitting diode light was placed 1 m below the green safelight of a 20W light bulb (Fuji Safelight Filter-4, manufactured by Fuji Photo Film Co., Ltd.).
The film was developed as described above after being left at a distance of 0 seconds and 3 minutes, and the Capri density was measured. Table 1 shows the results of the evaluation of sensitivity, color contamination, and safelight safety as described above.

(Developer - 1 formulation) Water 720-
Ethylenediaminetetraacetic acid disodium salt 4f Sodium hydroxide 441 Sulfite
45f carbonated soda
2&4f boric acid
t6 is potassium bromide 1t hydroquinone 569 diethylene glycol 3995-methyl-benzotriazole α2t bilazo ν
Add α7 to water
1 is shown in Table 1. Compared with Samples-2dk1 and -5 containing the compound 1-4 of the present invention alone, safelight safety was achieved without loss of sensitivity to a light emitting diode light source having a maximum at 660 nm. It can be seen that the processing rate is improved and the color staining of the processing degree is also very small.

Furthermore, sample-4, which is a combination of compound 1-4 of the present invention and ll-7, greatly improves safelight safety without worsening color staining after treatment, compared to Kanjian-3.
Moreover, it can be seen that the sensitivity does not decrease with respect to a light emitting diode light source having an emission maximum at 660 nm, and the photographic characteristics are not adversely affected.

Table 1 411 Addition amount q/m" 112 (Capri by 7-7 light) = (Capri concentration of sample left for 3 minutes) - (Capri concentration of sample left for 0 seconds) 113 Color stain comparison compound after treatment [mu] Implementation vAU2 Using the emulsion prepared in Example 1, 5-ethyl-2[3-ethyl-benzothiazolinylidene-methylidene]-5-[5-ethyl-4-methylthi] was added as a spectral sensitizing dye. azolinylidene-etherithene]-rhodanine iodide salt and 4,4'-bis(di-naphthoxy-pyrimidylamine)stilbene-2,2'-disulfonic acid disodium salt (1 mole of silver halide) 20q of each were added, and compounds belonging to -Momonana [13 and [11] and a compound represented by [mu] as a comparative compound were added in the types and amounts shown in Table 2.Furthermore, the same additives as in Example 1 were added. Add
Furthermore, as a fluorescent brightener, 2,5-bis(5'-terpenezoxazolyl(2))thiophene 4f
'ff, sodium dodecylbenzenesulfonate 10f
The above-mentioned optical brightener was dissolved in ethyl acetate and dispersed in gelatin, and the above-mentioned optical brightener was added so that it contained 201Q/m" at the time of coating.
It was coated to a thickness of 17 m.

These samples were subjected to wedge exposure using He-1ie laser light, and then heated at 38°C using developer-2 having the following composition.
The film was developed for 20 seconds, fixed with the fixing solution of Example 1, and then washed with water and dried. In addition, a sample unexposed to He-Me laser light was left in the same manner as in Example gAU1 and processed as described above.

Evaluation was carried out in the same manner as in Example 1, and the results are shown in Table 2.

(Developer solution-2 formulation) H,O about 70〇- Ethyl V-diaminetetraacetic acid 2 Monosodium salt 2.82 Potassium hydroxide 11525-Methylbenzotriazole 1lL0822-Mercapto-benraimidazole-5-sulfonic acid sodium [L321- Phenyl-5-pyranolidone α42 sulfite 67? carbonated water salt
11F potassium bromide
55t hydroquinone
25? From Table 2, sample-2 containing compound 1-4t- of the present invention alone has a maximum response to He-1ie laser at 632.8 nm compared to -1 and -5. It can be seen that the safelight safety is improved without compromising sensitivity, and the color contamination after processing is also very low. Furthermore, the compound of the present invention! -4 and ■-8 are combined in sample 11 and 4 is -
2, significantly improves safelight safety without worsening post-processing color staining compared to 652.-3, and 652.
It can be seen that the sensitivity to the He-Me laser light source emitting light at 8 nm is not reduced and the photographic properties are not adversely affected.

2nd table Tatami 1 addition amount ag/m” Tatami 2 (Fog due to safelight) = (Capri concentration of sample left for 3 minutes) - (Fog density of sample left for 0 seconds) Wavelength showing color contamination yield after Tatami 3 treatment Example 3 Compounds belonging to the general formula [IL(...]) were added to a 14% gelatin aqueous solution in the types and amounts shown in Table 3.

Furthermore, the same additives as in Example 911 were added, and gelatin was coated on a subbed polyethylene terephthalate support with a protective layer to give an IL of 797 m''. ℃, humidity 10%, and 65qh, and was left in an atmosphere of temperature 40℃ and humidity 80% for 3 days.Then, the light absorption spectrum of each sample was measured, and the wavelength (2M
The light absorption amount of the sample was measured and compared with the value of the sample measured immediately after coating. The rate of change in the optical absorption spectrum of the dye under each atmosphere was evaluated using the following relational expression.

The results are shown in Table 3.

According to the results of Table 3, the rate of change in light absorption spectrum, samples containing the compound represented by the general formula [1] of the present invention and the general formula [...]
〇-Mixed Na 5 t 6 t 7 +8
．． It can be seen that the rate of change in the 9- and 10-ri optical absorption spectra is small, indicating that the stability over time is excellent.

Table 3 Well addition amount q/m” 1988 Patent Application No. 16258 2. Name of invention Silver halide photographic material 3. Person making the amendment Relationship to the case: Patent applicant Address: 210 Nakanuma, Ashigara City, Kanagawa Prefecture Name (520) Fuji Shasei Film Co., Ltd. Specification 6. Contents of correction: We will submit a clean copy of the detailed statement (with no changes to the contents).

Claims (1)

[Claims] At least one dye compound represented by the following general formula (1)
A silver halide photographic light-sensitive material characterized by containing a species and at least one dye compound represented by the following general formula (II). General formula (I) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ General formula (II) ▲ Contains mathematical formulas, chemical formulas, tables, etc. ▼ In general formula (I), R_1 and R_2 are an alkyl group, an aryl group, and a cyano group, respectively. , -COOR_5, -CO
NR_5R_6, -COR_7, -SO_2R_7, -
SOR_7, -SO_2NR_5R_6, -OR_5,
-NR_5R_6, -NR_6COR_7, -NR_5
CONR_5R_6 or -NR_6SO_2R_7 (where R_5 and R_6 represent a hydrogen atom, an alkyl group, or an aryl group, R_7 represents an alkyl group or an aryl group, and R_5 and R_6 or R_6 and R_7 are connected to form a 5- to 6-membered ring. ), R_3, R
_4 each represents a hydrogen atom or an alkyl group. Q_1,
Q_2 each represents an aryl group, X_1 and X_2 represent a bond or a divalent linking group, Y_1 and Y_2 each represent a sulfo group or a carboxyl group, L_1 and L_
2 and L_3 each represent a methine group. n is 0, 1 or 2, m_1, m_2 is or 2, p_1
, p_2 is 0, 1, 2, 3 or 4, q_1, q_2 is 1
, 2 or 3. In general formula (II), X and Y may be the same or different, represent an electron-withdrawing group, and X and Y may be linked to form a ring. R_1_1 and R_1_2 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_1_3 and R_1_4 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 R_1_3 and R_
1_4 may be connected to form a 5- to 6-membered ring. Also, R_1_1 and R_1_3, R_1_2 and R_1_
4 may be connected to each other to form a 5- to 6-membered ring. Above X, Y, R_1_1, R_1_2, R_1_3, R
At least one of _1_4 has a sulfo group or a carboxyl group as a substituent. L_1_1, L_1_2, and L_1_3 each represent a methine group. k represents 0 or 1.