JPH0414037A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To facilitate decoloring of the photosensitive material to lower sensitivity to the visible light, and to enhance sensibility to infrared rays by incorporating a combination of a specified dye and at least one of specified dye groups. CONSTITUTION:This photosensitive material contains the dye of formula I for preventing irradiation or halation, and at least one of the dye groups of formulae II - IV for imparting safelight safety. In formulae I - IV, each of R1 and R21 is alkyl; each of Z1, Z2, Y1, and Y2 is an atomic group necessary to form a prescribed ring; each of L1, L2, L3, L11, L12, L13, L21, and L22 is methine; each of X1 and X21 is an anion; each of R11 and R12 is alkyl, aryl, or the like; each of Q11 and Q12 is methylene; each of Y11 and Y12 is H, alkyl, or the like; Z21 is an atomic group necessary to form a prescribed hetero ring; R22 is aryl; Z31 is a carbon ring or the like; R31 is aryl or the like; each of n1, n21, and m21 1 or 2; each of m11 and m12 is 0 - 5; each of n11 and n32 is 0, 1, or 2; and n31 is 0 or 1.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a silver halide photographic light-sensitive material having a dyed hydrophilic colloid layer, and more specifically, a silver halide photographic material having a dyed hydrophilic colloid layer.
having at least one hydrophilic colloid layer containing a water-soluble dye with a longer wavelength absorption maximum and being photochemically inert and easily bleached and/or eluted during photographic processing. The present invention relates to a silver halide photographic light-sensitive material comprising at least one hydrophilic colloid layer containing a water-soluble dye having an extreme absorption wavelength shorter than 750 nm.

(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 single-layer 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. In order to prevent blurring of images, that is, ration, a colored layer is provided between the photographic emulsion layer and the support, or on the surface of the support opposite to the photographic emulsion layer. Such a colored layer is called an antihalation layer. In the case of multilayer color photosensitive materials, an anti-ration layer may be placed between each layer.

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

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) It must be photochemically inert, meaning that it will not have an adverse effect on the performance of the silver halide photographic emulsion layer in a chemical sense.
For example, reduced sensitivity, latent image regression, or no capri.

(3) No harmful coloration remains on the photographic light-sensitive material after processing by being bleached or dissolved away during the photographic processing process.

Many dyes that absorb visible light and even ultraviolet light are known to meet these conditions. but,
At present, there are few dyes that have absorption in the infrared region of the spectrum, that is, 750 nm or more, and satisfy the conditions (1), (2), and (31) described above.

For example, JP-A-62-123454 and JP-A-6355544.
A heptamethine cyanine dye having an indolenine nucleus is described in the issue. However, these dyes
It has an extremely thick absorption wavelength of m or more, and when added to an infrared silver halide photographic material that has been spectrally sensitized to the infrared region of 750 nm or more, it is sufficient to prevent ... ration and f radiation. Effectively, in order to handle the sensitive material under bright safe light, which can be called a bright room, it was necessary to use a dye with a wavelength shorter than 750 nm because the absorption waveform is sharp.

(Object of the Invention) The first object of the present invention is to have a hydrophilic colloid layer colored with a water-soluble dye that does not have an adverse effect on the photographic properties of the photographic emulsion and is easily decolorized by photographic processing. An object of the present invention is to provide a silver oxide photographic material. A second object of the present invention is to provide a silver halogenide photographic material that has a good image, has sufficiently low sensitivity to visible light, and is highly sensitive to infrared light. It is.

(Structure of the Invention) The object of the present invention is to apply at least one dye represented by the following general formula (1) on a support and the following general formula (It), (
2) This was achieved by a silver halogenide photographic light-sensitive material having a layer containing at least one dye represented by the following.

General formula (I) In the formula, R1 and R2 may be the same or different from each other and represent a substituted or unsubstituted alkyl group, and Zl and Z2 each form a substituted or unsubstituted benzo condensed ring or naphtho condensed ring. Represents the necessary nonmetallic atomic group. ¥1,
Y2 may be the same or different from each other and represents a group of nonmetallic atoms necessary to form a cyclic structure via the 3-position carbon of the indole nucleus. However, the dye molecule has at least three acid groups (eg, sulfo group, carboxy group, etc.). L
1, R2, and R3 represent a substituted or unsubstituted methine group, Xl is an anion, and nl is 1 or 2, and is 1 when the dye molecule forms an inner salt. The alkyl group represented by R1 and R2 above is preferably a lower alkyl group having 1 to 5 carbon atoms (e.g., methyl, ethyl, n-7',
n-butyl group, etc.), and may have a substituent (for example, a sulfo group, a carboxy group, a hydroxyl group, etc.). More preferably, R1 and R2 have 1 to 1 carbon atoms and have a sulfo group.
5 represents a lower alkyl group (for example, 2-sulfoethyl, 3-sulfopropyl, 4-sulfobutyl group, etc.), and Y
1 and Y2 represent a cycloalkane ring (eg, cyclobutane, cyclopentane, cyclohexane, cyclohebutane group, etc.), a tetrahydrobilane ring, an N-methylpiperidine ring, etc. via the carbon atom at the 3-position of the indole nucleus.

Substituents of the benzo-fused ring or naphtho-fused ring formed by the nonmetallic atom group represented by Zl and Z2 include a sulfo group, a carboxy group, a hydroxyl group, a halogen atom (for example, F, Cz, Br, etc.), an ano group, Substituted amine groups (e.g. dimethylamino, diethylamino, ethyl-4
-sulfobutylamine/&, di(3-sulfopropyl]amine group, etc.), or a substituted or unsubstituted alkyl group having 1 to 5 carbon atoms bonded to the ring directly or via a divalent linkage (for example, a methyl group) , ethyl group, propyl group, butyl group (preferred substituents include sulfo group, carboxyne group, hydroxyl group, etc.), and divalent linking groups include, for example, -C)-, -NH8O2- -NHC
OO-1-NHCONH--Co.

C0-1-802- and the like are preferred.

The methine group represented by Li-R2 and R5 is preferably an unsubstituted methine group, but it may have a substituent. Examples of the substituent include a substituted or unsubstituted lower alkyl group having 1 to 5 carbon atoms (e.g. methyl group, ethyl group, 3-hydroxypropyl group, benzyl group, 2-sulfoethyl group, etc.), halogen atom (e.g. F, CL, Br, etc.), substituted or unsubstituted aryl group (e.g. hafeyl group, 4-
chlorphenyl group, etc.), lower alkoxy group (e.g.,
methoxy group, ethoxy group, etc.). In addition, the substituents of the methine group represented by Ll, L2, and L3 combine to form a 5-membered ring (e.g., cyclopentene ring) or a 6-membered ring (e.g., 4,4-dimethylcyclohexene ring) containing three methine groups. You can leave it there.

Specific examples of the anion represented by Xl include halogen ion (Cz-1Br-1I), p-toluenesulfonic acid ion, and ethyl sulfate ion.

Specific examples of the dye compound represented by general 2 (1) used in the present invention are shown below, but the scope of the present invention is not limited thereto.

o3e Deafness 0sNa O5e OsK Next, the dye represented by the general formula (II) will be explained in detail.

General formula (n) In the formula, R11 and R12 are each an alkyl group, an aryl group, a cyan group, -COOR,5, -CONR,5R,6, -C
O 几, 7.502R17, -8OR4,, -8O2NR
+sR++6, -OR,5, -NR,5R,6, -NR
1,5cOR+7, -NR,5CONR,5R,6 or -NR,6SO2R,, (where R,5-R,6 represents a hydrogen atom, an alkyl group or an aryl group, and R15 and R
, 6 or n+6 and n+7 may be connected to form a 5- or 6-membered ring. ), Q++ and C12 represent a methylene group, Y++ and Y j 2 each represent a hydrogen atom, an alkyl group, a sulfo group, a carboxy group, or an aryl group having at least one sulfo group or a carboxy group, m11, m12 represents 0, l, and 2.3.4.5, respectively. nu represents 0.1.2. RN, R12, n+
5, R'+6, n+7, YN and Y12 include alkyl groups having 1 to 8 carbon atoms (for example, methyl, ethyl, n-propyl, inpropyl, n-butyl, t-butyl, n- amyl, n-hexyl, n-octyl, isoamyl), and substituents (e.g. F,
C1, Br halogen atom, phenyl, hydroxyl group, sulfo group, carboxy group, cyano group, alkoxy group (e.g. methquine, ethoxy, hydroxyethquine), aryloxy group (e.g. phenoxy, p-methoxyphenoxy), amine group, May have a substituted amine group (e.g. dimethylamino, diethylamino). R11, n+
2. The aryl group represented by 15, R46, and 'R17 (e.g. ehafel, nafnal) is preferably a phenyl group, and a substituent (e.g. halogen atom such as fluorine, chlorine, bromine, etc., sulfo group, carboxyl group) is preferable. , a hydroxyl group, a cyano group, an alkyl group having 1 to 4 carbon atoms (eg, methyl, ethinope n-propyl), an alkoxy group (eg, methoxy/, ethoxy), or an aryloxy group (eg, phenoquine)].

The aryl group having at least one sulfonic acid group or carboxylic acid group represented by Yll or Y12 is preferably a phenyl group or a naphthyl group. 4 alkyl group (e.g. methyl, ethyl), alkoxy group (e.g. methoxy, ethoxy halogen atom (F, Ct, Br)
, carbamoyl group (e.g. methylcarbamoyl, ethylcarbamoyl), sulfamoyl group (e.g. ethylsulfamoyl), cyano group, nido a group, alkylsulfonyl group (e.g. methanesulfonyl), arylsulfonyl group (e.g. benzenesulfonyl), It may have an amino group (eg, dimethylamino, diethylamine), an acylamino group (eg, acetylamino), a sulfonamide group (eg, methanesulfonamide), or a hydroxyl group.

The methylene group represented by Qll and C12 may have a substituent (eg, methyl, ethyl, hydroxyl group, etc.).

Examples of the 5- or 6-membered ring formed by linking n+5 and R16 or R16 and RR include a piperidine ring, a morpholine ring, a pyrrolidine ring, and a pyronthone ring.

Lll, L +2. The methine group represented by L 13 has a substituent c such as methyl, ethyl, cyano, phenyl,
chlorine atom, sulfoethyl].

In the above general formula (ffJ), the sulfo group, carboxyl group, and enol moiety of the pyrazolone ring may be in free form or in salt form (
For example, Na salt, K salt, (02H5)3NH salt, pyridinium salt, ammonium salt) may be formed.

In the above general formula (II), preferred is Y +
1, YI2 represents a sulfonic acid group, or m11
=: m 12 = 1, and YN and Y+2 represent a phenyl group having at least one sulfonic acid group.

Specific examples of dyes represented by the general formula (Ill) are shown below, but the present invention is not limited thereto.

(ll-1) (It-2) (II-3) (■ 4) Hs H5 (■ (JL; f-13 CH5 (II-9) (■ (■ (■ (n-7) (n-8 ) H5 H5 (■ S Os K S Os K (It-14) (It-15) (If-18) (If-19) (II-17) (II-20) CCH2)ssOsNa (GH2)ssυxNa 03Na 0sNa The dye represented by the general formula (11) is
No. 49-99620, No. 50-145125, No. 50-147712, No. 59-111640, No. 6
2-273527, JP-A No. 62-79483, JP-A No. 6
Nos. 2-110333 and 63-2045, or can be synthesized by a similar method.

Next, the dye represented by general formula (2) will be explained in detail.

, Z21, in the formula, Z2+ represents a group of nonmetallic atoms necessary to form a heterocycle of benzthiazole, naphthothiazole, benzoxazole, naphthoxazole, indole or pen-indole, and a benzene ring, naphthalene, etc. forming the above-mentioned heterocycle The ring has a substituent (for example, a lower alkyl group such as methyl or ethyl group, an alkoxy group such as methoxy or ethoxy group, a halogen atom such as F, Ct, or Br, a sulfo group, a carboxy group, an amino group, or a cyano group). divalent linking group (for example, -NH3O2-1-Nl(C
OO-1NHCONH-5-coo--co-1-80
A substituted or unsubstituted alkyl group may be bonded to the ring via a ring (such as 2-). R21 represents a substituted or unsubstituted alkyl group, preferably a lower alkyl group having 1 to 5 carbon atoms (for example, methyl, ethyl, n-propyl, n-
-amyl group, etc.] and a substituent (e.g., sulfo group,
carboquine group, hydroxyl group, etc.). More preferably, a lower alkyl group having 1 to 5 carbon atoms (for example, 2-
sulfoethyl 3-sulfopropyl% 4-sulfobutyl group, etc.). LH1L22 represents a methine group 02
1 represents l or 2, and X21 represents an anion (for example, C
t,, Br-1I fl tonohalogen ion, p-
toluenesulfonic acid ion, etc.). m 2 +
is 1 or 2, and 1 when the dye molecule forms an inner salt.
It is. R22 represents a substituted or unsubstituted aryl group, and examples of the substituent include an alkyl group (e.g., methyl, ethyl group, etc.), a cyano group, a sulfo group, a carboxy group, a halogen atom (F, CL-Br, etc.), an amino group, Substituted amine groups (e.g. dimethylamino, di(2-sulfoethyl)amino, di(3-sulfopropyl)amino groups, etc.),
or a divalent linking group (e.g. -0--NH8O2--
NHCOO-1-NHCONH-1-COO--CO-
Substituted or unsubstituted alkyl groups having 1 to 5 carbon atoms (e.g., methyl, ethyl, propyl groups, etc. (substituents include sulfo groups, carboxy groups, hydroxyl groups, etc.) bonded to the aryl group via ~5O2-, etc.) preferred)). Further, the substituent may form a ring (eg, tetrahydroquinolin-6-yl) with the aryl group. However, the dye molecule must contain at least one acid group (eg, sulfo group, carboxy group, etc.).

Specific examples of the dye represented by general formula (2) are shown below, but the present invention is not limited thereto.

(In-1) (I[l-2) (I[[-3) (lff-4) (III-7) (III-5) CI! -8) (I[l-6) CI [l-9) 2H5 SO6゜ (III-11) (III-12) SO3゜ 5 (J5K l θ O3 SO3゜ SO3゜ (III-15) SO,.

([1-16) Next, the dye represented by the general formula will be explained in detail.

General formula (1v) In the formula, Q represents a carbocyclic or heterocyclic ring forming group, LSI,
L32 and L5S represent a methine group, and R31 represents an aryl group or a heterocycle-forming group. ns+ represents 0 or 1, and n32 represents 0.1.2, but n5+ and n32 are never 0 at the same time.

Q is a carbocyclic ring such as 1,3-cyclopentadione, 1,3-17 dandione, pyrazolone, inoxacilone, barbituric acid, thiobarbital acid, 3-ocinetheonaphthene, rhodanine, 2-thiohydantoin, 2-thioxazolidine Represents a heterocycle-forming group such as dione, pyrazolopyridine, or quinolone. L31LS2. L15
represents a methine group, but alkyl groups having 1 to 3 carbon atoms (e.g. methyl, ethylnato), phenyl groups, benzyl groups,
It may be substituted with a 7enethyl group, a hydroxy group, an acyl group, a halogen atom, or the like. Furthermore, the substituents of the methine group may form a ring (for example, 5,5-dimethyl-1-cyclohexen-1-yl-3-yritene).

The dye represented by the general formula (IV) preferably has an acid group (eg, a sulfo group, a carboxy group, etc.) in the molecule. Each acid group includes its salts (eg, alkali metal salts such as sodium, potassium, etc., organic ammonium salts such as ammonium, triethylammonium, pyridinium, etc.).

Examples of the dye represented by the general formula (IV) include dyes represented by the following general formulas 0V)-1 and 2).

Beat -1 (transition) -2 (Q4I) Y4+ f147 R31, R52, L5S and n5+ are as described above.

R34 and R55 represent a methine group, and nss is 1 or 2. R41 is the same as R11 described above in the general formula (U), and Q41, mu, and Y41 are also the general formula Qlt-m++
, Yll are shown, respectively. R42, R45, and Z41 are general ceremonial masters, and are the same as R22, R21, and Z21, respectively.

Specific examples of dyes represented by general formulas are shown below, but the present invention is not limited thereto.

(J'i'-1) (Q41 Suichi-Y41 o3K (IV-5) (IV-6) (IV-4) 80, K (IV-7) O3S (■ (■ (■ CH.

(IV-11) CH.

(■-12) (■ CH2CH2SO3I( (■ (IV-20) (■ 03K (■ Solvent] and added to the coating solution for a hydrophilic colloid layer of the present invention.

Two or more of these dyes can also be used in combination.

The specific amount of dye used varies depending on the purpose and is difficult to set uniformly, but it is generally 10 f/d to 1 d/d, especially 10
-3f/n? Preferred amounts can be found in the range ˜0.52˜.

The photographic dye represented by the general formula (11) of the present invention is particularly effective for the purpose of preventing irradiation, and when used for this purpose, it is mainly added to the emulsion layer.

The dye represented by the general formula (1) is also particularly useful as an antihalation dye, in which case it is added to the back side of the support or to a layer between the support and the emulsion layer.

The photographic dyes of the present invention represented by the above general formulas (II), (2) and (2) are particularly useful as dyes that provide safelight safety, and in this case, other wavelengths may be used as needed. It is added to layers (such as protective layers) located on top of the photographic emulsion layer in combination with a light-absorbing dye.

In addition, the photographic dyes of the present invention can also be advantageously used as filter dyes.

The photographic dye of the present invention can be introduced into the desired photographic constituent layer by a conventional method. That is, a solution of a dye at an appropriate concentration may be added to an aqueous solution of a hydrophilic colloid serving as a binder for a photographic constituent layer, and this solution may be coated on the support or other constituent layers.

In the present invention, the dye may be added to any of the hydrophilic colloid layers constituting the silver halide photographic material.
Examples include a protective layer, a silver halide emulsion layer, an antihalation layer, and a back layer.

In the present invention, when the dye is contained substantially only in the non-photosensitive hydrophilic colloid layer, it is sufficient to prevent the dye from diffusing from the non-photosensitive hydrophilic colloid layer to the emulsion layer. For example, a method may be used in which a silver halogenide emulsion layer is coated and completely set, and then a non-photosensitive hydrophilic colloid layer containing a non-diffusible dye is coated on this emulsion layer. Furthermore, when simultaneously coating an emulsion layer and a non-photosensitive hydrophilic colloid layer using a multilayer simultaneous coating method, it is most preferable to add a non-diffusible dye or a polymer mordant together with the dye to the non-photosensitive hydrophilic colloid layer. .

Examples of the light-sensitive material of the present invention include black-and-white photographic materials and color photographic materials.

Examples of the former include photosensitive materials for printing and infrared photosensitive materials. At this time, two or more silver halide emulsion layers may be provided, but one layer is usually sufficient. Application@Amount is 17~~82/W? A range of is desirable.

The silver halide used in the present invention may be, for example, silver chloride, silver bromide, silver iodide, silver chlorobromide, silver chloroiodide, silver iodobromide, or silver chloroiodobromide.

In the case of black and white photosensitive materials, the average grain size of silver halide is 1
．． It is preferably 0 μm or less, particularly preferably 0°7 μm or less.

The silver halide grains in the photographic emulsion may be so-called regilar grains with regular crystal structures such as cubes, octahedrons, and tetradecahedrons, or may have irregular crystal shapes such as sweet spherical shapes. , one with crystal defects such as twin planes, or a composite form thereof.

The grain size of the silver halide may be a monodisperse emulsion with a narrow distribution, or a polydisperse emulsion with a wide distribution.

The silver halide photographic emulsion that can be used in the present invention can be produced by a known method, for example, Research Disclosure (RD), A 17643 (December 1978), 2
pp. 2-23, “1. Emulsion Preparation”
The method described in "Paration and Types" and Toiya 18716 (November 1979), p. 643 can be followed.

The photographic emulsion used in the present invention is described in "Physics and Chemistry of Photography" by Grafkide, published by Paul Montell (P.

Glafkides, Chimie et Physi
que Photogra-phique Paul
Montel, 1967), "Photographic Emulsion Chemistry" by Duffy, published by Focal Press (o, p.

Duffin, Photographic Emul
sion Chemistry (Focal Pres.
s, 1966), "Manufacture and coating of photographic emulsions" by Zelikman et al., published by Focal Press (V, L, Zel
ikman et al., Making and Co.
ating Photographic Emulsi
on, Focal Press.

1964).

When forming the silver halide grains used in the present invention, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, and thioether compounds (e.g., U.S. Pat. No. 3,271,157) are used as silver halide solvents to control grain growth.
No. 3,574.628, No. 3,704,13
No. 0, No. 4,297,439, No. 4,276,3
No. 74, etc.), thione compounds (e.g., JP-A-53-14)
No. 4,319, No. 53-82.408, No. 55-
77.737, etc.), amine compounds (e.g., JP-A No. 5
4-Zoo, No. 717, etc.) can be used.

In the present invention, water-soluble rhodium salts and water-soluble iridium salts can be used.

In the present invention, the soluble silver salt and the soluble halogen salt may be reacted by any method such as a one-sided mixing method, a simultaneous mixing method, or a combination thereof.

It is also possible to use a method in which particles are formed in an excess of silver ions (so-called back-mixing method).

As one type of simultaneous mixing method, a method in which the pAg in the liquid phase in which silver halide is produced can be kept constant, that is, the so-called Chondrald double jet method. According to this method, the crystal form is regular and A silver halide emulsion with near uniform grain size is provided.

The silver halide emulsion used in the method of the present invention may or may not be chemically sensitized.

In the case of chemical sensitization, ordinary sulfur sensitization, reduction sensitization, noble metal sensitization, and combinations thereof are used.

More specific chemical sensitizers include allylthiocarbamide,
Sulfur sensitizers such as thioureas, thiosulfates, thioethers and cystine; botium chloroaurate.

Orus, thiosulfate and Potassum chlorovaladate (Potassum chloropa1lad)
Noble metal sensitizers such as tin chloride, reduction sensitizers such as phenylhydrazine and reductone, and the like.

The silver halide emulsion used in the present invention is spectrally sensitized with a known spectral sensitizing dye, if necessary. The spectral sensitizing dye used is Research Disclosure (
Research Disclosure) No. 176
The material described in Vol. A 17643, Section (2) (December issue, 1978) can be used.

The silver halide photographic material of the present invention is particularly preferably applied when the silver halide emulsion is infrared sensitized so as to have extreme sensitization in the wavelength region of 750 nm or more. The sensitizing dye for infrared sensitization is not particularly limited, but tricarbocyanine dyes and/or 4-quinoline nucleus-containing dicarbocyanine dyes are preferred from the viewpoint of sensitization performance and safety. When silver halogenide emulsion is sensitized by infrared spectral sensitization,
Sometimes the stability of emulsions in solution can deteriorate.

In order to prevent this, water-soluble bromide or water-soluble iodide can be added to the emulsion.

Among the tricarbocyanine dyes used for infrared sensitization, those represented by the following general formula (Va) or (Vb) are particularly useful.

General formula (Va) (X 4+) n4+ 1 General formula (vb) In the formula, R4j and R42 may each be the same or different, and each represents an alkyl group (preferably 1 to 8 carbon atoms, for example, a methyl group). , ethyl group, propyl group, butyl group, pentyl group, heptyl group, etc.], substituted alkyl group (e.g., carboxy group, sulfo group, cyano group, halogen atom (e.g., dung atom, chlorine atom, bromine atom, etc.) ), hydroxy group, alkoxycarbonyl group (up to 8 carbon atoms, e.g. methoxycarbonyl group, ethoxycarbonyl group, benzyloxycarbonyl group), alkoxy group (up to 7 carbon atoms, e.g. methoxy group, ethoxy group, propoxy group, butoxy group, benzyloxy group, etc.), aryloxy group (e.g. phenoxy group, 8 or less atoms, e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbamoyl group (e.g. carbamoyl group, N
, N-dimethylcarbamoyl group, morpholinocarbamoyl group, piperidinocarbamoyl group, etc.), sulfamoyl group (e.g. sulfamoyl 3.N).

N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), aryl group (e.g. phenyl group, p-hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group, a-naphthyl group, etc.), etc. represents an alkyl group (the number of carbon atoms in the alkyl moiety is 6 or less; however, two or more of these substituents may be substituted into the alkyl group in combination).

几 and 0 represent a hydrogen atom, a methyl group, a methoxy group, or an ethoxy group.

R45 and R44 each represent a hydrogen atom, a lower alkyl group (e.g. methyl group, ethyl group, propyl group, etc.), a lower alkoxy group (e.g. methoxy group, ethoxy group, propoxy group, butoxy group, etc.), phenyl group, benzyl group .

R45 is a hydrogen atom, a lower alkyl group (for example, a methyl group,
ethyl group, propyl group, etc.), lower alkoxy group (e.g. methoxy group, ethoxy group, propokine group, butoxy group, etc.), phenyl group, benzene substituted or unsubstituted alkyl group (alkyl group having 1 to 18 carbon atoms, Preferably 1 to 4, such as methyl group, ethyl group, propyl group, butyl group, benzyl group, fe, -ruethyl group), aryl group (such as phenyl group, naphthyl group, tolyl group, p
-chlorophenyl group, etc.), and W41 and W42 can also be linked to each other to form a 5- or 6-membered nitrogen-containing heterocycle.

D40 represents the atomic group necessary to complete a divalent ethylene bond, e.g. ethylene or triethylene, and this ethylene bond is supported by one, two or more suitable groups, e.g. Alkyl groups (e.g. methyl, ethyl, propyl, isopropyl, butyl, etc.)
, a halogen atom (for example, a chlorine atom, a bromine atom, etc.), or an alkoxy group (having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, an inpropoxy group,
butoxy group, etc.).

D41 and D42 each represent a hydrogen atom. however,
D41 and D42 can also work together to form a divalent ethylene bond as defined above.

Z40 and Ztl each represent a nonmetallic atomic group necessary to complete a 5- or 6-membered nitrogen-containing heterocyclic ring, such as a thiazole nucleus [e.g., benzothiazole, 4-chlorpentthiazole, 5-chlorpentthiazole, 6 -Chlorbenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole,
6-Methylbenzothiazole, 5-bromobenzthiazole, 6-)'bromobenzthiazole, 5-iodobenzylthiazole, 5-phenylbenzthiazol-
5-methoxybenzothiazole, 6-methylbenzothiazole, 5-ethoxybenzothiazole, 5-carboxybenzotheazole, 5-ethoxycarbonylbenzothiazole, 5-7enethylbenzothiazole, 5-fluoropenzothianol, 5-trifluoromethylbenzothiazole, 5.6 dimeterbenzothiazole, 5-
Hydroxy-6-methylpenzotheanol, tetrahydrobenzothiazole, 4-phenylbenzothiazole,
naphtho[2,1-d]thiazole, naphtho[1,2d]
Thiazole, naphtho(2,3-d)thiazole, 5-methoxynando[1,2-d,]thiazole, 7-ethoxynaphtho[2,1-d]thiazole, 8-methoxynaphtho[2,1-d]thiazole , 5-Metkinnuff) [:2
, 3-d] thiazole, etc.], selenazole core [e.g. benzimidazole, 5 chlorpenzoselenazole, 5
-methoxybenzimidazole, 5-methylbenzimidazole, 5-hydroxybenzoxazole, naphthoC2゜1-d]zelenazole, naphtho[1,2-d]zelenazole, etc.], oxazole nucleus [benzoxazole, 5-chlorobenzoxazole, 5-Methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzoxazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenyl/soxazole, 5-hydroxybenzoxazole, 5- Carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorbe/dioxazole, 6-medoxybenzoxazole, 6-
Hydroquine benzoxazole, 4,6-dimethylbenzoxazole, 5-ethoxybenzoxazole,
naphtho[2,1-d)oxazole, naphtho[1,2-
d]oxazole, naphtho[2,3-d]oxazole, etc.], quinoline nucleus [e.g. 2-quinoline, 3-methyl-2-quinoline, 5-ethyl-2-quinoline, 6-methyl-2-quinoline, 8- Fluoro-2-quinoline, 6-
medoxy-2-quinoline, 6-hydroxy-2-quinoline, 8-chloro-2-quinoline, 8-fluoro-4-quinoline, etc.], 3,3-dialkylindolenine core (e.g., 3,3-dimethylindolenine, 3 .3-diethylindolenine, 3.3-dimethyl-5-cyanoindolenine, 3.3-dimethyl-5-methoxyindolenine,
3.3-dimethyl-5-methylindolenine, 3,3-
dimethyl-5-chlorindolenine, etc.), imidazole cores (e.g., 1-methylbenzimidazole, 1-ethylbenzimidazole, 1-methyl-5-chlorobenzimidazole, 1-ethel-5-chlorobenzimidazole, 1-methyl -5,6-dichlorobenzimidazole, 1-ethyl-5,6-dichlorobenzimidazole, 1-alkyl-5-methoxybenzimidazole,
1-Methyl-5-cyanobenzimidazole, 1-ethyl-5-cyanobenzimidazole, 1-methyl-5-
Fluorobenzimidazole, 1-ethyl-5-fluorobenzimidazole, 1-phenyl-5,6-dichlorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-phenylbenzimidazole, 17-ethyl-5-chlorobenzimidazole, 1-methyl-5-trifluoromethylbenzimidazole, 1-
ethyl-5-trifluoromethylbenzimidazole,
1-ethylnaf) [1,2-d) imidazole, etc.)
, pyridine nuclei (for example, pyridine, 5-methyl-2-pyridine, 3-methyl-4-pyridine, etc.). Among these, thiazole nuclei and oxazole nuclei are preferably used. More preferably, a benzothiazole nucleus, a naphthothiazole nucleus, a naphthoxazole nucleus, or a benzoxazole nucleus is advantageously used.

X41 represents an acid anion.

n41 represents 1 or 2.

Particularly useful among the 4-gynoline nucleus-containing dicarbonanine dyes used in the present invention are the following general formulas (VC) (X42) n42-1 where R46 and R47 have the same meanings as R41 and R42, respectively. represents.

R48 represents the same meaning as R43. However, R411 is preferably a lower alkyl group or a benzyl group.

V4+ is a hydrogen atom, a lower alkyl group (e.g. methyl group,
ethyl group, propyl group, etc.), alkokene group (e.g. methoxy group, ethoxy group, butoxy group, etc.), halogen atom (e.g. fluorine atom, chlorine atom, etc.), substituted alkyl group (e.g. trifluoromethyl group, carboxymethyl group, etc.) represents.

Zn2 represents the same meaning as ZnO and Z4+.

X42 represents the same meaning as X41.

m4+, n42, and p each represent l or 2.

Specific examples of the sensitizing dye used in the present invention are shown below. However, the present invention is not limited to these sensitizing dyes.

(V-2) (V-6) (V-10) C21-I 5 SO5 Shi2H5 H3 C2■(5 (V-14) (V-15) (■ (■ (V-22) (■ (■ ■ tO4 2H5 ■ 2H5 2H5 (V-18) (■ (■ (■ CCH2)3sOs C2I■5 (CI-12)4So3 C2I-■5 (V-31) V-33) (V-38) (CH2) 20H (CI(2)3SO3 2H5 tOa (■ C2■-■5 (V-35) H2C0O (■ (V-42) C5H,.

t04 The above-mentioned infrared sensitizing dye used in the present invention is 5X10'mole-5X10' mole per mole of silver halide,
Preferably from 1×10 to 6 mol to 1×10′ mol, particularly preferably from 2×10′ mol to 1×10′ mol
It is contained in silver halide photographic emulsions at 0%.

The infrared sensitizing dye used in the present invention can be directly dispersed into the emulsion. In addition, these can be prepared using a suitable solvent,
For example, it can be dissolved in methyl alcohol, ethyl alcohol, methyl cellosolve, acetone, water, pyridine, or a mixed solvent thereof, and added to the emulsion in the form of a solution.

Ultrasonic waves can also be used for dissolution. Further, as a method of adding the above-mentioned infrared sensitizing dye, US Pat.
69,987, etc., a method in which a dye is dissolved in a volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion, Japanese Patent Publication No. 46
A method of dispersing a water-insoluble dye in a water-soluble solvent without dissolving it and adding this dispersion to an emulsion, as described in US Pat. No. 3,822,135, etc. , a method of dissolving a dye in a surfactant and adding the solution to an emulsion; JP-A-51-7462-
A method of dissolving a red-shifting compound as described in No. 4 and adding the solution to an emulsion;
A method such as that described in Japanese Patent No. 80826 is used, in which a dye is dissolved in an acid substantially free of water, and the solution is added to an emulsion. Other additions to emulsions include U.S. Patent No. 2,
No. 912,343, No. 3,342,605, No. 2
, No. 996,287, No. 3,429,835, etc. can also be used. Also above - formula (Va), (
The infrared sensitizing dye Vb) may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but it is of course possible to disperse the infrared sensitizing dye in any step of the preparation of the silver halide emulsion. can also be dispersed.

The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. For example, U.S. Patent No. 3.703,3
No. 77, No. 2,688,545, No. 3.397,
No. 060, No. 3,615,635, No. 3.628
, 964, British Patent No. 1,242,588, British Patent No. 1
, No. 293,862, Special Publication No. 43-4936, No. 44
-14030, No. 43-10773, U.S. Patent No. 3
, 416,927, Japanese Patent Publication No. 43-4930, U.S. Patent No. 3,615,613, U.S. Pat.
The sensitizing dyes described in No. 1, etc. can be used.

In the present invention, a compound represented by the following general formula (VD) can be used for the purpose of further enhancing the supersensitizing effect and/or for the purpose of further improving the storage stability.

General formula (Vl) \ SO,M In the formula, -A- represents all divalent aromatic residues, and these are -
803M group [where M represents a hydrogen atom or a cation (eg, sodium, potassium, etc.) that provides water solubility. ]
May contain.

8- is usefully selected from the following -A1 or -A2-, for example. However, if R31, R52, R33 or R34 does not contain -A, -A
, - is selected from the group.

Such. Here, M represents a hydrogen atom or a cation that provides water solubility.

-A2-: R+5+, R5°, Rrss and R54 are each a hydrogen atom, a hydroxy group, a lower alkyl group (the number of carbon atoms is preferably 1 to 8. For example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group) groups), alkoxy groups (preferably 1 to 8 carbon atoms, such as metquine, ethoxy, propoxy, metquine, etc.), aryloxy groups (e.g., Fe,! xy group, naphthoxy group, 0-troxy group% p-sulfophenoxy group],... rogene atom (chlorine atom, bromine atom, etc. if kept), heterocyclic nucleus (
For example, morpholinyl group, piperidyl group, etc.), alkylthio group (for example, methylthio group, ethylthio group, etc.), heteroclylthio group (for example, benzothiazolylthio group,
(benzimidazolyl group, phenyltetrazolylthio group, etc.), arylthio group (eg, phenylthio group, tolylthio group), ami7 group, alkylamino group or substituted alkylamino group.

(For example, methylamino group, etelamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di(β-hydroxyenal)amino group, β-sulfoetheramino group) group), arylamino group,
or a substituted arylamino group (e.g. anilino group, 0-
Sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, 0-toluidino group, m-)luidino group, p
-) Luidino group, 0-carboxyanilino group, m-carboxyanilino group, p-carboxyanilino group, 0-chloroanilino group, m-chloroanilino group, p-chloroanilino group, p-aminoanilino group, 0- anisidino group,
m-anisidino group, p-anisidino group, 0-acetaminoanilino group, hydroxyanilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group, etc.), heterocyclylamino group (e.g. 2-benzothia zolylamino group, 2-biladyl-amino group, etc.), substituted or unsubstituted aralkylamino groups (e.g. benzylamino group, 0-anisylamino group, m-anisylamino group, p-arylamino group, etc.), aryl group ( For example, phenyl group), mercapto group. R5+, R
52, R53, and R54 may be the same or different from each other. When -A- chooses from the group of 2-,
At least one of R51, R52, R55, and R54 must have one or more sulfo groups (which may be free acid groups or may form salts). W is -CH
= or -N-, preferably -CH= is used.

Next, specific examples of compounds included in general formula (M) used in the present invention will be given. However, the present invention is not limited only to these compounds.

(M-1) 4.4'-bis[4,6-di(benzothiazolyl-2-thio)pyrimidine-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt (Vl-2) 4. 4'-bis[4,6-di(benzothiazolyl-2-aminocopyrimidin-2-ylamino)]stilbene-2,2'CM-3) (■-4) (M-5) CM-6) (■ -7) Monodisulfonic acid disodium salt 4,4'-bis[4,6-di(naphthyl-2-oxy)]
Pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt 4,4'-bis[4,6-di(naphthyl-2-oxy)]
pyrimidin-2-ylamino]pipeny/zyl-2,2'-nsulfonic acid disodium salt 4,4'-bis(4,6-dianilinopyrimicin-2-
ylamino)stilbene-2,2'-disulfonic acid disodium salt 4.41-bis[4-chloro-6-(2-su2thyloxy)pyrimidine-2-ylaminocobiphenyl-2,2'-disulfonic acid disodium salt Sodium salt 4.4'-bis[4,6-di(1-phenyltetrazolyl-5thio)pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt (■-8) 4 .4'-bis[4,6-di[benzimidazolyl-2-thio]pyrimidin-2-ylamino]stilbene-2,2' disulfonic acid disodium salt CM-9) 4.4'-bis(4,6-diphenylene) , noquinpyrimidin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (W-10) 4,4'-bis(4,6-cyphenylthiopyrimidin-2-ylamino)stilbene-2 , 2'-disulfonic acid disodium salt (M-11) 4,4'-bis(4,6-dimercabutobyrimidin-2-ylamino)piphenyl-2,2'-disulfonic acid disodium salt CM-12 ) 4.4'-bis(4,6-dianilitutriazin-2-ylamino)stilbene-2,2
'-Disulfonic acid disodium salt (Vl-13) 4.4'-bis(4-anilino-6
-Hydroxyk-triazi/-2-ylamino)snarbene-2.2'-disulfonic acid disodium salt (■-14) 4.4'-bis[4-su7teramino6-7nilinotriazin-2-ylamino)stilbene -2,2'-Disodium disulfonate Among these specific examples, (M-1) to (M-12) are preferred, particularly (■-1), (W-2), (Vl-3),
(■-4), (W-5), and (M-7) are preferred.

- The compound of formula (M) is advantageously used in an amount of about 0.01 to 5 grams per mole of silver halide in the emulsion.

The ratio (weight ratio) of the above-mentioned infrared sensitizing dye of the present invention to the compound represented by formula (■) is infrared sensitizing dye/-
The compound represented by the general formula (1) is preferably in the range of 171 to 1/100, particularly preferably in the range of 172 to 1,150.

The compound represented by the general formula (■) used in the present invention can be directly dispersed into an emulsion, or it can be dispersed in a suitable solution I.
It can also be dissolved in a bacterial medium (for example, methyl alcohol, ethyl alcohol, methyl cellosolve, water, etc.) or a mixture thereof and added to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid in accordance with the method for adding sensitizing dyes. They can also be dispersed and added into the emulsion by the method described in JP-A-50-80119.

In the present invention, compounds of the following general formula (■) can be further used in combination.

- Formula (■) In the formula, Z61 represents a group of nonmetallic atoms necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as thiazolium (
For example, thiazolium, 4-methylthean'rium, beni/anthionylium, 5-methylbenzothiazolium, 5-chlorobenzothiazolium, 5-methoxybenzothiazolium, 6-methylbenzimidazolium, 6-methylbenzothiazolium,
Medoxybeni/thiazolium, naphtho[1,2-d
, ]thiazolium, naph) [2,1-d]thiazolium, etc.), oxacilliums [e.g. oxacillium, 4
-Methyloxacillium Benzoxacillium, 5-
chlorobenzoxacilium, 5-7 aerpenzoxacilium, 5-methylbenzoxacilium, nand[1,2-d]oxacillium, etc.), imidazoliums (e.g. 1-methylbenzimidazolium, l- Propyl-5-dichlorobenzene: /Tuimitan°ium, 1-ether-5,6-dichlorobenzene/7 (Midazolium, 1
-allyl-5-trichloromethyl-6-talolopenzimidazolium, etc.), selenazoliums [e.g., benzoselenazolium, 5-chlorobenzoselenazolium,
5-mef fiv represents benzoselenazolium, 5-methoxybenzoselenazolium, nando[1,2-d]selenazolium, etc.). 'R61 represents a hydrogen atom, an alkyl group (having 8 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, etc.), or an alkenyl group (such as an allyl group). R62 represents a hydrogen atom, a lower represents an alkyl group (e.g. methyl group, ethyl group, etc.).X6. represents an acid anion (e.g. Ct-1
Among Z6+, thiazoliums are preferably used. More preferably, substituted or unsubstituted benzothiazolium or naphthothiazolium is used.

Specific examples of the compound represented by the general formula (■) are shown below. However, the present invention is not limited to only these compounds.

(■-1) CH5 (■-2) (■-6) (■-3) CH3 (■-79 CH2-CH,=CH2 (■-4) CH2-CH,,-CH2 (■-8) CH2-CH,,=CH2 (■-5) CH3 (■-9) ? 2H5 3H7 (■-10) (■-14) CH.

(■-11) 2H5 (■-12) 2H5 2H5 (■-15) 2H5 C4H.

(■-16) (Vll-13) 2H5 (■-17) (■-18) The compound represented by formula (■) above is about 0.01 to 5 grams per mole of silver halide in the emulsion. Advantageously used in amounts of.

The ratio (weight ratio) between the above-mentioned infrared sensitizing dye of the present invention and the compound represented by the formula (■) is as follows: Infrared sensitizing dye of the present invention/-compound represented by the general formula (■) = 171 ~1/
A range of 300 is advantageously used, especially 1. /2~11
A range of 50 is advantageously used.

The compound represented by the general formula (■) used in the present invention can be directly dispersed in an emulsion, or can be dispersed in a suitable solvent (for example, water, methyl alcohol, ethyl alcohol,
It can also be dissolved in a mixed solvent using two or more of these solvents and added to the emulsion. In addition, it can be added to the emulsion in the form of a solution or a dispersion in a colloid according to the method of adding sensitizing dyes.

The compound represented by the general formula (■) may be added to the emulsion before or after the addition of the infrared sensitizing dye of the invention described above.

Alternatively, the compound of the formula (■) and the infrared sensitizing dye may be dissolved separately and added separately to the emulsion at the same time, or they may be mixed and then added to the emulsion.

Various compounds can be added to the photographic emulsion of the present invention in order to prevent a decrease in sensitivity and the occurrence of fog during the manufacturing process, storage or processing of the light-sensitive material.

These compounds include nitrobenzimidazole, ammonium chloroplatinate, 4-hydroxy-6-methyl-1,3,3a, 7-thitraazaindene, l-phenyl-5-mercaptotetrazole, and many other heterocyclic compounds. A large number of compounds such as mercury compounds, mercapto compounds, and metal salts have been known for a long time. An example of a compound that can be used is "The
ory of thePhotographic Pr
Examples of the fine compounds described in pages 344 to 349 of "Ocess" (3rd edition, 1966), citing original documents, include U.S. Pat.
, 694,716, etc.: U.S. Pat. No. 2,886.437 and U.S. Pat. No. 2,444.
, 605, etc.; Urazoles, described in U.S. Patent No. 3,287.135, etc.; Sulfocatechols, described in U.S. Patent No. 3,236,652, etc.; British patents. No. 623, 44
Oximes described in U.S. Pat. No. 8, etc.; U.S. Pat.
No. 403.927, No. 3,266,897, No. 3
Mercaptotetrazoles, nitrones, nitroindazoles, and polyvalent metal salts described in U.S. Pat. No. 2,839,405, etc.;
ts); thiuronium salts (thiuronium 5
alts): Examples include palladium, platinum, and gold salts described in U.S. Pat. No. 2,566,263 and U.S. Pat. No. 2,597,915.

Silver halide photographic emulsions are prepared using a developing agent such as hydroquinones; catechols; aminophenols; 3-pyrazolidones; ascorbic acid and its derivatives; reductones, phenylenediamines, or a combination of developing agents. can be contained. The developing agent may be incorporated into the silver halide emulsion layer and/or other photographic layers (eg, protective layers, interlayers, filter layers, antihalation layers, bank layers, etc.). The developing agent may be dissolved in a suitable solvent or as described in U.S. Pat.
368 and in the form of a dispersion as described in French Patent No. 1,505,778.

As a development accelerator, for example, U.S. Pat. No. 3,288.6
No. 12, No. 3,333,959, No. 3.345.
No. 175, No. 3,708,303, British Patent No. 1.
No. 098,748, West German Patent No. 1,141,531
No. 1,183,784, etc. can be used.

The photographic emulsion of the present invention may contain an inorganic or organic hardener. Examples include chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), N-methylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) ), active vinyl compound (1,3,5-1-lyacryloyl-hexahydro-5-)'J azine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-[β-(vinylsulfonyl)fropion amide], active halogen compounds (2,4-dichloro-
6-hydroxy-S-)riazinato), mucohalogen acids (mucochloric acid, mucophenoxychloric acid, etc.)
Inoxazoles, dialdehyde starch, 2-chloro-6-hydroxytriazinylated gelatin, and the like can be used alone or in combination. Specific examples include U.S. Pat.
No. 2,983,611, No. 2,992,109, No. 3,047,394, No. 3,057,723, No. 3
, No. 103,437, No. 3゜321.313, No. 3,
No. 325,287, No. 3,362.827, No. 3,5
No. 39,644, No. 3,543,292, British Patent 6
No. 76,628, No. 825,544, No. 1,270,
578, German Patent No. 872,153, German Patent No. 1,090
, No. 427, Special Publication No. 34-7, 133, No. 46-18
It is mentioned in issue 72 etc.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared using the present invention may contain coating aids, antistatic properties, smoothness improvement, emulsification dispersion, adhesion prevention, and photographic property improvement (e.g.
Various surfactants may be included for various purposes such as development acceleration, high contrast, and sensitization.

For example, saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol/polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters) , polyalkylene glycol alkyl amines or amides, silicone polyethylene oxide adducts), glycidol derivatives (e.g. alknylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, alkyl esters of sugars, etc. Nonionic surfactants; alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonate, alkylnaphthalene sulfone MtM, alkyl sulfates, alkyl phosphates, sters, N-acyl-N-alkyl taurine kind,
Contains acidic groups such as carboxy groups such as sulfosuccinates, sulfoalkyl polyoxyethylene alkylphenyl ethers, polyoxyethylene alkyl phosphates, etc., sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. Anionic surfactants; amphoteric surfactants such as aminohydrogens, aminoalkyl sulfonic acids, aminoalkyl sulfates or phosphoric acid esters, alkyl betaines, amine oxides; alkylamine salts,
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, square ring quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocycles can be used.

When using a mordant, it is preferable to use an anionic surfactant and an amphoteric surfactant together in order to facilitate application and improve mordant properties. These surfactants may be added to the non-photosensitive hydrophilic colloid layer coating solution or to the emulsion layer coating solution. The usage amount and usage ratio are arbitrary.
It can be easily determined by experiment.

The anionic group of the anionic surfactant used in the present invention is a sulfonic acid group, a carboxylic acid group, a phosphoric acid group, etc., and the hydrophobic part is a hydrocarbon, a partially or fully fluorinated hydrocarbon, etc. .

Typical anionic surfactants preferably used in the present invention are listed below, but the present invention is not limited thereto.

[A-1] 几71 R,o-C0N4CH2+So5M However, R70 is a saturated or unsaturated hydrocarbon group having 3 to 20 carbon atoms and its fluorine substituted product, and 几71 is a hydrogen atom,
A methyl group, an ethyl group or a propyl group. n is 1-2
It is an integer of 0, and 1 to 8 are particularly preferable. M is a monovalent alkali metal, with Na and K being particularly preferred.

[A-2] [A-3] In [A-2] and [A-3], R70, M, and n are the same as in general formula [A-11]. a represents 0, 1 or 2. m is an integer of 1 to 6, particularly preferably 2 to 4.

[A-4] CH2C00R70 M-03S-CH-COOR,.

[:A-5] Ryo O505M [A-6] [A-4), [A-5], (A-6), R, o
, M have the same meanings as in the general formula [:A-1].

[A-73 However, R71 and M have the same meaning as in general formula [A-1), and m has the same meaning as in general formula CA-2).

[A-8] [A-9:] and m has the same meaning as in general formula [A-2).

Specific examples of particularly preferably used anionic surfactants are as follows.

C11H25C0NHCH2So3NaCyP,
5CONH(CH2)2SOsNaCH3 C6H+7CON(CH2)2SO5K[A-8], [
A-9], R72 is a sulfate or unsaturated hydrocarbon having 3 to 22 carbon atoms in which the hydrogen moiety is fluorinated, preferably 7 to 18 carbon atoms. R71, M is the general formula [A
-1), the same C8P17 SO2NHCCH2)
scOONaC,7F33SO2NH(CH2)4CO
ONaCBF27S02NH(CH2)sOPo(01
()2CH2-COOC. H.

N a O s S C H C O O C a
H 17C,H,5-0-SO3X C+2H2sO-SO3Na The amphoteric surfactant used in the present invention is a surfactant that has both an anionic group and a cationic group in the - molecule to form an inner salt. It is represented by the following general formula CB).

General formula [B) θ ■ -C In the general formula [B], A represents an anionic residue containing an anionic group such as a sulfonic acid group, a carboxylic acid group, or a phosphoric acid group, and C0 represents an organic cationic residue. .

Specific examples of particularly preferably used amphoteric surfactants are as follows.

B-1 (10-carboxydecyl) dimethyldodecylammonium hydroxide B-2 (2-carboxyethyl) dimethyldodecylammonium hydroxide B-3 (3-sulfopropyl) dimethyldodecylammonium hydroxide B-4 (4-sulfobutyl) Dimethyldodecylammonium hydroxide B-5-(2-carboxyethyl)dimethyloctadecyl ammonium hydroxide B-6(3-sulfopropyl)dimethyloctadecyl ammonium hydroxide B-7(carboxymethyl)dimethyloctadecyl ammonium hydroxide B-8( Carboxymethyl)dimethylundecylcarbamoylpropylammonium hydroxide B-9(3-sulfobutyl)dimethylundecylcarbamoylpropylammonium hydroxide B-101-(10-carboxydecyl)pyridium hydroxide B-111-(10-sulfobutyl) (eitodecyl) pyridium hydroxide B-123-carboxy-1-dodecylpyridinium hydroxide B-131-(1-carboxytridenruviridinium hydroxide) Improves the sharpness of the legs of the characteristic curve and produces high-quality halftone dots and For purposes such as obtaining line images, polyalkylene oxide compounds (for example, alkylene oxides having 2 to 4 carbon atoms, such as ethylene oxide, propylene-1,2-oxide, butylene-1,2-oxide, etc., preferably ethylene oxide) are used. A condensation product of a polyalkylene oxide consisting of at least 10 units of polyalkylene oxide and a compound having at least one active hydrogen atom such as water, aliphatic alcohol, aromatic alcohol, fatty acid, organic amine hexitol derivative, or two or more types of Polyalkylene oxide compounds such as Pronk copolymers of polyalkylene oxides are preferably used. Specifically, the polyalkylene oxide compounds include polyalkylene glycols, polyalkylene glycol alkyl ethers, polyalkylene/glycol aryl ethers [alkylaryl] ethers, polyalkylenes, etc. Glycol esters, polyalkylene glycol fatty acid amides, polyalkylene glycol amines, polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, etc. can be used.The molecular weight must be 600 or more.

The number of polyalkylene oxide chains is not limited to one in the molecule, and two or more may be included. The lateral polyalkylene oxide chains may then consist of fewer than 10 alkylene oxide units, but the total number of alkylene oxide units in the molecule must be at least 10. If there is more than one polyalkylene oxide chain in the molecule, each of them may consist of different alkylene oxide units, such as ethylene oxide and propylene oxide. The polyalkylene oxide compound that can be used in the present invention preferably contains from 4 to 100 alkylene oxide units.

Specific compounds include JP-A-50-156423 and JP-A-52-10813.
Polyalkylene oxide compounds described in No. 0 and JP-A-53-3217 can be used. These polyalkylene oxide compounds may be used alone or in combination of two or more.

When these polyalkylene oxide compounds are added to a silver halide emulsion, they are dissolved in a suitable aqueous solution or in a water-miscible low boiling point organic solvent, and added at an appropriate time before coating. Preferably, it can be added to the emulsion after chemical ripening.

These polyalkylene oxide compounds are preferably used in an amount of 1.times.10.sup.8 mol to 1.times.10@-2 mol per mol of silver halide.

The above polyalkylene oxide compound is not added to the emulsion, but can be used in non-photosensitive hydrophilic colloid layers such as intermediate layers, protective layers, etc.
It may also be added to a filter layer, etc.

Gelatin is advantageously used as a binder or protective colloid for photographic emulsions, but hydrophilic colloids can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; hydroxyethyl cellulose,
Cellulose derivatives such as carboxymethylcellulose and cellulose sulfate esters; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinyl A wide variety of synthetic hydrophilic polymeric materials can be used, such as single or copolymers of imidazole, polyvinylpyrazole, and the like.

As the gelatin, in addition to lime-treated gelatin, acid-treated gelatin may be used, and gelatin hydrolysates and gelatin enzymatically decomposed products can also be used.

Examples of gelatin derivatives include gelatin and vegetable compounds such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkansaldoas, vinyl sulfonamides, Frey/imide compounds, polyalkylene oxides, and epoxy compounds. The product obtained by reacting is used. Specific examples are U.S. Patent Nos. 2,614,928, 3,132,945, 3,186,846, and 3
, No. 312,553, British Patent No. 861,414, No. 1
, No. 033,189, No. 1,005,784, and Japanese Patent Publication No. 42-26845.

The gelatin graft polymer is a gelatin grafted with a single (homo) or copolymer of vinyl monomers such as acrylic acid, methacrylic acid, derivatives thereof such as esters and amides, acrylonitrile, styrene, etc. can be used. Particularly preferred are graft polymers with polymers which are compatible with gelatin to some extent, such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like. Examples of these are U.S. Pat. No. 2,763,625, U.S. Pat.
It is described in No. 2,956,884, etc.

Typical synthetic hydrophilic polymer substances include, for example, West German Patent Application (OLS) No. 2,312,708 and U.S. Patent No. 3,62.
No. 0.751, No. 3,879,205, Special Publication No. 1977-
It is described in No. 7561.

The photographic emulsion of the present invention may contain a dispersion of a water-insoluble or sparingly soluble synthetic polymer for purposes such as improving dimensional stability. For example, alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, glycidyl (meth)acrylates, (meth)acrylamides, vinyl esters (e.g. vinyl acetate), acrylonitrile, olefins, styrene, etc. alone or in combination; It is possible to use polymers containing bile combinations such as acrylic acid, methacrylic acid, a, β-unsaturated dicarboxylic acid, hydroxyalkyl (meth)acrylate, sulfoalkyl (meth)acrylate, and styrene sulfonic acid as monomer components. can.

For example, U.S. Patent Nos. 2,376,005 and 2,73
No. 9.137, No. 2,853,457, No. 3,062
, No. 674, No. 3,411,911, No. 3,488,
No. 708, No. 3,525,620, No. 3,607,2
No. 90, No. 3,635,715, No. 3,645,74
No. 0, British Patent No. 1,186,699, British Patent No. 1,307,
Those described in No. 373 can be used.

Any photographic development method may be applied to the light-sensitive material of the present invention. Developing agents used in the developer include dihydroxybenzene-based developing agents, 1-phenyl-3-pyrazolidone-based developing agents, p-aminophenol-based developing agents, etc. -pyrezolidones and dihydroxymethyl 7M or p-aminophenols and dihydroxybenzenes)
Can be used. The light-sensitive material of the present invention may also be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl pisulfite and hydroquinone.

In the above, dihydroxybenzene-based developing agents include, for example, hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone, toluhydrohydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dimethylhydroquinone, etc. 1-722-3-pyrazolidone type developing agents include l-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-3-pyrazolidone, 4-hydroxymethyl-4-methyl-1-phenyl -3-pyrazolidone, 4,4-dihydroxymethyl-1-phenyl-3-pyrazolidone, etc., and p-aminophenol, N-methyl-p-aminophenol, etc. are used as the p-aminophenol developing agent.

A compound that provides free sulfite ions, such as sodium sulfite, potassium sulfite, potassium metabisulfite, and sodium bisulfite, is added to the developer as a preservative. In the case of an infectious developer, sodium formaldehyde bisulfite may be used, which provides almost no free sulfite ions in the developer.

As alkaline agents for the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium sodium carbonate, sodium acetate, potassium triphosphate, jetanolamine, triethanolamine, etc. are used. The pH of the developer is usually set to 9 or higher, preferably 9.7 or higher.

The developer solution may also contain organic compounds known as anticapri agents or development inhibitors. Examples include azoles such as benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobeni/dimidazoles, mercaptothiadiazoles. , aminotriazoles, benzotriazoles,
Nitrobenzotriazoles, mercaptotetrazoles (%i'ζ1-phenyl-5-mercaptotetrazole), etc.; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxazolinthione; niazaindenes, such as triazaindenes, tetraazaindene (% 4-hydroxy substitution (1
, 3, 3a, 7) tetrazaindenes), pentaazaindene, etc.; benzenethiosulfonic acid, benzenesulfinic acid, benzenesulfonic acid amide, sodium 2-mercaptopepzimidazole-5-sulfonate, and the like.

The developer that can be used in the present invention may contain the same polyalkylene oxide as described above as a development inhibitor. For example, polyethylene oxide having a molecular weight of 1,000 to 10,000 can be contained in a range of 0.1 to 10 t/l.

It is preferable to add nitrilotriacetic acid, ethylenediaminetetraacetyincund, triethylenetetraaminehexaacetyincund, diethylenetetraaminepentaacetyincund, etc. as a water softener to the developer that can be used in the present invention.

As the fixer, one having a commonly used composition can be used.

As the fixing agent, in addition to thiosulfates and thiocyanates, organic sulfur compounds known for their effectiveness as fixing agents can be used.

The fixing solution may contain a water-soluble aluminum salt as a hardening agent.

The fixer can also contain a complex of ethylenediaminetetraacetic acid and trivalent iron ions as a sulfurizing agent.

Processing temperature and processing time are set appropriately, but usually 18℃~5
A processing temperature of 0 DEG C. is suitable, while rapid processing of 15 to 120 seconds using a so-called automatic processor is preferred.

Next, the present invention will be explained in more detail with reference to Examples.

However, the present invention is not limited to these examples.

Example 1 Emulsion (A) is prepared according to the following formulation.

Solution I was kept at 40° C., and Solution 2 was added thereto under vigorous stirring. After aging at 40°C for 30 minutes, the pH was lowered to 6°0, gelatin 1002 was added, dissolved, cooled, solidified, shredded, washed with water and desalted.

After each of the emulsions prepared in this way was dissolved at 50°C to a pH of 6.5 and a pAg of 8.9,...silver chloride 1
40 μm of sodium thiosulfate per mole and 15 μg of ammonium gold thiocyanate per mole of silver halide were added, and chemical ripening was carried out at 55° C. for 60 minutes. After ripening, 1-phenyl-5-mercaptotetrazole was added at an amount of 300 μm per mole of silver halide.

This emulsion was divided into several parts, and after adding 50 μ of sensitizing dye V-6, 450 μ of compound M-5, and 700 μ of compound ■-3 per mole of silver halide, the emulsion was left at about 40°C for 45 minutes. After stabilizing the spectral sensitization effect, stabilizer,
After adding a coating aid and a hardening agent, the mixture was coated on a paper support laminated with polyethylene and dried to obtain a sample. The amount of silver coated was 1.8 f/m'. Sample 1 was prepared by providing a gelatin protective layer on this emulsion layer.

On the other hand, as shown in Table 1, the dye of the general formula (11) was added to the above emulsion in an amount of 5 to 50%, and the dyes of the formulas (■), (2), and Samples 2 to 9 were made in the same manner.

This sample was exposed to light using a sensitometer having a light source with a color temperature of 5,400° and a dark red filter that transmits light with a wavelength longer than 700 nm attached to the light source. Subsequently, each sample was developed using D-72 developer for 90 seconds at 20°C.
After stopping, fixing, and washing with water, strimbs with a predetermined black and white image were obtained.

MACBETHTD- manufactured by Macbeth Corporation in the United States
The concentration was measured using a 504 densitometer to obtain the infrared light sensitivity.

The optical density reference points used to determine sensitivity are all at a density of 0.
The score was 75.

Safelight properties are achieved by stacking Fujifilm's Safelight Builter Flat 4 with Toshiba color glass filter IRA-05 and paraffin paper and using an IOW tungsten lamp for 2m.
After irradiation for 20 minutes at a distance of , evaluation was made based on fog (capri after safelight irradiation) when development was performed.

Regarding the image quality, adjust the light amount to give a density of 1.8 and expose, observe the image at the boundary between the unexposed area and the exposed area with a microscope, and if the image of the darkened area is sharp, it is graded as A and defective. The evaluation was divided into three levels, with C1 being C1 and B being in between.

From the above results in Table 1, it can be seen that sample 3.4.7.8 of the present invention has good image quality and can improve safelight suitability with a low sacrifice in sensitivity. That is,
The present invention provides a photosensitive material that has high image quality, high sensitivity, and can be handled under bright safe light.

Example 2 Mixed ripening and chemical sensitization were carried out in the same manner as in Example 1,
A silver bromide emulsion was prepared.

To this emulsion, 70 μg of V-25 was added per mole of silver halogenide.
Add 350■ of compounds of and ■-3 and 550■ of ■-2 and leave at 40℃ for 45 minutes to stabilize the spectral sensitization effect, then add stabilizer, coating aid, and hardening agent. From, the amount of silver coated on the polyethylene terephthalate film was 3.9 β
It was applied so that

On this emulsion layer, A-12 was added as a coating aid to 3η height and B
-8 to 1.5f/f? methyl methacrylate polymer 52/rr? as a matting agent. Sample 10 was prepared by adding 1 layer of A or B as a mordant and forming a gelatin protective layer with a thickness of 1.0 μm.
．． I made 15.

On the other hand, in the emulsion layer, the dye of general formula (1) is 7.5 μ/n?
Each sample 10.1 was present as shown in Table 2.
Sample 11.16 was prepared in the same manner as in Example 5.

Also - dye of formula (It), (2), (goods) at 30η/
rr? Samples 10, 11, 15, and 16 were present, respectively.
Samples 12 to 14 and 17 to 19 were made in the same manner.

Mordant A H3 Mordant B The film sample thus prepared was evaluated in the same manner as shown in Example 1 by exposing it to light, stopping development, and washing with water after fixing.

To evaluate the residual color, check the coloring (
Decolorization of the dye (insufficient decolorization) was visually judged.

Evaluation was made on a four-point scale: A with almost no residual color, B with residual color but no practical problem, C with poor residual color, and D with extremely large residual color.

The results are shown in Table-2.

From the above results in Table 2, it can be seen that the case of the present invention is excellent in that there is little decrease in sensitivity, less capri is produced after safelight irradiation, and there is little residual color.

Claims (1)

[Scope of Claims] A layer containing at least one dye represented by the following general formula (I) and at least one dye represented by the following general formulas (II), (III), or (IV) on a support. A silver halide photographic material comprising: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1 and R_2 may be the same or different and represent a substituted or unsubstituted alkyl group, and Z_1
, Z_2 each represent a group of nonmetallic atoms necessary to form a substituted or unsubstituted benzo-fused ring or naphtho-fused ring. Y_1 and Y_2 may be the same or different from each other and represent a group of nonmetallic atoms necessary to form a cyclic structure via the 3-position carbon of the indole nucleus. However, the dye molecule must have at least three acid groups. L_1, L
_2 and L_3 represent a substituted or unsubstituted methine group,
X_1 represents an anion. n_1 is 1 or 2, and is 1 when the dye exhibits an inner salt. ) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_1_1 and R_1_2 are an alkyl group, an aryl group, a cyano group, -COOR_1_5, and -CONR_, respectively.
1_5R_1_6, -COR_1_7, -SO_2R_
1_7, -SOR_1_7, -SO_2NR_1_5R
_1_6, -OR_1_5, -NR_1_5R_1_6
, -NR_1_6COR_1_7, -NR_1_5CO
NR_1_5R_1_6 or -NR_1_6SO_2R
_1_7 (here R_1_5, R_1_6 are hydrogen atoms,
represents an alkyl group or an aryl group, R_1_7 represents an alkyl group or an aryl group, R_1_5 and R_1
_6 or R_1_6 and R_1_7 may be connected to form a 5- or 6-membered ring. ), Q_1_1, Q_1
_2 represents a methylene group, Y_1_1 and Y_1_2 each represent a hydrogen atom, an alkyl group, a sulfo group, a carboxy group, or an aryl group having at least one sulfo group or a carboxy group, m_1_1 and m_1_2 each represent 0, 1, 2 , 3, 4, 5. n_1_1 is 0,
Represents 1 and 2. ] General formula (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, Z_2_1 is a nonmetallic atom necessary to form the heterocyclic nucleus of benzthiazole, naphthothiazole, benzoxazole, naphthoxazole, indole, or benzindole) represents a group. R_2_1 represents a substituted or unsubstituted alkyl group, R_2_2 represents a substituted or unsubstituted aryl group. L_2_1 and L_2_2 represent a methine group, and n_2_
1 represents 1 or 2. X_2_1 represents an anion, m_2_1 represents 1 or 2, and is 1 when the dye molecule forms an inner salt. However, there is at least 1 in the dye molecule.
It shall have 100 acid groups. ) General formula (IV) ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ (In the formula, Z_3_1 represents a carbocyclic or heterocyclic ring forming group, R_3_1 represents an aryl group or a heterocyclic ring forming group, n_3_1 represents 0 or 1, n_3_2 is 0, 1,
2, but n_3_1 and n_3_2 are never 0 at the same time. )