JPH021837A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce sensitivity of a silver halide photographic sensitive material for visible rays and to elevate the sensitivity thereof to infrared rays by incorporating specified two kinds of dye into the silver halide photographic sensitive material compsn. CONSTITUTION:A dye expressed by the formula I which is effective for prevention of irradiation and prevention of halation, and a dye expressed by the formula II which is effective for providing safety against safelight, are incorporated into the title sensitive material. In the formulas, each R1 to R6 is an alkyl group; each Z1 and Z2 is an atomic group necessary for forming a benzo condensed ring or a naphtho condensed ring; each L1 to L3 is a methine group; X1 is an anion; n1 is 1 or 2; each R11 and R12 is an alkyl group, aryl group, etc.; each Q11 and Q12 is a methylene group; each Y11 and Y12 is sulfonic acid group, carboxylic acid group, etc.; each m11 and m12 is 1 to 5. Further, a desired tricarbocyanine pigment and/or a 4-quinoline nucleus-contg. dicarbocyanine pigment may be added for the purpose of sensitization to infrared rays.

Description

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

(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 side farther from the support than the photographic emulsion layer of the photographic light-sensitive material.

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.

The light scattered during or after passing through the photographic emulsion layer is 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 is returned to the photographic emulsion layer.
In order to prevent image blurring, that is, halation, which is caused by the use of photographic materials, a colored layer is provided between the photographic emulsion layer and the support, or 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 a multilayer color photosensitive material, an antihalation l-layer may be placed between each layer.

Coloring the photographic emulsion layer to prevent a decrease in image sharpness (this phenomenon is commonly referred to as irradiation) due to scattering of light in the photographic emulsion layer. is also carried out.

These layers to be colored often consist of existing aqueous colloids, so for their coloring water-soluble dyes are usually incorporated into the layers. This dye must satisfy the following conditions.

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

(2) Photochemically inert. In other words, the performance of the halogenated photographic emulsion should not be adversely affected in a chemical sense, such as deterioration of pests, latent image regression, or fog.

(3) Is it bleached during the photographic processing process? No. 8 must be removed to leave no harmful coloration on the photographic material after processing.

Many dyes that absorb visible light or ultraviolet rays 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 above-mentioned (I1 (2) (3+) condition.

For example, JP-A-62-123454 and JP-A-63-5554.
No. 4 describes a heptamethine cyanine dye having an indolenine core. However, these dyes
It has a maximum absorption wavelength of 750 nm or more, and is sufficiently effective for preventing halation and irradiation when added to infrared silver halide photographic materials that are spectrally sensitized to the infrared region of 750 nm or more. However, in order to handle this sensitive material under bright safe light, which can be called a bright room, it is necessary to use a dye with a wavelength shorter than 750 nm in combination because the absorption waveform is sharp.

Among dyes with absorption maximum wavelengths shorter than 750 nm, oxonol dyes with two pyrazolone nuclei have little negative effect on photographic emulsions and have the property of being decolorized in processing solutions containing sulfites. It has been used as a dye for photosensitive materials as a long-lasting and useful dye.

For example, British Patent Nos. 506,385 and 1,177.
No. 429, No. 1,311,884, No. 1338.79
No. 9, No. 1,385,371, No. 1.467.214
No. 1,433. ' No. 102, 1,553.51
No. 6, JP-A No. 48-85, 130, JP-A No. 55-161.
No. 233, No. 59-111.640, No. 62-273
Oxonol dyes having a pyrazolone nucleus are known, such as those described in No. 527-2. However, even if these dyes have a small shadow 9 on the photographic emulsion itself, it is thought to be caused by spectral sensitization in unnecessary areas or by desorption of the sensitizing dye for spectrally sensitized emulsions. It has the disadvantage of causing a decrease in sensitivity.

(Problems to be Solved by the Invention) The first object of the present invention is to create a hydrophilic colloid colored with a water-soluble dye that does not adversely affect the photographic properties of a photographic emulsion and is easily decolorized by photographic processing. An object of the present invention is to provide a silver halide photographic material having layers. A second object of the present invention is to provide a silver halide photographic material that has a good image, has sufficiently low sensitivity to visible light, and is highly sensitive to infrared light. .

(Means for Solving the Problems) An object of the present invention is to provide at least the following general formula (I) on a support.
) and at least a dye represented by the following general formula (II).

General formula (I) %Formula% (In the formula, R1, R2, R3, R4, R5 and R6 may be the same or different from each other and represent a substituted or unsubstituted alkyl group, and Zl and Z2 are each Indicates a group of nonmetallic atoms necessary to form a substituted or unsubstituted benzo-fused ring or naphtho-fused ring.

However, Rl+ R2+ R1+ R4, R5, Rh,
Z 1 and Z2 represent groups that allow the dye molecule to have at least 3 acid groups. L, , L, , R3 represent a substituted or unsubstituted methine group, and Xl represents an anion. nl is 1 or 2, and is 1 when the dye forms an inner salt. ) General formula (II) [wherein R11, R, □ are each an alkyl group, an aryl group, a cyano group, -COOR, , -CONR,, R, 6,
COR,...5O2R1? , -3OR, ,5o2NR
,,R,6,-OR,9,-NR1,R16,NR,,
COR,,,NR+ s CON R+ s R+
b or -NR,6SO□RI7 (here RIS, RI6
represents a hydrogen atom, an alkyl group or an aryl group, and R1
7 represents an alkyl group or an aryl group, and RIS and R1
6 or R11, and R17 may be connected to form a 5- or 6-membered ring. ), Q + + and Q1□ each represent a methylene group, and Y15 and Y1□ each represent a sulfonic acid group, a carboxylic acid group, or an aryl group having at least one sulfonic acid group or carboxylic acid group. m1□
represent 1.2.3.4 or 5, respectively. ]General formula (I)
In the above, the alkyl group represented by R1, R2, R3, R4, R1 or R6 is preferably a lower alkyl group having 1 to 5 carbon atoms (e.g. methyl group, ethyl group, n-propyl group, n-butyl group, isopropyl group). , n-pentyl group, etc.), and may have a substituent (for example, a sulfonic acid group, a carboxylic acid group, a hydroxyl group, etc.). More preferably, R1+ and R4 have sulfonic acid groups and have 1 to 5 carbon atoms.
represents a lower alkyl group (e.g. 2-sulfoethyl group, 3-sulfopropyl group, 4-sulfobutyl group, etc.),
Rz, Rz, Rs, and R6 are each preferably a methyl group or an ethyl group.

2. Substituents of the benzo-fused ring or naphtho-fused ring formed by the nonmetallic atom group represented by 22 include a sulfonic acid group, a carboxylic acid group, a hydroxyl group, a halogen atom (for example, F, CI, Br, etc.), a cyan group, and a substituent. Amino group (
For example, dimethylamine group, diethylamino group, ethyl-
4-sulfobutylamino group, di(3-sulfopropyl)
amino group, etc.), or a substituted or unsubstituted group having 1 to 5 carbon atoms bonded to the ring directly or via a divalent chain group
Alkyl groups (e.g. methyl, ethyl, propyl)
J, methyl group, etc. (preferred substituents include sulfonic acid group, carboxylic acid group, hydroxyl group, etc.), and divalent linking groups include, for example, -ON HCO, N
HS Oz, N)I COO-N HCO
N H--COO--CO-SO,-, etc. are preferred.

Ll, L2. The methine group represented by L3 is preferably an unsubstituted methine group, but it may also have a substituent JAW, and examples of the substituent include a substituted or unsubstituted lower alkyl group having 1 to 5 carbon atoms (e.g. methyl group, ethyl group). group, 3-hydroxypropyl group, benzyl group, 2-sulfonidel group, etc.),
Halogen atoms (e.g. F, Cj', Br, etc.), substituted or unsubstituted oryl groups (e.g. phenyl group, 4-chlorophenyl group, etc.), lower alkoxy groups (e.g. methoxy group, ethoxy group, etc.), Examples include.

In addition, the substituent of the methine group represented by L l + L z and L 3 is bonded to form a 5-membered ring containing three methine groups (
For example, a cyclopentene ring) or a 6-membered ring (for example, a 4.
4-dimethylcyclohexene ring).

Specific examples of the anion represented by Xl include halogen ions (Cj!-, Br-1''), I)-toluenesulfonic acid ions, and ethyl sulfate ions.

Specific examples of the dye compound represented by the above-mentioned format (I) used in the present invention are shown below, but the scope of the present invention is not limited thereto.

/ / / / (I-4) CI-2) (I-5) (C)L2)2 ob (CH2)2 03K (I-3) (I-6) 0e to 803 CI-8) δO″3 ([-13) (CH2)4 ob (I-14) (I-15) o3G (■ (CH2)4 (CH2)4 o3K (I-12) So, K (I-16) (CH2).

So, K (I-17) (I-18> So, H YuN (C2H5)3 0r To So3 (CH2) 4 (CH2)4 OF S　O3N　a (I-20) (CH2)3 (CH2)3 Oe ONa (I-21) (CH2).

(CH2)4 oi o3K (I-25) (I-26) CI-27) 03K (■ (I-23) (I-28) (I-29) (CH2/).

SO? (I-30) (CH2)3 0Q (CH) OK (C12).

In S03, the dye represented by the format ([) is Japanese Patent Application Laid-open No. 6212345.
No. 4 or No. 63-55544, or can be synthesized by a similar method.

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

The alkyl groups represented by R1, R1□, RIS, R16 and R17 include alkyl groups having 1 to 8 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-
butyl, isobutyl, t-butyl, n-amyl, n-hexyl, n-octyl, isoamyl) are preferred, and substituents (for example), halogen atoms such as chlorine, bromine, phenyl group, hydroxyl group, cyano group, alkoxy groups (e.g. methoxy, ethoxy, tosyl, hydroxyethoxy), ori-luoquine groups (e.g. phenoxy, p-methoxyphenoquine)
, carboxyl group, sulfo group, amino group, substituted amino group (eg dimethylamino, diethylamino)].

Ro, R12, R15% R16 and R1? The aryl group (for example, phenyl, naphthyl) represented by is preferably a phenyl group, and a substituent (for example, a halogen atom such as fluorine, chlorine, or bromine, a sulfo group, a carboxyl group, a hydroxyl group, a cyano group, a carbon number of 1 to 4) It may have an alkyl group (eg, methyl, ethyl, n-propyl), an alkoxy group (eg, methoxy, ethoxy), or an alkoxy group (eg, phenoxy).

Y, YlzT: The aryl group having at least one sulfonic acid group or carboxylic acid group is preferably a phenyl group or a naphthyl group, and substituents other than the sulfonic acid group or carboxylic acid group [e.g. ~4 alkyl groups (e.g. methyl, ethyl), alkoxy groups (e.g. methoxy, ethoxy, halogen atoms (fluorine, chlorine, bromine)
, carbamoyl groups (e.g. methylcarbamoyl, ethylcarbamoyl), sulfamoyl groups (e.g. ethylsulfamoyl), cyanogen groups, nitro groups, alkylsulfonyl groups (e.g. methanesulfonyl), arylsulfonyl groups (e.g. benzenesulfonyl), amino groups (e.g. dimethyl amino, diethylamine), an acylamino group (eg, acetylamino), a sulfonamide group (eg, methanesulfonamide), or a hydroxyl group].

The methylene group represented by Qll-Ql□ may have a substituent (eg, methyl, ethyl, hydroxyl group, etc.).

RIS and R16 or RI6 and R1? Examples of the 5- or 6-membered ring formed by linking these include a piperidine ring, a morpholine ring, a pyrrolidine ring, and a pyrodone ring.

The methine group represented by LIl, LI□, and L12 may have a substituent (eg, methyl, ethyl, cyano, phenyl, chlorine atom, sulfoethyl).

In the above-mentioned form (II), the sulfo group, the carboxyl group, and the enol moiety of the pyrazolone ring are both in the '1m1FJl type and in the salt form (eg, Na salt, I(salt, (CZ II)).

NH salt, pyridinium salt, ammonium salt).

Preferred formats (IT) above are Y, Y
lz represents a sulfonic acid group, or m, ,=m,
, = l, and YI1%YI2 represents a phenyl group having at least one sulfonic acid group.

Specific examples of dyes represented by the general formula (formerly) are shown below.
The present invention is not limited to these.

11-] SO, Na 5O,Na ■ l-3 C11゜ C11□ 1″＼ノ Kenno ■ ■ C1(2 CI+□ ■ ■ C1bClbSOJ CIl, CII□SO, If ■ ■ I-11 ■-12 ■ ■ ■ ■ ■ ■ ■ C11゜ 5u coNa ■ ■ U(L;1h)4Sυ=Na 0(Clh)asOJa ■ L ■ ■-24 ■ ■ ■ (C11□)asOJ (C11□), SO, to! ■-25 C11゜ C1+□ I ■ (C11□), So, K (Cllz) tsOJ [1-31 ■ (C11□), SO, K (C11□) to sso3 B C11゜ ■ C11! ■ ■-40 C1l□ C11! ■ ■ ■ ■-41 ■ ■ ■ ■ ■ ■ (Cllz) 1sOJa (C1lz) 3sOINa ■ ■ ■ ■-53 ■ C1(.

CI+3 ■-55 ■-57 (CII2) 5sOxK (CI(t) 1sOJ -C The dye expressed by formula (+1) is JP-A-49=512
No. 5, No. 49-99620, No. 50-145125,
No. 50-147712, No. 59111640, No. 6
No. 2-273527, Japanese Patent Application No. 62-79483, No. 6
2-110333 or can be synthesized by a similar method.

The above-mentioned dye is dissolved in a suitable solvent (eg, water, alcohol (eg, methanol, ethanol, etc.), methyl cellosolve, etc., or a mixed solvent thereof) and added to the coating solution for the hydrophilic colloid layer of the present invention.

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

The specific amount of dye to be used varies depending on the purpose and is difficult to determine uniformly, but in general, the preferred amount is within the range of 10g/nf-1g/bo, especially 10-'g/nf-1g/b, and 5g/b. can be found.

The photographic dye represented by the above-mentioned type (I) 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.

Dyes of type (I) above are also particularly useful as antihalation dyes, in which case they are added to the backside of the support or to the layer between the support and the emulsion layer. .

The photographic dyes of the above-mentioned form (■) of the present invention are particularly useful as dyes for imparting safelight safety, in which case they may be combined, if necessary, with dyes that absorb light at other wavelengths. It is added to layers (such as protective layers) located on top of the photographic emulsion layer.

In addition, the photographic dye of the present invention can be advantageously used as a filter dye.

The photographic dye of the present invention can be introduced into the desired photographic constituent layer by a conventional method. That is, it is sufficient to add a solution of a dye at an appropriate concentration to an aqueous solution of a hydrophilic colloid as a binder for a photographic constituent layer, and apply this solution onto 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 halide 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. .

The light-sensitive materials of the present invention include color photographic materials as well as black-and-white 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 IM is usually sufficient. The amount of coated silver is preferably in the range of Ig/ni to 8g/ITf.

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 in-situ 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 regular grains having a regular crystal structure such as a cube, octahedron, or dodecahedron, or may have an irregular crystal shape such as a spherical shape. It may be 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, as described in Research Disclosure (
RD), Sou 17643 (December 1978), 22-
Page 23, “1. Emulsion preparation
ration and types)” and the same, Nn
18716 (November 1979), p. 643.

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 Phys
ique PhotoBraphiqueI'aul
Montel+ 1967), by Duffin [Photographic Emulsion Chemistry J, published by Focal Press, CG, F, Duff
inPhotographic EmulSion C
hemistry (Focal Press.

1966), “Manufacture and Coating of Photographic Emulsions” by Zelikman et al.
, published by Focal Press (V, L, Zelikma
neL al, Making and C
oating Photographic Emulsi
on, Focal Press, 1964), etc. It can be prepared using recognized methods.

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. 3,271,155) are used as silver halide solvents to control grain growth.
No. 7, No. 3574628, No. 3,704,130
No. 4゜297.439, No. 4,276.37
No. 4, etc.), thione compounds (e.g., JP-A-53-144)
No. 319, No. 53-82, 408, No. 55-77
．． 737, etc.), amine compounds (e.g., JP-A No. 54-
No. 100,717, 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 root 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 PAg is kept constant in the liquid phase in which silver halide is produced, that is, the so-called Chondrald-Daffludient method, can be used. According to this method, the crystal form is regular. This gives a silver halide emulsion with nearly uniform grain size.

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 sulfur enhancers such as Allyl thiocarbamide, thiourea, thiosulfate, thioether and cystine;
Potass:m chloro Pa1ladate
Metal sensitizers such as t' such as ) can include reduction sensitizers such as tin chloride, phenylhydrazine, and reductone.

The silver halide emulsion used in the present invention is spectrally sensitized with a known spectral sensitizing dye, if necessary. Research Disclosure for the spectral sensitizing dye used
(Research Disclosure) No. 176
Volume, Nα17643. Those described in Section (I, February 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 a sensitization maximum in a wavelength range of 750 nm or more. Sensitizing dyes for infrared sensitization are not particularly limited, but tricarbocyanine dyes and/or 4-quinoline nucleus-containing dicarbocyanine dyes are preferred from the viewpoint of exacerbation performance and safety. Infrared spectral enhancement of a silver halide emulsion may sometimes deteriorate the stability of the emulsion in a solution state. 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 having the following general formula (I[[a) or (If
fb).

-Formation (Illa) hl tK (X crystal) +1g+-1 General formula (Illb) ZI x (X word) nz+-1 In the formula, R2+ and Rzffi may be the same or different, and each represents an alkyl group ( Preferably a carbon atom number of 1 to 8, such as a methyl group, an ethyl group, a propyl group,
butyl group, pentyl group, heptyl group, etc.), substituted alkyl group (for example, carboxy group, sulfo group,
A cyano group has a halogen atom (e.g. fluorine atom, chlorine atom, bromine atom, etc.), a hydroxy group, an alkoxycarbonyl group (8 or less carbon atoms, e.g. a methoxycarbonyl group, an ethoxycarbonyl group, a benzyloxycarbonyl group), an alkoxy group ( 7 or less carbon atoms, e.g. methoxy group, ethoxy group, propoxy group, butoxy group, benzyloxy group), aryloxy group (e.g. phenoxy group, p-tolyloxy group, etc.), acyloxy group (
3 or less carbon atoms, e.g. acetyloxy group, propionyloxy group), acyl group (8 or less carbon 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 L N,N-dimethylsulfamoyl group, morpholinosulfonyl group, etc.), aryl group (e.g. phenyl group, p -hydroxyphenyl group, p-carboxyphenyl group, p-sulfophenyl group,
an alkyl group (the number of carbon atoms in the alkyl part is 6 or less) substituted with an α-naphthyl group, etc. However, this substituent is 2
A combination of two or more may be substituted with an alkyl group. ).

R2° represents a hydrogen atom, a methyl group, a methoxy group, or an ethoxy group.

R23 and RZ4 each represent a hydrogen atom, a lower alkyl group (for example, a methyl group, an ethyl group, a propyl group, etc.), a lower alkoxy group (for example, a methoxy group, an ethoxy group, a propokine group, a butoxy group, etc.), a phenyl group, or a benzyl group. .

R2S is a hydrogen atom, a lower alkyl group (e.g. methyl group,
ethyl group, propyl group, etc.), lower alkoxy group (e.g. methoxy group, ethoxy group, propoxy group, butoxy group, etc.), phenyl group, benzene, each substituted or unsubstituted alkyl group (alkyl moiety has 1 to 18 carbon atoms, Preferably, 1 to 4 represent a methyl group, an ethyl group, a propyl group, a butyl group, a benzyl group, a phenylethyl group), an aryl group (such as a phenyl group, a naphthyl group, a tolyl group, a P-chlorophenyl group, etc.), and W21 and It can also be linked with Wtt to form a 5- or 6-membered nitrogen-containing heterocycle.

D2° represents a group of atoms necessary to complete a divalent ethylene bond, e.g. ethylene or triethylene, and this ethylene bond is replaced by one, two or more suitable groups, e.g. Alkyl W (e.g. methyl group, ethyl group, propyl group, isopropyl group, butyl group, 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 isopropoxy group,
butoxy group, etc.).

D□ and D2□ each represent a hydrogen atom. However, D
zI and D2□ can also work together to form a divalent ethylene bond having the same meaning as above.

Z2° and Zt+ each represent a nonmetallic atom nγ necessary to complete a 5- or 6-membered nitrogen-containing heterocycle, such as a thiazole nucleus [e.g., benzodeazole, 4-chlorobenzothiazole, 5-chlorobenzothiazole, 6 -Chlorbenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole,
6-methylbenzothiazole, 5-bromobenzothiazole, 6-promohenzothiazole, 5-iodobenzothiazole, 5-phenylbenzothiazole, 5-methoxyhenzothiazole, 6-ethoxybenzothiazole,
5-Ethoxybenzothiazole, 5-carpoxyhenzo'thiazole, 5-ethoxycyclobenzothiazole, 5-phenylated ndzothiazole, 5-fluorobenzothiazole, 5-trifluoromethylbenzothiazole, 56-dimethyl Benzothiazole, 5-hydroxy 6-methylbenzothiazole, tetrahydrohendithiazole, 4-phenylbenzothiazole, naphthoC2,1-d)thiazole, naphtho[1°2-d]thiazole, naphtho(2,ld)thiazole, 5 -methoxynaphthoC1,2-d)thiazole, 7-ethoxynaphtho(2,1-d)thiazole, 8-methoxynaphthoC2
,1-d) Thiazole, 5-methoxynaphthoC2,3-
d) thiazole], zelenazole core [e.g. henzoselenazole, 5-chlorobenzimidazole, 5-methoxybenzozelenadur, 5-methylbenzimidazole, 5-hydroxybenzozelenazole, naphtho(2
, 1-d) zelenazole, naphtho(I, 2-d) zelenazole, etc.], oxazole core [benzoxazole,
5-chlorobenzoxazole, 5-methylbenzoxazole, 5-bromobenzoxazole, 5-fluorobenzothiazole, 5-phenylbenzoxazole, 5-methoxybenzoxazole, 5-trifluorobenzoxazole, 5-hydroxybenzoxazole, 5 -carboxybenzoxazole, 6-methylbenzoxazole, 6-chlorobenzoxazole, 6-
Methoxybenzoxazole, 6-hydroxybenzoxazole, 4.6-dimethylbenzoxazole, 5
ethoxyhenzoxazole, naphtho[2,ld]oxazole, naphtho(I,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-dimethyl-5-cyanoindolenine, 33-dimethyl-5-
methoxyindolenine, 33-dimethyl-5-methylindolenine, 33-dimethyl-5-chloroindolenine, etc.), imidazole core (e.g. l-methylbenzimidazole, l-ethylhenzimidazole, IJ methyl 5-chlorobenzo Imidazole, 1-ethyl-5-chlorobenzimidazole, ■-methyl-5,6-dichlorobenzimidazole, 1-ethyl-56-dichloro-\
Nzimidazole, ■-alkyl-5-methoxyhencyimidazole, l-methyl-5-cyanobenzimidazole, l-ethyl-5-cyanohencyimidazole, 1-methyl-5-fluorobenzimidazole, 1-ethyl-5
-fluorobenzimidazole, I phenyl-5,6-
Dichlorobenzimidazole, 1-allyl-5,6-dichlorobenzimidazole, 1-allyl-5-chlorobenzimidazole, 1-phenylhenzoimidazo-1
1 niphenyl-5-chlorobenzimidazole, ■
-methyl-5-trifluoromethylbenzimidazole, 1-ethyl-5-trifluoromethylbenzimidazole, 1-ethylnaphtho(I,2-d)imidazole, etc.), pyridine nuclei (e.g. pyridine, 5-methyl-2-pyridine, -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.

XZ+ represents an acid anion.

nz+ represents 1 or 2.

Particularly useful among the 4-quinoline nucleus-containing dicarbocyanine dyes used in the present invention are those having the following general formula (Iffc) (XB) nzz I where R1b and Rz7 are the same as Rz+ and R2□, respectively. represents meaning.

R2B represents the same meaning as R23. However, RZI+ is preferably a lower alkyl group or a benzyl group.

VZ+ is a hydrogen atom, a lower alkyl group (for example, a methyl group,
ethyl group, propyl group, etc.), alkoxy 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.) ).

Z2□ represents the same meaning as Z2° and Ll.

X2□ represents the same meaning as XZ+.

m2.・n's P represents l or 2, respectively.

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

(III-/) 02H5 2H5 (III-7) 2H5 ■− CH2COOH ■− ■− r- (III-/J) r■-7j＞ Cm-/9) (m-20) (I[l-27) (III-/　Otsu) (III-/7) (II[-/r) C'ff1-. 22) ([[[-j hiro) knee α04- ti5t,;6t,;,1-15 c'O4- knee 2H5 (llll-2j) (■-kot) ([l-27) ([1-J/) (■ 3 pieces) (Ill-JJ) (llll--1! f) ■− (I[1--2ri) (,CH2)3S03- (IU-JO) (I [[-J 4') (CH2)3S03- (III-Jj) (C)12)2(JH r- (■-36) (C1(□)4S(J3- (CH2)4SO3- ■− CH2C(J(J- (■-37) (I [I-4' 0) (■-JJ’n 2I-i5 ■− (ill-4/) C.

(III-JP) (■-g, 2) tO4- α04- The above-mentioned infrared sensitizing dye used in the present invention contains j×10−7 mol to J′×10−3 mol per mol of silver halide, Preferably /X/0-67k~/X/0.
3 moles, particularly preferably λ×l0-6 moles! ×70-
It is contained in a silver halide photographic emulsion in a proportion of 4 moles.

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 cellosol, 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 Patent No. 3. l
A method in which a dye is dissolved in a completely volatile organic solvent, the solution is dispersed in a hydrophilic colloid, and this dispersion is added to an emulsion, as described in the specification of LT.
1. Do not dissolve water-insoluble dyes as described in t-2≠/rj, etc. Dispersion in an aqueous solvent and addition of this dispersion to the entire emulsion: US Patent No. J,! 2. Z, /
3! A method of dissolving a dye in a surfactant and adding the solution into an emulsion as described in the specification; JP-A-Shoyo/-7
A method of dissolving a red-shifting compound* as described in No. 4<A, 2≠ and adding the solution into an emulsion;
- A method such as that described in JP-A No. 5 O-RORST, in which a dye is dissolved in a substantially water-free acid and the solution is added to an emulsion, is used. Other additions to emulsions include U.S. Patent No. λ.

R/Co, 3μ3, same No. 3.34L2. The methods described in tOJ No., λ, 7ri 6.2g 7, 31 Iwakota, r3yo, etc. can also be used. The infrared sensitizing dye of Formation (I) above may also be uniformly dispersed in the silver halide emulsion before being coated on a suitable support; It can be distributed in any process.

The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. For example, U.S. Patent No. J, 703.
No. 377, same No. 2. tl#,! ;It! No. J,
3F7.01.0, same No. 3. t/j.

No. 136, same No. 3. Otsu, 2g, A4 number, British patent cylinder 7.2≠2. J'r! No. 1. Kota 3. and No. 22,
Japanese Patent Publication No. J-4t936, Japanese Patent Publication No. 4t≠-741030, Japanese Patent Publication No. J-70773, US Patent No. 3≠/M, 227
No. 3, U.S. Patent No. 3. /, /!
;, No. 1/3, No. 3. T/,! ;.

A3.2, same No.3. t/7. ．． 2 Tata No. 3゜/
, 3, the sensitizing dyes described in No. 72/, etc. can be used.

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

General formula (IV) In the formula, -A- represents all covalent aromatic residues, and these are -
SO3M group [where M represents a hydrogen atom or a cation (eg, sodium, potassium, etc.) that provides water solubility.

] may be included.

-Person-( is useful, for example, selected from the following -A1 or -A2-. However, R, 3, R, 3□, R3B
Or when R31 does not contain -5O3Nf, -A-
is selected from the group -A1-.

-A-2S (J3M \ \ 803M 03M 50M 503M 803M 03M 5OM S (J3M, etc.) where M represents a hydrogen atom or a cation that confers water solubility.

-A2-: R, a Xrt, 3 and "34 each represent the hydrogen source 31'
32 children, hydroxy group, lower alkyl group (the number of carbon atoms is preferably /-ff. For example, methyl group, ethyl group, n
-propyl group, nFdutyl group, etc.)) alkoxy group (preferably 7 to g carbon atoms, e.g. methoxy group, ethoxy group, propoxy group, butoxy group, etc.), aryloxy group (e.g. phenoxy group, naphthoxy group, 0-
troxy group, p-sulfophenoxy group), halogen atom (e.g. chlorine atom, bromine atom, etc.), heterocyclic nucleus (
morpholinyl group, piperidyl group, etc.), alkylthio groups (e.g. methylthio group, ethylthio group, etc.),
Heterocyclylthio groups (e.g. benzothiazolylthio group, benzimidazolyl group, phenyltetrazolylthio group, etc.), arylthio groups (e.g. phenylthio group, tolylthio group), amine groups, alkylamino groups or substituted alkylamino groups (e.g. methyl Amine group, ethylamino group, propylamino group, dimethylamine group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di(β-hydroxyethyl)amine group, β-sulfoethylamino group ),
Arylamino group or substituted arylamino group (e.g. anilino group, 0-sulfoanilino group, m-sulfoanilino & p-sulfoanilino group, o-toluidino group, m
-toluidino 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), heterocyclylamino group (
(e.g., copenzothiazolylamino group, copyraziluamino group, etc.), substituted or unsubstituted aralkylamino groups (e.g., benzylamino group, o-anisylamino group, m
-anisyl amino group, p-anisyl amino group, etc.),
Represents an aryl group (such as a phenyl group) or a mercapto group. "al, R, 2, FL, R54 may be the same or different from each other. When -Am is selected from the group -A2-, R3, R-1□, R, R3, At least one of them must have one or more sulfo groups (which may be free acid groups and may form salts).W represents -ch= or -N=, preferably -CH= is used.

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

(IV-/) 4',≠'-bis[≠, t-di(penzothiazolyl-corchio)pyrimidin-2-ylaminocystilbene-2, co'-disulfonic acid disodium salt (IV--2) lA, μ'-bis[≠, t-di(penzothiazolyl-co-amino)pyrimidin-2-ylamino)]stilbene-2,2'-disulfonic acid disodium salt IV-J) μ,≠'-bis[g , O-di(naphthyl-λ-oxy)pyrimidin-2-ylamino]stilbene-22,2'(IV-μ) (IV-1 (IV-,4) (IV-7) (IV-J') - Disulfonic acid disodium salt≠, Gl-bis[≠, 2-di(naphthyl-2-oquine)pyrimidine-koylamino]bibenzyl!, 21-disulfonic acid disodium salt≠, G'-binu (<z ,,4-dianilinopyrimidine-
choylamino) stilbene-,2,,! '-Disulfonic acid resin sodium salt, μ'-bis[≠-chloro- (2-naphthyl) hirimishin-choylamino] biphenyl-! .

λ'-disulfonic acid resin sodium salt 4t 4/, '-bis[μ,6-di(/-phenyltetrazolyl-tthio)pyrimidine-λ-ylamino]styrine-, 2. ．． 2'-disulfonic acid disodium Shiohiro, g'-bis[μ, Otsu-di(penzimidazolylucochio)pyrimi(■-ta) (IV-/0) (IV-//) (N-/ 2) ('N-73> zin-koylamino], stilbene-2,2'-disulfonic acid disodium salt 41, , tl /--bis(μ, z-diphenoquinopyrimidin-2-ylamino) stilbene -2,2'-disulfonic acid disodium salt μ,μ'-bis(I,LIA-diphenylthiopyrimidin-2-ylamino) Stilbene-+2,2'-disulfonic acid disodium salt≠ 1)/-bis(≠ , O-dimercaptopyrimidine-λ-ylamino) biphenyl = λ 2/-disulfonic acid disodium salt 4t, ≠/-bis(lLl, /,-dianilino-triazin-2-ylamino) stilbeneco, 2'-disulfonic acid Disodium salt 4L, Hiro'-bis(≠-anilino 2-hydrokyltriazin-2-ylamino)stilbene-2,2'-disulfonic acid disodium salt (IV-/μ) ≠, ≠'-bis[≠- Disodium naphthylamino-A-anilinotriazine-co-ylamino)stilbene-1,2'-disulfonate Among these specific examples, (IV-/) to (■-/ko) are preferable, especially NV -/), (■-ko), CN-3),
(IV-'l), NV-1, and (IV-7) are preferred.

The compound of general formula (IV) is silver chloride 1 in the emulsion.
Approximately 0.0 per mole. From O/Gram! Advantageously used in gram quantities.

The ratio (weight ratio) of the above-mentioned infrared sensitizing dye of the present invention and the compound represented by -formation (IV) is as follows: infrared sensitizing color chart/
Compound represented by general formula (IV)=//l~//1
The range 00 is advantageously used, especially //, 2 to //!
A range of 0 is advantageously used.

The compound represented by the general formula (IV) used in the present invention can be directly dispersed in an emulsion, or can be dispersed in a suitable solvent (for example, methyl alcohol, ethyl alcohol, methyl cellulose, water, etc.) or a mixed solvent thereof. It can also be added to the emulsion by dissolving it in the emulsion. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid. They can also be dispersed and added into the emulsion by the method described in Japanese Patent Application Laid-open No. Shoyo Q-10//R.

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

-Formation (V) In the formula, Z41 represents a group of nonmetallic atoms necessary to complete a J-membered or O-membered nitrogen-containing heterocycle, such as thiazoliums (
For example, thiazolium, Hiro-methylthiazolium, benzothiazolium, j-methylbenzothiazolium,! -Chlorobenzothiazolium,! -methoxybenzothiazolium, t-methylbenzothiazolium, 2-methoxybenzothiazolium, naphtho(/, z-d) thiazolium, nand[λ,/-d) thiazolium, etc.), oxacilliums (e.g. oxacillium , ≠-methyloxacillium, benzoxacillium, !-chlorobenzoxacilium, !-7enylbenzoxazolium, !-
Methylbenzoxacilium, naph) [:/,, 2-d
)oxacillium etc.), imidazoliums (e.g. /
-methylbenzothiazolium, /-furopyru-5-chlorobenzimidazolium, /-ethyl-! , z-dichloropenzimidazolium, /-allyl-! -trichloromethyl-6-chloro-benzimidazolium), selenazoliums [e.g. benzoselenazolium,! -Chlorobenzoselenazolium,! -Methylbenzoselenazolium,! -Methoxybenneselenazolium, naphtho (
/, 2-d) selenazolium, etc.]. ”
4-1 is a hydrogen atom, an alkyl group (the number of carbon atoms is r or less,
For example, methyl group, ethyl group, propyl group, butyl group, pentyl group, etc.), alkenyl group (for example, allyl group, etc.)
represents. R"?Z represents a hydrogen atom or a lower alkyl group (e.g. methyl group, ethyl group, etc.). X41 represents an acid anion (e.g. CI Br I-1α04p-4
Among Z41, thiazoliums are preferably used. More preferably, substituted or unsubstituted benzothiazolium or naphthothiazolium is advantageously used.

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

(V-/) (V-2) (V-1 (V-J) (V-7) CH2-CH=CH2 (V-Hiroshi) (V-r) CH2-CH=CH2 2H5 (V-j) (V-7) (V-70) (V-/4') (V-//) (V-/r) (V-/ko) (V-71 CV-/3) 2H5 (V-/7 ) (V-/etc.) The compound represented by the above general formula (V) is advantageously used in an amount of about 0.0/gram to !gram per 17 silver halide in the emulsion.

The ratio (weight ratio) of the above-mentioned infrared sensitizing dye of the present invention and the compound represented by general formula (V) is as follows: infrared sensitizing dye of the present invention/-compound represented by general formula (V)=/ ／／〜／／
A range of 300 is advantageously used, in particular from //2 to //!
A range of 0 is advantageously used.

The compound represented by the general formula (V) 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. Other sensitizing dyes can be added to the emulsion in the form of a solution or a dispersion in a colloid.

The compound represented by general formula (V) 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 general formula (V) 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 chlorozolatinate, ≠-hydroxy-t-methyl-/, 3. BACKGROUND OF THE INVENTION A large number of compounds have been known for a long time, including many heterocyclic compounds, mercury-containing compounds, mercapto compounds, and metal salts, including Ja, 7-titraazaindene, and /-phenyl-y-mercaptotetrazole. An example of a compound that can be used is “The Th
eory of the Photographic P
rocess (3rd edition, 1946), pages 3≠≠ to pages 3≠, for example, the detailed compounds described in US Patent No. 1, i3i, o3♂, Thiazolium salts described in Ko, Otori≠, No. 7/6, etc.; US Patent No. 2. Il'1. ．． Azaindenes described in US Pat. No. 1137, US Pat. ko17. Urazoles described in US Patent No. 3. -231,. 61
Sulfocatechols described in British Patent No. 623, 414', R, etc.; U.S. Patent No. 2. qos.

Octopus No. 7, No. 3.2tt, No. 177, No. 3゜3ri7
Mercaptotetrazoles and nitrones described in Riza No. 7, etc.; nitroindazoles; U.S. Patent No. 2
．． ♂39.110! Polyvalent metal salts (Polyvalentmetal 5 alts) described in No.
US Patent Tube 3. ．． Thiuronium salt (thiuronium 5al) described in 2.20,132 etc.
ts ); US patent tube λ.

! At, 2I! , No. 3, same No. 2. ! 7. Examples include salts of noradium, platinum, and gold, which are described in No. 75.

Silver halide photographic emulsions contain developing agents such as hydroquinones; catechols; aminophenols; 3-pyrazolidones; ascorbic acid and its derivatives; reductones and phenylene diamines, or a combination of developing agents. be able to. 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, pack layers, etc.). The developing agent is dissolved in a suitable solvent, or the U.S. Patent Co., Ltd. octopus.

36f and French Painting Patent No. 1. ! 0! , No. 77g.

As a development accelerator, for example, 3.2 g of US patent cylinder? ,6
/ Ko No. 3,333. the law of nature! ri issue, same number 3.3≠! ,
/7, r number, 3.70, 303, British patent tube 1
,07f,74t? No., Rooster German Patent No. 1, /It/
, No. 4131, No. 1. /13゜7g≠ etc. can be used.

The photographic emulsion of the present invention may contain an inorganic or organic hardening agent. For example, chromium salts (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glitaraldehyde, etc.), hemethylol compounds (dimethylol urea, methylol dimethylhydantoin, etc.), dioxane derivatives (2,3-dihydroxydioxane, etc.) , active vinyl compound (/, 3.j-1-
lyacryloyl-hexahydro-3-triazine, bis(vinylsulfonyl)methyl ether, N,N'-methylenebis-[β-(vinylsulfonyl)flopionamide], etc.), active halogen compounds (21μm dichloro-
t-hydroxy-5-)riazinato), mucohalogen 1lffa (mucochloric acid, mucophenoxychlorol, etc.) isoxazoles, dialdehyde starch, -ichiroruotsu-hydroxytriazinylated gelatin, etc.
They can be used alone or in combination. A specific example is a US patent/? 70.36≠ issue, same co, 0♂00/9
No. 2,72A, /1.2, u, J'70.0/
No. 3, same, ri♂3.4iy, same 2゜992.109
No. 3.04t7, No. 3911, J, 0!7.7
No. 23, No. 3,103,1137, No. 3,3/, 3
/No.3, 3,32! ;、-? No. 7, 3.3t2,1
No. 27, 3,339. t≠≠ issue, same 3. ! 3.
No. 292, British patent No. 7, No. 62g, same guy! ≠
Hiroshi No. 1, λ70.1711, German patent ♂72.
/! No. 3, same/, 0ri O2≠27, special public show 3≠-7,
It is described in No. 133, No. 6-/♂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 condensate, polyethylene glycol alkyl ether a or u, p-lyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol alkylamines or amides, polyethylene oxide adducts of silicone), glycidol derivatives (e.g. alkenylsuccinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols,
Nonionic surfactants such as alkyl esters of sugars;
Alkyl carboxylates, alkyl sulfonates, alkylbenzene sulfonates, alkylnaphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkylsulfonate Anionic surfactants containing acidic groups such as carboxyne groups, sulfo groups, phospho groups, sulfate ester groups, phosphate ester groups, etc. such as polyoxyethylene alkyl phenyl ethers and polyoxyethylene alkyl phosphate esters; amino acids Ampholytic surfactants such as , aminoalkyl sulfonic acids, aminoalkyl sulfuric acid or halogen acid esters, alkyl betaines, amine oxides: alkyl amine salts,
Cationic surfactants such as aliphatic or aromatic μ-class ammonium salts, heterocyclic μ-class 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 coating solution for the non-photosensitive hydrophilic colloid layer or to the coating solution for the emulsion layer. 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-/) However, FL5゜ is a saturated or unsaturated hydrocarbon group having 3 to λ0 carbon atoms and a fluorine-substituted product thereof, and R5 is a hydrogen atom,
A methyl group, an ethyl group or a propyl group. n is/~2
An integer of 0 is preferred, especially /~♂. M is a heptavalent alkali metal, with Na and K being particularly preferred.

[A-2] (A-j) In [A-2] and (A-3), R and M2O1 n have the same meanings as in the general formula (:A-/:). a is 01/
or λ. m is an integer between /~B, especially λ~μ
is preferred.

[A-Hiro]

(A-s) R-0-8 (J3M [A-6] [8-ta] [A-Hiro], [A-yo], (A-1), R and M are general formula 1 :A-/) has the same meaning.

However, RM has the same meaning as di 1 in the general formula (A-/), and m has the same meaning as in the general formula [A-λ].

[A-za]

(A-J'), [A-ta], R5□ has 3 to 3 carbon atoms
The two hydrogen moieties are fluorinated saturated or unsaturated hydrocarbons, preferably having 7 to /r carbon atoms. FL5
, M have the same meaning in the general formula [:A-/,), m
is the same as in the general formula (:A-2,1).

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

A-/CHC0NHCH25o3Na 1 Eng 23 C7F,, C0NH(CH2)2SO3NaA-ta42L-≠ -j C7H15-0-803K A-// CHOS O3N a l 2 25 A-/+2 -J A-/3 C8F, 7 -8O2NH(CH2) 3CUONaA
-/II CF So NH(CH2)4COONaA-/
Yo013F2□To S02H(CH2)30PO(OH)2
A-/A-f The amphoteric surfactant used in the present invention refers to a different surfactant having both an anionic group and a cationic group in the molecule to form an inner salt, and the following: It can be expressed by general formula (B).

In the general formula CB), Ae represents an anionic residue containing an anionic group such as a sulfo/acid group, a carboxylic acid group, a phosphoric acid group, and C@ represents an organic cationic residue.

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

13-/(I0-carboxydecyl)dimethyldodecylammonium hydroxide B-2(!-carboxyethyl)dimethyldodecylammonium hydroxide B-3(J-sulfopropyl)dimethyldodecylammonium hydroxide B-4t (4L-sulfobutyl) Diethyldodecyl ammonium hydroxide 13-z (x-carboxydecyl) dimethyloctadecyl ammonium hydroxide B-O (3-sulfopropyl) dimethyl octadecyl ammonium hydroxide B-7 (carboxymethyl) dimethyl octadecyl ammonium hydroxide B-4 ( carboxydecyl) dimethylundecylcarbamoylpropyl anhydride B-ta (3-sulfobutyl)dimethylurin/decylcarbamoylpropylammonium hydroxide B-10/-(I0-carboxydecyl)pyridium hydroxide B-///-( I0-sulfatedecyl)pyridium hydroxide B-123-carboxy/dodecylpyridinium hydroxide B-/3/(/-carbogycitridecylpyridinium hydroxide) To improve the sharpness of the legs of the characteristic curve, For the purpose of obtaining high-quality halftone dots and line images, polyalkylene oxide compounds (for example, alkylene oxides having 2 to ≠ carbon atoms, such as ethylene oxide, propylene-1,2-oxide, butylene-/.

λ-oxide, preferably a polyalkylene oxide consisting of at least /Q units of ethylene oxide, water, aliphatic alcohol, aromatic alcohol, fatty acid,
It is preferable to use a condensation compound with a compound having at least one active hydrogen atom such as an organic amine or a hexitol derivative, or a block copolymer of two or more polyalkylene oxides. That is, as polyalkylene oxide compounds, specifically, polyalkylene glycols, fullylene glycol alkyl ethers, polyalkylene glycol aryl ethers (alkylaryl), ether polyalkylene glycol esters, polyalkylene/glycol fatty acids Amides, polyalkylene glycol amines, polyalkylene glycol block copolymers, polyalkylene glycol graft polymers, etc. can be used. It is necessary that the molecular weight is greater than or equal to t,oo.

The number of polyalkylene oxide chains is not limited to one in the molecule, but may be two or more. The lateral polyalkylene oxide chains may then consist of fewer than 70 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, for example ethylene oxide and propylene oxide. The polyalkylene oxide compound that can be used in the present invention preferably contains at least 1004 alkylene oxide units per lA or more.

Specific compounds include JP-A Shoj;0-/! 6μ23, Tokukai Sho! 2-1011
The polyalkylene oxide compounds described in No. 30 and JP-A-33-32/7 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 an aqueous solution of an appropriate concentration or in a low boiling point organic solvent that is miscible with water.
It can be added to the emulsion at any suitable time before coating, preferably after chemical ripening.

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

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

Gelatin is advantageously used as a binder or protective colloid in photographic emulsions, but other hydrophilic colloids can also be used. For example, gelatin derivatives, graphs of gelatin and other polymers), proteins such as albumin, casein, etc.: 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.

Gelatin derivatives can be obtained by reacting gelatin with various compounds such as acid halides, acid anhydrides, incyanates, bromoacetic acids, alkanesultones, vinyl sulfonamides, maleimide compounds, polyalkylene oxides, epoxy compounds, etc. The one obtained by doing so is used. Specific examples include U.S. Patent λ, A/μ, No. 2, No. 3,132, No. 3, No. 3, U.S. Pat. /g Otsu, ♂Hiroshi, same number 3
゜3/2,553, British Patent No. A/, ≠llA, Same/, 033. /No. 19, same/, 00! , 7r'A, special public Akihiro 2-26♂l! It is written in the number etc.

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 gelatin and polymers which are compatible to some extent with polymers such as acrylic acid, methacrylic acid, acrylamide, methacrylamide, hydroxyalkyl methacrylates and the like. Examples of these are U.S. Pat.
It is described in the same λ, Riyot2g♂≠ issue, etc. Typical synthetic hydrophilic polymer substances include, for example, the German Patent Application (OLS).
No. 2,312,7or, U.S. Pat. No. 3,620.7! / issue, same 3r7ri, 20! No., Tokuko Akihiro 3-73-t1.

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)acrylate, alkoxyalkyl (meth)acrylate-11glycidyl (meth)acrylate, (meth)acrylamide, vinyl ester (e.g. vinyl acetate), acrylonitrile, olefin, styrene, etc. alone or in combination, or these and acrylic Polymers containing a combination of acids, methacrylic acid, α, β-unsaturated dicarboxylic acids, hydroxyalkyl (meth)acrylates, sulfoalkyl (meth)acrylates, styrene sulfonic acid, etc. as monomer components can be used.

For example, a US patent! , 37 Otsu, oor issue, same co.

73F, No. 137, same 2. ♂３３． ≠! No. 7, 43,
Ot2, J7+ issue, same 3. II-//, No. 77, No. 3 Goi f, No. 7θ, No. 3. T-no! , No. 1O, same 3.
Otsu 07, 25'0, same 3. A3j, issue 7/j, same 3.
t≠! , No. 7GQ, British Patent/.

/, Otsu, 2 Meta No. 2, same/,, 307.373 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 dihydroquine benzene type developing agents, /-phenyl-3-pyrazolidone type developing agents, p-aminophenol type developing agents, etc. These can be used alone or in combination (for example, /-phenyl- (3-pyrazolidones and dihydroxybenzenes or p-aminephenols and dihydroxybenzenes) can be used. The photographic material of the present invention which has been developed may be processed with a so-called infectious developer using a sulfite ion buffer such as carbonyl bisulfite and hydroquinone.

In the above, examples of dihydroxy developing agents include hydroquinone, chlorohydroquinone, bromohydroquinone, isopropylhydroquinone,
Toluhydrohydroquinone, methylhydroquinone, 2
, 3-dichlorohydroquinone, 2. ! -Dimethylhydroquinone, etc., and no-phenyl-3-pyrazolidone-based developing agents include /-phenyl-3-pyrazolidone, l,l-dimethyl-/-phenyl-3-pyrazolidone, ≠-hydroxymethyl-t-methyl- /-phenyl-3-pyrazolidone, 74. li&-dihydroxymethyl-/-phenyl-3-pyrazolidone, etc.
As the p-amine phenol developing agent, p-amine phenol, N-methyl-p-amine phenol, etc. are used.

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 the alkaline agent for the developer used in the present invention, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, sodium acetate, tribasic potassium phosphate, jetanolamine, triethanolamine, etc. are used. The pH of the developer is usually set to 2.7 or higher, preferably 2.7 or higher.

The developer solution may also contain organic compounds known as antifoggants or development inhibitors. Examples include azoles such as nizothiazolium salts, nitroindazoles, nizimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles. , aminotriazoles, benzotriazoles,
Nitrobenzotriazole, mercaptotetrazoles (especially phenyl-mercaptotetrazole)
mercaptopyrimidines; mercaptotriazines: thioketo compounds such as oxazolinthione; azaindenes, such as triazaindenes, tetraazaindenes ('% hydroxy-substituted (/,
3.3a.

7) Tetrazaindenes), pentaazaindenes; benzenethiosulfonic acid, benzenesulfinic acid,
Benzene sulfonic acid amide, λ-mercaptobenzimidazole-! - Sodium sulfonate.

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 may be contained in a range of 60,000 to 1,000 to 10,000 y/l.

It is preferable to add all of the water softeners such as nitrilotriacetic acid, ethylenediaminetetraacetin incand, triethylenetetraamine-xaacetic acid, and diethylenetetraamine interacetyl acid to the developing solution 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 to be effective 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.

The processing temperature and processing time are set appropriately, but usually /r'c-
-eo'c processing temperature was appropriate, while so-called automatic developing machine was used/! It is preferable to perform rapid processing of ~lλO seconds.

Next, the present invention will be explained in more detail using Example 91J.

However, the present invention is not limited to these preferred embodiments.

Example 1 Silver iodobromide grains were precipitated by the double jet method, subjected to physical ripening and desalting treatment, and then chemically ripened to obtain a silver iodobromide (iodine content/, 1 molt) emulsion. . The average diameter of the silver halide grains contained in this emulsion was 0.28 microns. 0.60 mol of silver halide was contained in 1 kg of this emulsion.

Weigh out 1 kg of this emulsion, dissolve it by heating at 40"C, add 30n+g of 1[1-6 aggravating dye, compound IV-5
280 mg.

Compound V-3 was added in an amount of 440+ng, and mixed and stirred. Next, 35 ml of a 1.0% by weight aqueous solution of 1-hydroxy-3,5-dichlorotriazine sodium salt was added,
Furthermore, surfactants A-12 and B-8 were added at 1.0% each.
45ml of a wt% aqueous solution was added and stirred.

This finished emulsion was coated onto a cellulose triacetate film base to a dry film thickness of 5 microns.

Sample 1 was prepared by providing a gelatin protective layer on top of this emulsion layer.

On the other hand, in the emulsion layer, as shown in Table 1, the dye of general formula (I) was added at 5 mg/bo, and the dye of -formation (II) or Comparative Dyel or Comparative Dye 2 was added at 25+ ng/each.
Samples 2 to 9 were made in the same manner as Sample 1 except that rrr was added.

This film sample was subjected to light simulated exposure using a sensitometer with a light source with a color temperature of 2854"K and a dark red filter (SC-74) manufactured by Fuji Photo Film Co., Ltd. attached to the light source. After exposure, the following composition was developed. The strip was developed using a solution for 3 minutes at 20°C, stopped, and then subjected to a fixing bath, followed by washing with water to obtain a strip with a predetermined black and white image. Density measurements were performed to obtain sensitivity and fog.

Sensitivity was expressed as the reciprocal of the exposure amount giving a density of 1.5.

Composition of developer water 5
00 ml N-methyl-p-aminophenol 2.2 g Anhydrous sodium sulfite 96.0 g Hydroquinone 8.8 g Sodium carbonate hydrate 56. Og potassium bromide
Add 5.0 g water
11 The results obtained are shown in Table 1 as relative values.

(Note) In Table 1, I) Relative sensitivity: Reciprocal of the exposure meter giving a density of 1.5, sample 1 is set to 100.

2) Fog after irradiation with safelight: Safelight filter Nα4 made by Fuji Film ■ was stacked with Toshiba color glass filter I RA-”05 and paraffin paper, irradiated with an IOW tungsten lamp for 20 minutes at a distance of 2m, and then developed. Fog when

3) Image quality: The amount of light was adjusted to give an i4 degree of 4.0, and the image of the boundary between the unexposed area and the exposed area was observed using a microscope.

If the image of the darkened area is sharp, grade A, and if the image is defective, grade C8.
The evaluation is divided into three stages with the middle being B.

(01Dy e 1)ye ■ From the above results, it can be seen that samples 4.7.8 of the present invention have good image quality and can improve safelight suitability with a low sacrifice in sensitivity. That is, the present invention has resulted in 11 J3 optical materials that have high image quality, a high beam angle of 8 degrees, and can be handled under bright safety light.

EXAMPLE 2 In the same manner as in Example 1, chlorobromide milk powder (29 mol% of l'3r, average particle size 0.27 microns) was prepared using IW.

4-hydroxy-6methyl 13 was added to this emulsion as a stabilizer.
350 μ of 3a,7-chitrazaindene were added.

42rL1g of m-25 per 1kg of this emulsion, IV-
3 of Compound 21Off1g and Compound V-2 at 340■
and then l-hydroquine-3 as a hardening agent.
, 2.2 g of 5-dichlorotriazine sodium salt, II
31 g of an ethyl acrylate polymer dispersion was added to improve the '2M and coated on a polyethylene terephthalate film so that 1r+ (silver ψ 3.9 g per film).

On this emulsion layer, 3g/3g of A-12 was added as a coating aid.
% and 13-8 at 1.5 g/l, add 5 g/l of methyl methacrylate polymer as a matting agent, and add 1 g/+l of A or B as a mordant to protect gelatin. A test sample 410.16 was prepared by providing layers such that the film thickness was 1.0 μm.

On the other hand, samples 10.16 and 10.16 were added to each emulsion layer except that 7.5% of the dye of general formula (I) was present in the emulsion layer as shown in Table 2.
Sample If, 17, was prepared in the same manner as .

Also - ship type (It) or Dye for comparison 1. Dy
Samples 12-
15. Mordant A that made 18-21] 1 Before mordanting 11F3 +C11□-C1l. -(C11□~Cl
1) q.

The film sample thus prepared was first exposed through a dark 2 color filter (Fuji Photo Film sample, 5C-72), developed with the following developer at 20°C for 14 minutes, and then stopped.
After fixing, it was washed with water. The density was determined using a P-type densitometer manufactured by Fuji Photo Film, and the sensitivity and fog value were determined. The optical 01 degree reference point for determining 13 degrees was at T7 of (Capri+1.0).

The results are shown in Table 2.

Double 31 and four methol 0.31 g Anhydrous sodium sulfite 39.6 g Hydroquinone 6.0 g Anhydrous sodium carbonate 18.7 g Potassium bromide
0.86 g citric acid
0.68 8 Mekkuruma Potassium Sulfite Add 1.5g water
The exposure conditions of 142 safelight were the same as in Example 1.

For residual color test, unexposed sample 1 was developed and colored after washing with fixed blue water (
Insufficient decolorization/decolorization of Dyeing 1) was visually judged. Evaluation was made on a four-rank 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.

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

19rJ person for patent Fuji Photo Film Co., Ltd.

Claims (1)

[Scope of Claims] A silver halide photographic photosensitive material comprising, on a support, at least a dye represented by the following general formula (I) and at least a dye represented by the following general formula (II). material. General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_1, R_2, R_3, R_4, R_5 and R_6 may be the same or different from each other and represent a substituted or unsubstituted alkyl group, Z_1 and Z_2 are
Indicates the nonmetallic atomic group necessary to form a substituted or unsubstituted benzo-fused ring or naphtho-fused ring, respectively. However, R_1, R_2, R_3, R_4, R_5, R
_6, Z_1 and Z_2 represent groups that allow the dye molecule to have at least 3 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 forms 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_5
R_1_6, -OR_1_5, -NR_1_5R_1_
6, -NR_1_6COR_1_7, -NR_1_5C
ONR_1_5R_1_6 or -NR_1_6SO_2
R_1_7 (here, R_1_5 and R_1_6 represent a hydrogen atom, an alkyl group, or an aryl group, R_1_7 represents an alkyl group or an aryl group, and R_1_5 and R_
1_6 or R_1_6 and R_1_7 are connected to 5 or 6
A member ring may be formed. ), Q_1_1, Q_
1_2 each represents a methylene group, Y_1_1, Y_1
_2 each represents a sulfonic acid group, a carboxylic acid group, or an aryl group having at least one sulfonic acid group or carboxylic acid group, and m_1_1 and m_1_2 are respectively 1, 2, 3,
Represents 4 or 5. ]