JPS6256954A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To obtain an excellent spectral sensitizing effect by disposing silver halide (AgX) emulsion layers into which specific compds. and sensitizing dyes are incorporated in combination. CONSTITUTION:>=1 Layers of the AgX emulsion layers contg. >=1 sensitizing dyes expressed by formula I [n is 0, 1, m is 1, 2. R1 is a (un)substd. alkyl, R2-R4 are respectively H, alkyl, alkoxy, hydroxy, etc., R2 and R3, R3 and R4 or R2 and R4 may form a condensed 6-membered ring. Z1 and Z2 are respec tively 5-6-membered ring forming atom groups and the ring thereof may be condensed with other rings. L1, L2 are (un)substd. methine and >=1 compds.] expressed by formula II (A is a divalent arom. residue R11-R14 are respectively H, hydroxy, alkyl, alkoxy, aryloxy, halogen atom, heterocyclic group, etc., where one or more among A, R11-R14 has a sulfo group. W is -CH= or -N=) are disposed. The photographic sensitive material having the excellent special sensitization is obtd. by combining such sensitizing dyes expressed by formula I and the compds. expressed by formula II and having the storing color sensitiz ing effect and adding the same to the emulsion.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a silver halide photographic emulsion, and more particularly, it relates to a silver halide photographic emulsion that is spectral sensitized by at least two types of sensitizing dyes and organic compounds that mutually exhibit supersensitizing effects. This invention relates to subsilver halide photographic emulsions.

(Prior Art) It is well known that the addition of certain dyes is extremely effective as a means of increasing the photosensitivity of silver halide photographic emulsions. In this case, the nine dyes added to the silver halide photographic emulsion are adsorbed to the silver halide grains in the emulsion, adding a longer wavelength absorption band to the absorption band specific to silver halide. This is called "spectral sensitization."

On the other hand, in light-sensitive materials, by adding a second kind of specifically selected organic compound in addition to the spectral sensitizing dye, the spectral sensitivity can be significantly increased, and this effect is due to the supersensitizing effect. known as. Generally, the addition of a second organic compound or inorganic substance often does not increase the sensitivity or even decreases the sensitivity.
Supersensitization can be said to be a unique phenomenon, and extremely strict selectivity is required of the sensitizing dye and the second organic compound or inorganic substance used in this combination. Therefore, what appears at first glance to be a subtle difference in chemical structure significantly affects this supersensitizing effect, and it is difficult to obtain a supersensitizing combination simply by predicting from the chemical structural formula.

(Problems to be Solved by the Invention) An object of the present invention is to provide a silver halide photographic material with improved photosensitivity.

Another object of the present invention is to provide a significantly sensitized silver halide photographic material.

(Means for Solving the Problems) The above-mentioned object of the present invention is to provide at least one sensitizing dye represented by the following general formula (I) and the following general formula (II).
This could be achieved by having at least one silver halide photographic emulsion layer containing at least seven of the compounds represented by:

General Formula (I) In the above general formula (I), each substituent is shown as follows. That is, n represents O or /, m represents / or λ. R
1 represents a substituted or unsubstituted alkyl group, R2,
R3 and R4 may be the same or different from each other and represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a substituted or unsubstituted amine group, or a halogen atom, and R2 and R3, R3 and R4, or R2 and R4 may be fused & to form a ring. Zl is! Represents an atomic group necessary to form a membered ring or a two-membered ring, and these rings may have a substituent or be fused with another ring. z2 represents a j-membered ring and an atomic group necessary to form a t-membered ring, and these rings may have a substituent or be fused with another ring. LH and R2 may be the same or different and each represents a methine group or a substituted methine group.

General formula (III where A represents all divalent aromatic residues. R11, R12
, R13, and R14 are each a hydrogen atom, a hydroxy group,
Alkyl group, alkoxy group, aryloxy group, halogen atom, heterocyclic nucleus, heterocyclylthio group, arylthio group, amino group, substituted or unsubstituted alkylamino group,
It represents a substituted or unsubstituted arylamino group, a substituted or unsubstituted aralkylamino group, an aryl group, or a mercapto group.

However, at least one of A, R11, R12, R13 and R14 has a sulfo group. W is -CH=,
Or represents -N=.

Next, the general formula (Il will be explained in detail.

Each substituent of the compound represented by general formula (I) is preferably the substituent shown below.

That is, R1 is an unsubstituted alkyl group having a carbon number of it or less (for example, a methyl group, an ethyl group, a propyl group, a butyl group, a methyl group, an Ofder group, an acyl group, a dodecyl group, an octadecyl group, a vinylmethyl group, a cyclohexyl group, etc.). ) ik is a substituted alkyl group (as a substituent, for example, a carboxy group,
Sulfo group, cyano group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom), hydroxy group, alkoxycarbonyl with the following number of carbon atoms! (For example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxylcarbonyl group, etc.), number of carbon atoms! The following alkoxy groups (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), monocyclic group having 10 or less carbon atoms (e.g. phenoxy// group, p-tolyloxy group, etc.) carbon Acyloxy groups with a number of 3 or less (e.g. acetyloxy, propionyloxy, etc.), acyl groups with a carbon number of less than 3 (e.g. acetyl, propionyl, benzoyl, mesyl, etc.), carbamoyl groups (e.g. carbamoyl, N, N -dimethylcarbamoyl group, morpholinocarbonyl group, piperidinocarbonyl group, etc.), sulfamoyl group (e.g. sulfamoyl group, N,N-dimethylsulfamoyl group, morpholinosulfonyl group, piperidinosulfonyl group, etc.) having a carbon number of io or less Aryl group (e.g. phenyl group,
An alkyl group having a carbon number of lt or less substituted with ≠-chlorophenyl group, ≠-methylphenyl group, α-naphthyl group, etc.) is preferable.

The alkyl groups for R2, R3, and R4 are preferably lower alkyl groups having carbon numbers of l to ≠ (for example, methyl, ethyl, isopropyl, butyl, etc.), and the alkoxy groups have carbon atoms of l to ≠. Alkoxy groups (eg, methoxy, ethoxy, propoxy, butoxy, etc.) are preferred.

The halogen atom for R2-R4 is preferably a fluorine atom, a chlorine atom, or a bromine atom.

The substituted or unsubstituted amino group of R2-R4 is, R21 and R22 may each be the same or different, and a hydrogen atom, a lower alkyl group with carbon number l-≠ (
For example, methyl group, ethyl group, propyl group, butyl group, etc.)
, an acyl group having a carbon number of λ to ♂ (for example, an acetyl group, a propionyl group, a benzoyl group, -, etc.) is preferable.

MakuR21 and IL22 are connected to each other, and a member ring or t
It is also preferable to form a membered ring.

Furthermore, R21 and/or R22 may be bonded to the benzene ring of the benzobylane nucleus to form a condensed, j-membered or 6-membered ring.

Zl represents a group of atoms necessary to form a member fM, and the ring is, for example, a thiazole nucleus (e.g. thiazole,
Hiro-methylthiazole, ≠-phenylthiazole, j-
Methylthiazole! -Phenylthiazole, ≠, j-
Dimethylthiazole, ≠,! -diphenylthiazole,
≠, (2-tunyl)thiazole, etc.), benzothiazole nuclei (e.g. benzothiazole, ≠-chlorobenzothiazole, j-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, μm methylbenzothiazole, j- Methylbenzothiazole, b-methylbenzothiazole, j.

-dimethylbenzothiazole, j-bromobenzothiazole, t-bromobenzothiazole,! -trifluoromethylbenzothiazole, j-phenylbenzothiazole, Hiro-methoxybenzothiazole, j-methoxybenzothiazole, 6-methoxybenzothiazole,! −
Karpoki 7 benzotheazole! -cyanobe/zothiazole, yo-fluorobenzothiazole, j-ethoxybendithiazole, tetrahydrobenzothiazole, j,
z-dimethogishibe/zothiazole,! -hydroxybenzothiazole, O-hydroquine benzothiazole, etc.),
naphthothiazole nuclei (e.g. naphtho-C/, 2-dlthiazole, naphtho[λ.

/-d]thiazole, naphtho[λ, J-d]thiazole,! -methoxynaphtho[:j,/-d)thiazole,!
=Etoki/Naphtho [), /-d] Thiazole,! -methoxynaphtho(/, 2-d)thiazole, 7-medoxynaphtho(/, ?-d]thiazole, etc.), oxazole nucleus (e.g. t-methyloxazole, j-methyloxazole, ≠-phenyloxazole, ≠, S- diphenyloxazole, Hiro-ethyloxazole, ≠, j-dimethyloxazole, j-phenyloxazole, etc.),
Benzoxazole nucleus (e.g. benzoxazole,!
-Chlorobenzoxazole, j-methylbenzoxazole, j-phenylbenzoxazole, 6-methylbenzoxazole, j,6-dimethylbenzoxazole, ≠, 6-dimethylbenzoxazole,! -Methoxybenzoxazole,! -Ethoxybenzoxazole, j-fluorobenzoxazole, 6-medoxybenzoxazole,! -hydroxybenzoxazole, t-hydroxybenzoxazole, etc.), naphthoxazole core (e.g. naph) (/, U-d) oxazole, naph) [,2,/-d) oxazole, naphtho[λ
, J-d) oxazole, etc.), selenazole nuclei (e.g. selenazole, Hiro-methylselenazole, l-phenylselenazole, ≠).

j-diphenylselenazole, etc.), benzoselenazole core (e.g. benzoselenazole, j-chlorobenzoselenazole, !-methylbenzoselenazole, j-methoxybenzoselenazole, j-phenylbenzoselenazole, etc.), naphthoselena sol nucleus (e.g. naff) (/, J
-d: ] selenazole, naphtho[λ,/-d) selenazole, naphtho[λ, j-d] selenazole, etc.), thiazoline nucleus (e.g. thiazoline, Hiro-methylthiazoline, ≠
- phenylthiazoline, etc.), oxazoline core (e.g. j
, t-dimethyloxazoline, etc.), inoxazole nuclei (e.g., !-methylisoxazole, etc.), benzisoxazole nuclei (e.g., benzisoxazole, etc.),
j, J-Sia/l/-IF Ruindolenin nucleus (e.g. 3
．． 3-dimethylindolenine, J,j,j-)dimethylindolenine, j-chloro-J, J-dimethylindolenine, j-ethoxycarbonyl-3,3-dimethylindolenine, etc.), copyridine nucleus (e.g. pyridine, j-
methylpyridine, etc.), goupyridine nucleus (e.g. pyridine, etc.), λ-quinoline nucleus (e.g. t-ethoxyquinoline,
6-ethylquinoline, t-chloroquinoline, za-fluoroquinoline, etc.), p-quinoline nucleus (e.g. ?-methylquinoline, t-fluoroquinoline, 2-chloroquinoline, etc.), l-isoquinoline nucleus (e.g. inquinoline, etc.)
, benzotellurazole nucleus (e.g. benzotellurazole% !-chlorobenzotellurazole, j-methylbenzotellurazole, j-methoxybenzotellurazole, etc.), naphthoteruazole nucleus (e.g. naph) (/,
ud) tellurazole, nut [λ,/-d] tellurazole, etc.) are preferred.

Z2 is preferably rhodanine ring, hydantoin ring, λ-
Thiohydantoin ring, oxazolidine-29 μm dione ring, λ-thioxazolidine-λ.

≠-dione ring, cochioselenazolidine-λ, cudio/ring, j-pyrazolone ring, indandione ring,! (≠H
)-isoxacilone ring, λ, ≠-chromandione ring,
≠, j-(/H1jHl pyridinedione ring, barbituric acid ring, coachiobarbituric acid ring, /, 3-dioxa/-μ, 6-dione ring, 3.J-pyrazolidinedione ring, to form Represents the required atomic group.

Further, these heterocycles represented by Z2 may have the following substituents.

As a substituent, carbon number 7 can be substituted with the following unsubstituted alkyl groups (e.g., methyl group, ethyl group, propyl group, butyl group, pentyl group, octyl group, decyl group, dodecyl group, octadecyl group, vinylmethyl group, cyclohexyl group, etc.) ) Mayu is a substituted alkyl group (for example, a carboxy group, a sulfo group, a cyan group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom), a hydroxy group, an alkoxycarbonyl group having less than 1 carbon atoms) (e.g. methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group, benzyloxylcarbonyl group, etc.), alkoxy groups with the following carbon atoms (e.g. methoxy group, ethoxy group, benzyloxy group, phenethyloxy group, etc.), carbon number 72 or less Substituted alkoxy groups (e.g. hydroxymethoxy group, co-hydroxyethoxy group, acetoxymethoxy group, λ-methoxyethoxy group, co-acetoxyethoxy group, etc.), aryl groups having 10 or less carbon atoms (e.g. phenyl group, Hiro-chlorophenyl group, etc.) group, ≠-methylphenyl group, α-naphthyl group, !”), monocyclic aryloxy group having io or less carbon atoms (e.g. hafenoxy group, p-)
(lyloxy group, etc.), acyloxy group having 3 or less carbon atoms (
For example, acetyloxy group, propionyloxy group, etc.)
, carbon number is the following acyl group (e.g. acetyl group, propionyl group, benzoyl group, mesyl group, etc.), carbon number lλ
The following carbamoyl groups (e.g. carbamoyl group, N, N
-dimethylcarbamoyl group, morpholinocarbonyl group,
49 dinocarbonyl group, -N-(J-N, N-dimethylaminopropyl)carbamoyl fi, N-(co-N
, N-diethylaminoethyl)carbamoyl group, N-(
j-morpholinopropyl)carbamoyl group, N-(J-
piperidinopropyl)carbamoyl group, N-(j-pyrrolidinopropyl)carbamoyl group, etc.), carbon number 72
The following sulfamoyl groups (e.g. sulfamoyl group, N
, N-dimethylsulfamoyl group, morpholinosulfonyl group, pyridinosulfonyl i, N-(J-N.

N-dimethylaminopropyl) sulfamoyl group, N-
(J-morpholinopropyl)sulfamoyl group, N-(
j-pi is lisinoprobyl) sulfamoyl group, etc.), dialkylamino groups having up to 1λ carbon atoms (e.g. dimethylamino group, diethylamino group, piperidino group, morpholino group, etc.), heterocyclic groups having up to 10 carbon atoms (e.g. λ-pyridyl group, 3-pyridyl group, 2-thiazole group, 2-benzothiazole crystal, tetrahydro-2-furanyl group, -
(furanyl group, etc.), alkyl group having up to 12 carbon atoms (alkyl group having up to 12 carbon atoms) (e.g.,
tij' phenyl group, p-chlorophenyl group, p-methylphenyl group, p-methoxyphenyl group, p-carboxyphel group, p-methoxycarbonylphenyl group, m
-acetylaminophenyl group, m-dimethylaminophenyl group, p-dimethylaminophenyl group), heterocyclic groups having io or less carbon atoms (e.g. copyridyl group, 3-pyridyl group, Hiro-pyridyl group, λ-thiazole group, λ-furanyl group, etc.) are preferred.

Ll and L2 represent a methine group or a substituted methine group, and the substituents include an alkyl group having 1-hi carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, etc.), and a 6-carbon alkyl group.
~io aryl group (e.g. phenyl group, λ-carboxyphenyl group, Hiro-methylphenyl group, λ-chlorophenyl a, etc.), substituted alkyl group having 7 to 2 carbon atoms (e.g. chloromethyl group, benzyl group, J-phenyl group) ethyl group,
3-phenylprobyl group, methoxyethyl group, etc.) are preferred. It is also preferable that nine substituents are linked to each other to form a t-membered ring on the methine chain.

The compound represented by general formula (I) can be synthesized by various synthetic methods, but for example, as shown in the reaction formula below,
An intermediate obtained by the reaction of a heterocyclic quaternary salt derivative having an active methyl group and a ≠-methyl-2-teocoumarin derivative (
It can be obtained by a condensation reaction between A) and intermediate CB).

Intermediate (A) During the reaction of the above formula, R1, R2, R3, R4, Zl, z2,
Ll, R2, n and m have the same meanings as explained in general formula (I).

'L3, R4, and R5 represent methine groups; alternatively, they represent substituted methine groups.

Xle and X2e represent an anion t-, specifically chloride, bromide, iosito, thiocyanate, nogu-chlorate, para-toluenesulfonate, tetrafluoroborate, etc.

p is /j is λ, and when intermediate [A] forms an inner salt, p is l.

Y represents a leaving group commonly used in dye synthesis, such as a substituted amino group (e.g. dimethylamino group, N-
methylanilino group, anilino group, N-acetylanilino group), alkoxy group (e.g. methoxy group, ethoxy group)
, an alkylthio group (eg, methylthio group, ethylthio group), etc.

In the condensation reaction, base catalysts such as triethylamine, pyridine, ≠-dimethyl, aminopyridine,
Sodium acetate, sodium hydroxide, etc. are used.

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

■-2 -J I-san-a knee ■-taeno l J-/ko I-/3 ■-/≠ i-/ta-it knee/ri■-20! -λλ Ni 23 ■-2 Hironi Ni-j Ni 27 ■-λri 1-3゜■-47 ■-≠2 ■-≠3 CH3 Next, a synthesis example of the compound represented by the general formula (I) of the present invention is shown below.

Synthesis Example - (Synthesis of Intermediate [A)) /-(1) j-ethyl-2-((≠-methyl-λ
H-chromene-koylidene) methyl) benzothiaturium p-1 lue/sulfonate 3-ethyl-λ-methylbenzothiazolium p-) luenesulfoner) u7r and 4'-) f-rue λ-thiocoumarin/It at 1zo0c After heating for 75 hours, methanol was added to the reaction mixture, followed by acetone and 200ml of ethyl acetate to form a homogeneous solution. When stirred at room temperature, crystals will precipitate. After taking the crystal t-F and washing it with a small amount of acetone, the crystal was added to a mixed solvent of methanol-〇lal and acetone≠θ- at room temperature, and then added to ethyl acetate for 20 minutes.
After adding 0 mjl and stirring for 30 minutes, remove P and wash with acetone to obtain the target /! r, Iff obtained. (Yield 1704) Brown crystals mpλro0c or more (decomposition)/-(2)J-)lifluoromethyl-3-ethyl-co((≠-methyl-,
-chromene-ylidene) methyl 1-benzothiazolium p-) luenesulfonate j -) IJ fluoromethyl-3-ethyl-λ-methylbenzothiazolium I) -) luenesulfonate,
After heating reaction of 2.379 and ψ-methyl-λ-thiocoumarin/, Of at /j00c for 2θ hours, 10 ml of methanol, then 10 ml of acetone, and 2 ml of ethyl acetate were added to the reaction mixture.
Add 0rrtl to make a homogeneous solution.

When cooled to room temperature, crystals precipitated. Collect the crystals, wash with a small amount of acetone, and add 1 liter of methanol at room temperature.
Add the crystals to a mixed solvent of 10 ral of acetone, 0 rnl of ethyl acetate, and 41! After stirring for O, remove P and wash with acetone to obtain the desired product, $79.

(Yield Section 6) Brown crystal m9272-273°C (decomposition)/-(31
j-chloro-3-ethyluko ((ψ-methyl-2H
-chromene-λ-ylidene)methyl)-benzothiazolium p-)rue/sulfonate j-chloro-3-ethyl-λ-methylbenzothia:/'
Lium p-toluenesulfonate/1. After heating reaction of /l and methyl-2-thiocoumarin r, ty at 1z00c for 23 hours, methanol was added to the reaction mixture. Then, 0ml of acetone, 1ml of ethyl acetate, and 1ml of ethyl acetate were added, and when the mixture was cooled to room temperature, crystals precipitated. Collect the crystals, wash with a small amount of acetone, and add methanol 2j111 at room temperature.
The crystals were added to a mixed solvent of 0ml of acetone and 1JOml of ethyl acetate, stirred for 20 minutes, filtered out and washed with acetone to obtain the desired product 7. I got it. (Yield !2) Brown crystals mp2rλ~213°C (decomposition)/-(411-methyl-3-ethyl-2-((Hiro-methyl-coH-chromen-2-ylidene)methyl)benzothiazolium, perchlorate j-Methyl-3-ethyl-methylbenzotheazolium I)-) luenesulfoner)j, 07t and ≠-methyl-cochinoccoumarin/, After heating reaction at 0fff/zo0c for 2j hours, 10rtl of methanol was added to the reaction mixture, and then 10ml of acetone and 20ml of ethyl acetate were added and cooled to room temperature to precipitate crystals. After taking the crystal fP and washing it with a small amount of acetone, 20 ml of methanol at room temperature,
Next, acetone port was added to make a homogeneous solution. Here is 60% perchloric acid! After adding V and stirring at room temperature for 30 minutes, the precipitated crystals were collected and washed with acetone to obtain the desired product 7.44.
I got 11. (Yield !j) Brown crystal mp270~Core j'C (decomposition)/-(51
j-methoxy-0? -ethyl-2-((4'-methyl-
λH-chromene-ylidene)methyl)benzothiazolium yosito! -Methoxy-3-ethyl-comethylbenzote 77'
Rium p-) Luenesulfo f-),? , /j7 and ≠−
Methyl-2-thiocoumarin/, Of 20 with izooC
After a heating reaction for an hour, methanol/j+++7 was added to the reaction mixture.
．． Add 2 ml of acetone to make a homogeneous solution. Sodium iodide/7f (71 ml solution in acetate) was added dropwise to this solution and stirred at room temperature to precipitate crystals. The crystals were collected, washed with a small amount of acetone, and washed with water at room temperature.
After adding crystals and stirring for 16 minutes, P was removed and washed with acetone to obtain the desired product. (Yield 3?%) Brown crystals mp273-27≠'c (decomposition)/-(6)j-ethylrouyo((4'-methyl-coH-chromene-coyritene)methyl)-naphtho[λ, t-d' ) Thiazolium Yosito 3-Ethyl-2-Methylnaphtho[Co,/-d) Thiazolium p-) Luenesulfonate Co, 27f and San-Methyl-Corchiofmarin I, ot21j00c were heated for 121 hours, and then methanol was added to the reaction mixture. rag and then 1xrul of acetone were added to make a homogeneous solution. 7°7f of sodium iodide (water solution) was added dropwise to this solution and stirred for 1 hour at room temperature, causing crystals to precipitate. Take the crystal,
After washing with a small amount of acetone, the crystals were added to 1 jrnl of water at room temperature and a mixed solvent of acetone/Jml, and after stirring for 11 minutes, P was removed and washed with acetate to obtain the desired products o and ry. (Yield -2f%) Brown crystal mp2r 060 or more (decomposition)/-(7
)! -ethyl-co-1(≠-methyl-λH-chromene-coylidene)methyl)naphtho[1,λ-d]thiazolium iosito3-ethyl-λ-methylnaphtho(/,u-d)thiazolium p-)luenesulfonateλ, core The target object 0, or ? '((Obtained.

(Yield 3.J-regret) Brown crystals mp/4cO~/lfi 2°C (decomposition)/-(81j, t-dimethyl-3-ethyl-2-
((gumethyl-2H-chromene-λ-ylidene)methyl)-benzothiazolium p-1 luenesulfonate! , t-dimethy) L-j-ethyl-2-methifrebenzothiazolium p-toluenesulfo-tokot, Of
Tohiro-Methyl-Cochmecmarine/3゜kotzoo
After heating reaction at c for 77 hours, methanol to
tal, then 100ml of acetone, 300ml of ethyl acetate
- was added, and when the mixture was cooled to room temperature, crystals were precipitated. After taking one crystal and washing it with a small amount of acetone, the crystal was added to a mixed solvent of methanol (10ml), acetone (10ml) and ethyl acetate (11ml) at room temperature, and after stirring for 20 minutes, P was taken and washed with acetone to obtain the desired product. λt was obtained. (Yield ≠ j) Brown crystal mp20/-JOj °C (decomposition)/-+9
) J-methyl-λ-((4cmmethyl-coH-chromene-ylidene)methyl)benzoxacilium
Perchlorateco, 3-dimethylbenzoxazolium p-toluenesulfoner) 1/S' and Hiro-Methyl-Corchiofmarin 1.21 with 1zoOC after heating reaction for io waiting time, add methanol/! to the reaction mixture! Add 1/2 ml of acetone to make a homogeneous solution. Add 1.0% sodium perchlorate to this solution. Ko? (
When the whole solution (water jm/solution) was added dropwise and stirred at room temperature, crystals were precipitated. After washing 1 liter of crystals with a small amount of acetate, pour 10 ml of room-temperature sewage. Methanol 10ml 1. Ethyl acetate O
The crystals were added to AT, separated and stirred, then P was collected and washed with ethyl acetate, yielding 0.3 tf of the desired product. (Yield /λ) Brown crystal mpλt -71"C (decomposition) Synthesis example -λ
(Synthesis of compound i-/) 3-ethyl-λ-((≠-methyl-2H-chromene-2
Add 3t of -ylidene)methyl)-benzothiazolium p-)luenesulfoner)/109 and j-(N-acetylanilinomethylene)-3-ethylrhodania to DMFJ 0rILt, and place on an oil bath at ioo° After heating, add 3.0 ml of triethylamine to C. The mixture was reacted by heating for 2j minutes, and after cooling, Improper Tools Ornl was added.

One precipitated semi-crystal was collected, washed with inzolopanol, and then recrystallized from methanol-chloroform to obtain the desired product.

02t-Tokutomo.

Dark green crystal melting point λt7°C (decomposition) λmax x ratio fnm (methanol/chloroform = li//vo1. ratio) S depth 7.07X105 Synthesis example-3 (synthesis of compound I-2) 3-ethyl-j, A-dimethyl-λ-((gumethyl-
2H-chromene-λ-ylidene) methyl) benzothiazolium p-) luenesulfonate J, Of! -(N
-acetylanilinomethyl/)-3-ethylrhodanine/, using the same method as in Synthesis Example 29, the target object o,
Got it.

Dark green crystal melting point 3oo0c or more λmax? 10nm (methanol/chloroform=
ri//VO1, ratio) ε21. Hirosan xios Synthesis example--Synthesis of compound 1-ti 3-ethyl-t,! -dimethyl-λ-((4'-methyl-2H-chromen-2-ylidene)methyl)benzothiazolium p-)rue/sulfonate/, Of and 1-(
In addition to N-acetylanilinomethylene)-/, j-dimethylthiohydantoin o, tt11DMFJII),
After heating to 100°C on an oil bath, add triethylamine 7-. After the reaction was heated for 20 minutes and cooled, the reaction mixture was purified through silica gel column chromatography (eluent: ethyl acetate) and recrystallized from methanol-chloroform to obtain the desired product 301n9.

Dark green crystal melting point λ7j-27r0C (decomposed) λmaz AArnm (chloroform) ε=6. -!
X104 Synthesis Example-j The following compounds were synthesized in the same manner as in Synthesis Examples 4 to 3.

Color tone and absorption maximum of the obtained compound (in methanol solution)
The details are shown in the table below.

Next, general formula (1[) will be explained in detail.

In the formula, -A- represents 2 (aromatic residue 'f of eJ:
These are -803M groups [where M is a hydrogen atom or a cation that provides water solubility (e.g. sodium, potassium, etc.)
-Represent. ] may also be included.

-Am is usefully selected from, for example, the following -A1- and -A2-. However, R11, R12゜It13
Or, when R14 does not include -Am, -Am is selected from the group -AI-.

-AI-; 505M SOaM SO3M 803M SO3M S03M SO3M 503M etc. Here, M represents a hydrogen atom or a cation that provides water solubility.

-A2-; R11, R12, R13, and R14 are each a hydrogen atom,
Hydroxy group, lower alkyl group (number of carbon atoms: /
, j are preferable, e.g. methyl group, ethyl group, n-propyl group, n-butyl group), alkoxy group (the number of carbon atoms is preferably /-r, e.g. methoxy group, ethoxy group, propoxy group, butoxy group) ), aryloxy groups (e.g., phenoxy, naphthoxy, o-troxy, p-sulfophenoxy, etc.), halogen atoms (
(e.g., chlorine atom, bromine atom, etc.), heterocyclic nuclei (e.g., morpholinyl group, lysyl group, etc.), alkylthio groups (e.g., methylthio group, ethylthio group, etc.), heterocyclylthio groups (e.g., benzothiazolylthio group, benzimidazolylthio group) , phenyltetrazolylthio group, etc.), arylthio group (e.g. phenylthio group, tolylthio group), amino group, alkylamino group or [ilt
Substituted acylamino groups include methylamino group, ethylamino group, propylamino group, dimethylamino group, diethylamino group, dodecylamino group, cyclohexylamino group, β-hydroxyethylamino group, di(β-hydroxyethyl)amino group, β-sulfoether amino group),
Arylamino group, m9 is a substituted arylamino group (e.g. anilino group, 0-sulfoanilino group, m-sulfoanilino group, p-sulfoanilino group, 0-)luidino group, m
-) luidino group, p-toluidino 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-anisidine M, o-acetaminoanilino group, hydroxyanilino group, disulfophenylamino group, naphthylamino group, sulfonaphthylamino group), heterocyclylamino group (
For example, λ-benzothiazolylamino group, λ-pyridylamino group, etc.], substituted or unsubstituted aralkylamino group (such as benzylamino group, 0-anisylamino group, m
-anisyl amino group, p-anisyl amino group, etc.),
Represents an aryl group (such as a phenyl group) or a mercapto group. R11, R12°R13, R14 may be the same or different from each other. When -person- is selected from -A2-, at least one of R11, R12, R13, and R14 has one or more sulfo groups (which may be free acid groups or may form salts). It is necessary to have one.

W represents -CH= or -N=, preferably -CH=
is used.

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

(IF-/) ≠, 4c'-bis[≠l 6-di(inzothiazolyl-λ-thio)pyrimidi7-J-ylaminocostilbene-λ,λ'-disulfonic acid disodium salt (π- λ) 1. 3′-bis[1t-di(benzothiazolyl-λ-amino)pyrimidine-choylamino)]stilbene-2,2′-disulfonic acid disodium salt (It-J) 4′, μ′-bis[Hiro, t -di(naphthyl-cooxy)pyrimidine-choylamino]stilbene-2,2'-disulfonic acid disodium salt +ll-4') μ,4t'-bis(p,,g-di(
Naphthyl-cooxy)pyrimidine-λ-ylamino]bibenzyl-λ,λ'-disulfonic acid disodium salt (II-jl ≠, Hiro'-bis(+L, +-dianilinopyrimidine-/λ-ylamino)stilbeneco, λ' -Disulfonic acid disodium salt (II-j) ≠, μ'-bis[darklo-6-(2-naphthyloxy)pyrimidin-2-ylamino]hyphenyl-λ.

λ'-Disulfonic acid resin sodium salt It-7) Acid disodium salt (■-♂) μI-bis[≠, 6-di(benzimidazolyl-2-thio)pyrimidin-2-ylaminocostilbene-2,2'-disulfonic acid disodium salt (II- Ta) Hiro, Hiro'-bis (≠, 6-diphethoxypyrimidine-choylamino) Stilbene-λ,2'-disulfonic acid disodium salt (It-10) Hiro, Hiro'-bis (≠, 1! 1-diphenylthiopyrimidine-choylamino) Stilbene-λ,2'-disulfonic acid disodium salt (][-//) 4C, da'-bis(≠, t-dimercaptopyrimidine-λ-ylamino) Biphenyl- λ, λ'-disulfonic acid disodium salt ([-/i 4(, Hiro'-bis(≠, 6-dianilituriazin-λ-ylamino) stilbene-λ 21-disulfonic acid disodium salt (I[-/ J) μ, φ′-bis(≠-anilino monohydrokylatriazine-koylamino)stilbene-λ, 21- disulfonic acid disodium salt (■-/Hiro) Hiro, g′-bis[l-su7 Tylamino-t-anilino-triazine-λ -ylamino)stilbene-λ9.2'-disulfonic acid disodium salt Among these specific examples: (It-/) ~ (■ ~ 1.2)
are preferable, especially (II −/), (II-2), (I
I-j), (■-≠), (II-j), (■~7), (
π-l) is preferred.

The dye of general formula (I) used in the present invention is per mole of silver halide! x10'-7 mo to ~jx10' mole,
Preferably /X10'-67k ~/X10-3 mol,
Particularly preferably λ×70 mol~! It is contained in the silver halide photographic emulsion in a proportion of x10"-' moles.

The dye of general formula (I) used in the present invention can be directly dispersed into an 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. The method for adding the dye of general formula (I) is described in U.S. Patent No. 3.
．． Hiro≦? , a method of dissolving a dye in a volatile organic solvent, dispersing the solution in a hydrophilic colloid, and adding this dispersion into an emulsion, as described in Japanese Patent Publication No. 2g No. 6-2. ≠/lj, etc., in which a water-insoluble dye is dispersed in a water-soluble solvent without dissolving it, and this dispersion is added to an emulsion; US Patent p. 3. rλ2゜13
A method of dissolving a dye in a surfactant and adding the solution to the entire emulsion as described in Specification No. 6; JP-A-31-711
A method of dissolving a red-shifting compound using a red-shifting compound as described in No. 24 and adding the solution into an emulsion; A method such as dissolving in an acid and adding the solution into an emulsion is used. Other additions to emulsions include US Pat. No. 2, RI/2I3≠3, US Pat. Tata T, No. 217, No. 3. Hiroki.

The method described in No. 131 and the like can also be used. 1+ The dye of general formula (I) above may be uniformly dispersed in the silver halide emulsion before being coated on a suitable support, but may of course be dispersed during any step of the preparation of the silver halide emulsion. be able to.

The sensitizing dye according to the present invention can be used in combination with other sensitizing dyes. For example, U.S. Patent No. J, 703.3
No. 77, same No. ko, try, sat No. 3,327,
No. 040, No. 3, 6/! .

No. 437, No. 3.6λI, P reference, British Patent No. 1I
Hayumi, No. 111, No. 7. λri J, No. 162, Tokuko Sho≠
3-data jA%, same 4c reference No. 030, same≠J-t
No. 0773, U.S. Patent No. 3゜Ifil&, No. 227, %
Kai Showa 44! -47930, U.S. Patent No. J, 411,6
No. 13, same No. J, t/j.

No. 132, same No. j, j/7. ．． 2ri No. 1, same No. 3゜43
Sensitizing dyes described in No. 1.7-7 and the like can be used.

The amount of the compound represented by the general formula (II) used in the present invention is from about 0°Ol gram per mol of silver halide in the emulsion! Advantageously used in duram quantities.

The ratio (weight ratio) of the dye represented by general formula (I) to the compound represented by general formula (II) is: dye represented by general formula (I)/-compound represented by general formula II) −
The range 17/, //j00 is advantageously used, in particular /
A range of /2 to l/λ00 is advantageously used.

The compound represented by the general formula (It) 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 cellosolve, water, etc.) or a mixed solvent thereof. It can also be added to the emulsion by dissolving it in 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. Also, Tokukai Showa 2O
They can also be dispersed and added into the emulsion by the method described in the Roti publication.

The silver halide emulsion that can be used in the present invention may be any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide, and silver chloride. Preferred silver halides are silver bromide, silver chlorobromide, silver iodobromide, or silver iodochlorobromide.

Silver halide grains in photographic emulsions may have regular crystal structures such as cubic or octahedral, or irregular crystal structures such as spherical, tabular, etc.
It may have a crystalline form (gular) or a composite form of these crystal forms. It may also consist of a mixture of particles of various crystalline forms.

The silver halide grains may have different phases inside and on the surface, or may consist of a uniform phase.

Grains in which the latent image is mainly formed on the surface (for example, negative emulsion) may be used, or grains in which the latent image is mainly formed in the grain (for example, internal latent image emulsion, pre-fogged and then direct inversion emulsion) may be used. ).

The silver halide emulsion used in the present invention has a thickness of 0.65 microns or less, preferably 0.3 microns or less, a diameter of preferably 0.1 micron or more, and grains with an average aspect ratio of 1 or more have a total projected area. It may be a tabular grain that occupies more than the jO coefficient of . tfI-1 average particle size
The emulsion may be a monodisperse emulsion in which particles having a particle size of 4 or less account for 21% or more of the number of particles.

The photographic emulsion used in the present invention is P. gelafchides (
"Chimie etPhy Photography" by P. Glafkidea)
sique Photographique)J (
Published by Paul Monte1, 12
1967], G.F. Duffin
in) “7 Photographic Emulsion Chemistry”
Chemistry)r)J (The 7 Orcal Press
TheF, oct-I Press, /゛Ribu6
(2013), Gui, K., Zelikman et al. (V, L, Za
likman etal) [Making and
Coating Photographic Emulsion (Ma
King and Coating Photogra
phic Emulsion) J (Four Force/L/-
Press Published by The Foaal Press, l
It can be prepared using the method described in Hironoshi et al. That is, any of the acidic method, neutral method, ammonia method, etc. can be used for the next complete reaction of soluble silver salt and soluble halogen salt, such as one-sided mixing method, simultaneous mixing method, or a combination thereof. Good too.

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 of keeping PAgt constant in the liquid phase in which silver halide is produced, that is, a so-called Chondrald double jet method can also be used.

According to this method, a silver halide emulsion with a regular crystal shape and a nearly uniform grain size can be obtained.

Two or more silver halide emulsions formed separately may be mixed and used.

In addition, during the formation of silver halide grains, silver halide solvents such as ammonia, rhodanpotash, rhodanammonium, thioether compounds (for example, U.S. Pat. No. 3.27/117, U.S. Pat. 57μ, 6λ1 No., same g, 3.70≠, /30 No., same≠, 2ri7゜4tj5', same No. μ, cocoa, 3
7μ, etc.), thione compounds (for example, JP-A No. 13-/Hirohiro, J/RI, Il & 53-r, No. 11)
-77゜737, etc.), amine compounds (for example, JP-A No. 1007/7), amine compounds (for example, JP-A No. 1007/7) can be used.

The formation of silver halide grains occurs during the physical ripening process.
Cadmium salt, zinc salt, talicum salt, iridium salt or a complex salt thereof, rhodium salt tx may be coexisting with a complex salt thereof, an iron salt, or an iron complex.

In addition, examples of internal latent image type emulsions used in the present invention include US Patent λ,! Octopus, No. 210, 3゜204.31
No.3, 3.4A Hiro 7.5P27, J, 76/, 2
No. 7, and No. 31 TaJ! Examples include conversion type emulsions, core/shell type emulsions, and emulsions incorporating different bridge metals as described in , 0/≠, etc.

Silver halide emulsions are usually chemically sensitized.

After chemical sensitization, for example, H Freezer (H
, Fr1eser) ed.
Photography Photography Project Mituto Zilbel Halogen-7”y (Di eGrundlage
n der PhotographiachenP
rozeaae mit Sllber-haloga
Akademische Verlagsgesel
lachaft.

The method described on page 734A can be used.

Namely, sulfur sensitization using sulfur-containing compounds that can react with activated gelatin and silver (e.g., thiosulfates, thioureas, mercapto compounds, rhodanine #I); reducing substances (e.g., stannous salts); , amines, hydrazine derivatives, formamidine sulfinic acid, silane compounds); noble metal compounds (e.g., total complex salts, complex salts of metals in Group I of the periodic table such as Pt, Ir, and Pd); The noble metal sensitization methods used can be used alone or in combination.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the manufacturing process, storage, or photographic processing of the light-sensitive material, or for stabilizing photographic performance. Namely, azoles such as benzothiazolium salts, nitroindanoles, triazoles, benzotriazoles, benzimidazole (substituted with nitro or halogen); heterocyclic mercazoto compounds such as mercaptothiazoles, mercaptobenzo Thiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially l-phenyl-!-mercaptotetrazole), mercaptopyrimidines; compounds; thioketo compounds such as oxazolinthione; azaindenes such as tetraazaindenes (especially ≠-hydroxy substituted (/r 3+ 'a+
7) Many compounds known as antifoggants and stabilizers can be added, such as tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; etc.

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

That is, it may contain a compound that can develop a color by oxidative coupling with an aromatic primary amine developer (for example, a phenylene diamine derivative, an amine phenol derivative, etc.) in a color development process.

For example, as a magenta coupler, ! - There are pyrazolone couplers, pyrazolobenzimidazole couplers, cyanoacetylcoumarone couplers, open chain acylacetonitrile couplers, etc. Yellow couplers include acylacetamide couplers (e.g. benzoylacetanilides, pivaloylacetanilides), etc., and cyan couplers Examples include naphthol couplers and phenol couplers. These couplers are preferably non-diffusive and have a hydrophobic group called a ballast group in the molecule. The coupler may be either ≠ equivalent or di-equivalent to the silver ion. It may be a colored coupler that has the effect of correcting the skin follicle, or a coupler that releases a development inhibitor during development (so-called DIR coupler).

In addition to DIR Cub 2-, the product of the coupling reaction is colorless and may contain a colorless DIR Cub compound that releases a development inhibitor.

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

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

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

For example, nonionic surfactants such as saponins (steroids), alkylene oxide derivatives (e.g. polyethylene glycol, polyethylene glycol alkyl ethers, glycidol derivatives, fatty acid esters of polyhydric alcohols, alkyl esters of sugars; alkyl carboxylates) , amphoteric surfactants such as alkyl sulfo-tRN, flukylbe/ze/sulfo/acid, alkyl sulfate esters; alkylamine salts, aliphatic or aromatic primary ammonium salts, heterocycles such as pyridinium, imidazolium, etc. Cationic surfactants such as high grade ammonium salts can be used.

In practicing the invention, other additives may be used in photographic emulsions, along with other hydrocolloids. Examples include anti-fading agents, inorganic or organic hardeners, anti-fogging agents, ultraviolet absorbers, mordants, plasticizers, latex polymers, matting agents and the like. Specifically, research disclosure (l1esearch D)
isclosure) Volume 776 (lri71.X[)R
It is described in D-t7a≠3, etc.

Further, in the photographic emulsion used in the present invention, a hydrophilic polymer such as gelatin is used as a protective colloid.

The finLahed emulsion is prepared on a suitable support such as baryta paper, resin coated paper, synthetic paper, triacetate film, polyethylene terephthalate film,
Other plastic bases are applied onto glass plates.

The dyes of the present invention are used with silver halide photographic emulsions for various color and black and white sensitive materials.

More specifically, color positive emulsions, color one-per emulsions, color negative emulsions, color reversal emulsions (which may or may not contain couplers), photosensitive materials for printing plates (e.g. lithium film, lithography), Emulsions used in photosensitive materials for X-ray recording (especially materials for direct and indirect photography using screens), emulsions used in photosensitive materials for X-ray recording (especially materials for direct and indirect photography using screens), and silver salt diffusion transfer processes (5ilver 5alt diff)
transfer procas+s)
K Emulsions used - Emulsions used in the color diffusion transfer process, die transfer process
emulsions used in silver dye bleaching methods, printouts*
Emulsion used for recording materials, Photon i: 4! (Direct Pr1nt image) Emulsion used in photosensitive building materials, Emulsion 1 used in photosensitive materials for heat development
Photosensitive materials for physical development (for example, British patent Pco 0,27
It is used together with emulsions, etc. used in

Exposure to obtain a photographic image may be carried out using a conventional method. i.e. natural light (sunlight), tungsten electric light,
Any of a wide variety of known light sources can be used, such as fluorescent lamps, mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, and cathode ray tube flying spots. The exposure time is from 171,000 seconds normally used in cameras to 7
In addition to exposure times as short as 171,000 seconds, exposure times as short as 171,000 seconds can be used, for example, using xenon flash lamps or cathode ray tubes.
/104 to //10% A 6 second exposure can be used, or an exposure longer than 7 seconds can be used.

If necessary, the spectral composition of the light used for exposure can be adjusted using a color filter. Laser light can also be used for exposure. "Also, exposure may be performed by light excited by electron beams, X-rays, r-rays, α-rays, etc. and then emitted from a phosphor.

Photographic processing of light-sensitive materials made using the present invention includes, for example, Research Disclosure (Research Disclosure).
Diseloaure) / Issue 7A, pages 2t-30 (
RD-/74≠3)K Any of the known methods and known treatment liquids as described above can be applied. This photographic processing may be either a photographic processing for forming a silver image (black and white photographic processing) or a photographic processing for forming a dye W (power 2-photographic processing), depending on the purpose. The processing temperature is usually chosen between /r'c and jOoC,
The temperature may be lower than /IOC or higher than zooc.

(Example) Next, examples according to the present invention are shown below, but the present invention is not limited thereto.

Example 70 moles of silver chloride, -ta! Morch's silver bromide and 0.
A sulfur-sensitized, parodanized silver emulsion consisting of j molar silver iodide was prepared. The average particle diameter of these silver rodanide particles is 0.3! Next time with rμ.

This emulsion was weighed/Kl into a pot, dissolved and mixed with the sensitizing dye represented by the general formula (I)K and the general formula (I
F) is added, and further Hiroshi-hydroxy-t-methyl-/,3°3a,7-chitrazaindene fO6J? After sequentially adding 1 mole of silver halide, 7 moles of dodecylbenzenesulfonic acid/silver halide, 0 mole of mucochloric acid, and 1 mole of It/silver halide, the mixture was coated on a polyethylene terephthalate film base to form a photographic material. Obtained.

These film samples were used as a light source with a color temperature of Irju"K and a 5c-to filter manufactured by Fuji Photo Film Co., Ltd. (a red filter that only transmits light with wavelengths longer than AOOnm, i.e., in this case, only light in the spectral sensitization region caused by the dye). )
I attached it to a light wedge exposure.

Separately, a second exposure was carried out to obtain a spectrogram using a diffraction grating spectrograph equipped with a tungsten light source with a color temperature of -666°.

After exposure, the strips were developed for 2 minutes using a developer having the composition shown below, stopped, subjected to a fixing bath, and further washed with water to obtain strips with a predetermined black and white image. The density and fog of this strip were measured to obtain the sensitivity and fog.

The optical density reference point that determined the sensitivity and fog is [Fog +
/, j).

Composition of developer Add water to make it.

When using, add 1 volume of water to make the working liquid.

The results obtained are shown in Tables 1 to J as relative values.90 The sensitizing dye of the general formula (I) is significantly sensitized by the combined use of the compound represented by the general formula (I[). That will be understood.

[Brief explanation of the drawing]

Figures 1 and 2 show the luminescence sensitivity curves obtained by using the sensitizing dye (I) alone and by the combination of the sensitizing dye (I) and the compound (I[l) according to the present invention. The numbers assigned to the curves in Figure 1 correspond to the numbers in the ctrogram column on the right side of Table 1, and the numbers on the curves in Figure 2 correspond to the numbers in the spectrogram column in Table 2. The vertical axis shows the sensitivity value, and the horizontal axis shows the wavelength. Patent applicant: Fuji Photo Film Co., Ltd.

Claims (1)

[Scope of Claims] At least one silver halide photographic emulsion layer containing at least one sensitizing dye represented by the following general formula (I) and at least one compound represented by the following general formula (II) A silver halide photographic material comprising: General formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, n represents 0 or 1, m represents 1 or 2.R_
1 represents a substituted or unsubstituted alkyl group, R_2
, R_3 and R_4 may be the same or different from each other and represent a hydrogen atom, an alkyl group, an alkoxy group, a hydroxy group, a substituted or unsubstituted amino group or a halogen atom, and R_2 and R_3, R_3 and R_4 or R
_2 and R_4 may form a fused 6-membered ring. Z_1 represents an atomic group necessary to form a 5-membered ring or a 6-membered ring, and these rings may have a substituent or be fused with another ring. Z_2 represents an atomic group necessary to form a 5-membered ring or a 6-membered ring, and these rings may have a substituent or be fused with another ring. L_1 and L_2 represent a methine group or a substituted methine group. ) General formula (II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (Here, A represents a divalent aromatic residue. R_1_1R
_1_2, R_1_3, and R_1_4 are each a hydrogen atom, a hydroxy group, an alkyl group, an alkoxy group, an aryloxy group, a halogen atom, a heterocyclic nucleus, a heterocyclylthio group, an arylthio group, an amino group, a substituted or unsubstituted alkylamino group, or a substituted or an unsubstituted arylamino group,
Represents a substituted or unsubstituted aralkylamino group, aryl group, or mercapto group. However, at least one of A, R_1_1, R_1_2, R_1_3, and R_1_4 has a sulfo group. W represents -CH= or -N=. )