JPS61282834A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To enhance sensitivity and to prevent fog by forming a silver halide emulsion layer contg. a combination of 2 kinds of sensitizing dyes represented by specified formulae on a support to form a photographic sensitive material. CONSTITUTION:A silver halide photographic sensitive material is formed by laminating on the support a silver halide emulsion layer contg. one of the sensitizing dyes represented by formulae I, and one of the sensitizing dyes represented by formula II and III, and in these formulae I, II, and III, each of Z1, Z2 is a pyrroline ring or pyriding ring or the like; each of R1, R2 is an aliphatic group X<->1 is a acid anion; n is 1 or 2; each of R3, R4 is H, alkyl, or aryl; each of R5, R11 is linked to a quternary ammonium; each of R7, R8, R9 is halogen, alkyl, aryl, or the like; each of R6, R10 is alkyl aralkyl, or the like; Y<-> is a counter ion: each of R3, R4, R5, R6 is same in either of formulae II and III, respectively; and each of R12, R13, R14 is alkyl or the like.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material), and more specifically, it relates to a silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material), and more specifically, a novel combination of at least two types of sensitizing dyes to produce strong colors. This invention relates to a photographic material that has been sensitized and has improved photographic properties.

[Prior Art J] It is generally known that when a sensitizing dye is added to a light-sensitive silver halide emulsion, the sensitive wavelength range of the silver halide emulsion is expanded and the emulsion is optically sensitized.

As optical sensitizing dyes used for such purposes, a large number of compounds are conventionally known.

In addition, in silver halide photographic materials having panchromatic spectral sensitivity characteristics, thiacarbocyanine or selenacarbocyanine is often used as a sensitizing dye for spectral sensitization of silver halide photographic emulsions.

However, in panchromatic photographic materials, it may be necessary to further spectral sensitize to blue light having a wavelength shorter than 50,001 but longer than the wavelength region of inherent sensitivity of silver halide. For example, this is required in a panchromatic photographic material used for three-color separation photography in a printing plate-making process. For such purposes, it is known to use abome O cyanine or dimethine merocyanine, or both, together with the above-mentioned thia-(or selena-)carbocyanine (eg, US Pat. No. 3,808,009).

However, such methods often result in fogging or decreased sensitivity to red light.

A combination of highly spectral sensitizers using two types of sensitizing dyes, which can be highly spectral sensitized from the red-sensitive region to the blue-sensitive region, was developed in
4-34535 and Japanese Patent Publication No. 54-38936, these combinations result in poor stability of the photosensitive material over time, and may cause fogging in photosensitive materials that have been subjected to long-term bonding.
Alternatively, there were drawbacks such as problems such as decreased sensitivity.

[Object of the Invention] The first object of the present invention is to provide a photosensitive material with improved photographic properties using a sensitizing dye that is highly sensitive and does not cause fogging.

The present invention further provides a silver halide photographic emulsion that is highly spectrally sensitized in at least one of the red region or edge region and the blue region by a combination of sensitizing dyes having good temporal stability in the sensitizing dye solution. That's true.

A further object of the present invention is to provide a black and white light-sensitive material or a color light-sensitive material that has excellent color sensitivity and stability over time by combining the above-mentioned sensitizing dyes.

[Structure of the Invention] As a result of various studies, the present inventors have found that the above object is to provide a light-sensitive material having at least one silver halide emulsion layer on a support, in which the silver halide emulsion layer has the following general formula [ I
] and at least one sensitizing dye represented by the general formula [I[
] or [111] in combination with at least one of the sensitizing dyes, and the present invention has been achieved based on this discovery.

General formula [I] [wherein zl and 72 are respectively pyrroline nucleus, pyridine nucleus, indolenine nucleus, benzimidazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus,
naphthoxazole nucleus, thiazoline nucleus, thiazole nucleus,
Indicate the atomic groups necessary to complete the benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus or naphthoselenazole nucleus, and R1 and R2 may each be substituted (if the carbon chain is an oxygen atom) or an aliphatic group which may be interrupted by a sulfur atom, and the aliphatic group having a small number of R1 and R2 (both of which have one of a hydroxy group, a carboxy group, and a sulfo group, 63 is an acid anion, n is 1 or 2, but when the dye forms an inner salt, n is 1.] General formula [1 [] [wherein, R3 and R4 are i) Each hydrogen atom or □ is an optionally substituted monovalent group, and at least one is an optionally substituted alkyl group or aryl group, preferably each hydrogen atom or each optionally substituted monovalent group. A good alkyl group or aryl group, at least one of which is an optionally substituted alkyl group or aryl group, respectively.

or ′ (11) A group of atoms that together complete a ring (preferably 5 to 6 members) fused to a ring containing tellurium and nitrogen, and preferably an aromatic fused directly to the ring containing tellurium and nitrogen. It is an atomic group that completes the aromatic ring fused to the □ group ring or the unbound aromatic ring fused to the ring containing tellurium and nitrogen.

R5 and R11 independently represent a quaternized W1 substituent, R
5 may cooperate with R1 to complete a preferably 5- to 6-membered fused heterocycle. Furthermore, R6 may cooperate with R'5 to complete a preferably 5- to 6-membered fused heterocycle.

R7, R8 and R9 are each hydrogen atom, halogen atom, alkyl, aralkyl, aryl, heterocycle, cyano, amino, alkylthio, arylthio, alkoxy,
Represents an aryloxy group or an acidic nucleus.

R5 and R9 each represent a hydrogen atom, alkyl, aralkyl, aryl, heterocycle, amino, cyano, alkylthio, arylthio, alkoxy, or aryloxy group. R6 and Rho (however ■-0) or R7
and R9 may preferably work together to form a 5- to 6-membered ring.<%R11 may work together with Rlo to preferably form a 5- to 6-membered fused heterocycle.

Q preferably represents an atomic group completing the nucleus of a 5- to 6-membered nitrogen-containing heterocycle, Y'''' represents a counter anion, and p represents 0 or a positive integer for combining ionic charges.

l and ■ each represent 0 or 1, and n represents 0.1 or 2. ] Below is a blank general formula [1] In formula 1, R3, R4, Rs and Re are general formula [I[]
is synonymous with

R12, R13 and Rs4 each represent a hydrogen atom, an alkyl, aralkyl, aryl, alkylthio, cyano, arylthio, alkoxy, or aryloxy group.

R12 and R14 may jointly preferably form a 5- to 6-membered ring.

q represents O or 1, and E represents an acidic nucleus. ] The naphthoxazole nucleus in the general formula [I] includes a naphthoN, 2-d ]oxazole nucleus, and a naphtho[2,
1-d ]oxazole nucleus, naphthothiazole nucleus has naphthoN, 2-d ]thiazole nucleus, naphtho[2,3-
d ]thiazole nucleus includes naa, toselenazole nucleus includes naphtho[2,1-d]selenazole nucleus, and the like. The aromatic hydrocarbon rings of these cores may have various substituents.

For example, halogen atoms (e.g. chlorine atom, bromine atom, fluorine atom), alkyl groups with up to 4 carbon atoms (e.g. methyl group, ethyl group, isopropyl group, 3-propyl group, butyl group), cyano group, carboxy group, carbon Furkylcarbonyl group with up to 4 carbon atoms (e.g. ethoxycarbonyl group), furkylcarbonyl group with up to 4 carbon atoms (e.g. acetyl group), alkylsulfonyl M with up to 4 carbon atoms (e.g. methylsulfonyl group), aromatic hydrocarbon groups (e.g. phenyl group, p-tolyl group), halogen-substituted alkyl group (e.g. trifluoromethyl group), drooxy group, alkoxy group having up to 4 carbon atoms (e.g. methoxy group, ethoxy group), or alkyl group having up to 4 carbon atoms Examples include carbonylamino groups (eg, acetylamino groups).

There are 4 carbon atoms on the 1-position nitrogen atom of the benzimidazole nucleus.
The indolenine nucleus The 3-position carbon atom of can have a lower alkyl group having up to 3 carbon atoms (for example, a methyl group) as a substituent.

At least one of R1 and R2 represents an aliphatic group having up to 8 carbon atoms substituted with either a hydroxy group, a carboxy group or a sulfo group, and the rest represent aliphatic groups having up to 8 carbon atoms. These aliphatic groups may further have other substituents (eg, hydroxy groups), and may also be aliphatic groups whose carbon chains are interrupted by oxygen or sulfur atoms.

Xt+? represents an acid anion, and n represents 1 or 2. When the dye normally forms an intramolecular salt, n is 1.

In addition to the above, specific examples of heterocyclic nuclei completed by Zl or Z2 include pyrroline, thiazoline, pyridine,
Examples include nuclei such as 3.3-dimethylindolenine, 3.3.6-drimethylindolenine, 6-chloro0-3.3-dimethylindolenine, and 3,3,5°6-titramethylindolenine. .

Furthermore, specific examples of the substituents represented by R1 and R2 are as follows. That is, methyl group, ethyl group, propyl group, butyl group, 2-methoxyethyl group, 2-ethylthioethyl group, 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxyethyl group, 2-carboxyethyl group. , 3-carboxyethyl group, 4-carboxybutyl group, 3-carboxybutyl group, 2(2-carboxyethoxy)ethyl group, 2-sulfoethyl group, 3-sulfopropyl group, 3-sulfobutyl group, 4-sulfobutyl group, These include 2-(3-sulfopropoxy)ethyl group, 2-hydroxy-3-sulfopropyl group, 3-sulfoboxyethoxyethyl group, vinylmethyl group, and the like.

Acid anions represented by It is.

Among the compounds represented by the above general formula [II], the compounds represented by the following general formula [I-1] are particularly useful.

General formula [I-1] In the formula, z3 and z4 are benzothiazole nucleus, naphtho[1,
2-d ] Thiazole nucleus, benzoselenazole nucleus, naphthoN, 2-d ] The atomic groups required to complete the selenazole nucleus, R1, R2, X (1? is the general formula [II
Hail the same meaning.

Particularly useful compounds in general formula [1-11] are compounds represented by either of the following general formulas [1-21 and [I-3].

General formula [I-2] In the formula, Z5 and z6 each represent a sulfur atom or a selenium atom, Wt and W2 respectively represent a hydrogen atom, a chlorine atom, a bromine atom, a fluorine atom, a methyl group, an ethyl group, a methoxy group, Or represents an ethoxy group. Rls and RlB each represent a methyl group, an ethyl group, a hydroxyalkyl group (e.g. β-hydroxyethyl group, β-hydroxyprobyl group, etc.), a carboxyalkyl group (e.g. carboxymethyl group, β-
carboxyethyl group, γ-carboxypropyl group, etc.),
Also, sulfoalkyl groups (e.g. β-sulfoethyl group, γ
-sulfopropyl group, γ-sulfobutyl group, δ-sulfobutyl group, etc.). However, at least one of R+s and RlG represents a carboxyalkyl group or a sulfoalkyl group. X31. and n is the general formula [l-11
I agree with you.

General formula [l-31 Z5, Z6, Wl, R15 and R16 in the general formula [l-31]
I agree with the statement in l-31.

Further, the compound represented by the general formula [1] or [II[] will be explained in more detail.

The ring completed by R3 and R4 in the general formulas [I[] and [1] is typically a 5- to 6-membered aromatic ring such as benzene, naphthalene, thiophene, benzothiophene, furan, benzofuran, and pyridine. These rings may be substituted.

Substituents include hydroxy and hydroxyalkyl groups (
(e.g., methoxy, ethoxy, β-methoxyethoxy, γ-carboxypropyl, etc.); oxy, etc.), aryloxy (e.g., phenoxy, p-lyolphenoxy, etc. groups), aryl groups (e.g., p-tolyl, phenyl, -monohydroxyphenyl, p-hydroxyphenyl, 2-hydroxyethyl, etc.) groups), /%Ogen atoms (e.g., chloro, fluorine, bromine, etc.), trifluoromethyl groups, amino groups (e.g., dimethylamino groups, diethylamino groups, etc.), cycloalkyl groups (e.g., cyclohexyl basis),
Siam L carbamoyl group (e.g. carbamoyl, N, N
- pentamethylenecarbamoyl, N,N-dimethylcarbamoyl, N,N-diethylcarbamoyl, etc.)
, an alkoxycarbonyl group (for example, an ethoxycarbonyl group), and an alkylthio group (for example, a methylthio group).

Examples of rings in which R4 and Rs or Rs and R6 are bonded and fused to a tellurium-containing heterocycle include the following.

The quaternized substituent represented by R5 and R11 is preferably an optionally substituted hydrocarbon group having 1 to 10 carbon atoms, such as an alkyl group (for example, an unsubstituted group such as methyl, ethyl, isobutyl, methoxyethyl, etc.). , sulfobutyl, carboxymethyl, sulfamoylethyl, carbamoylethyl, etc.), aryl group (e.g., phenyl, carboxyphenyl, etc.), aralkyl group (e.g., benzyl, phenethyl, etc.), allyl Examples include groups.

In one preferred form, R5 and Rn are substituted hydrocarbons (eg, alkyl or aryl groups) containing 1 to 8 carbon atoms.

Typical substituents include sulfo, sulfato, carboxy, droxy, carbamoyl, sulfamoyl, cyano, succinimino, trimethylsilyl, alkoxy, and sulfo-substituted alkoxy.

Specifically, sulfomethyl, sulfoethyl, sulfopropyl, sulfobutyl, sulfophenyl, sulfatomethyl, sulfatoethyl, sulfatopropyl, sulf7toptyl, sulf7tophenyl, carboxymethylboxypropyl, carboxybutyl, carboxyphenyl, hydroxyethyl. , hydroxypropyl, carbamoylmethyl; carbamoylethylcarbamoylpropylrubamoylphenyl, sulfamoylethyl, cyanoethyl, cyanopropyl, iminoethyl succinate, iminopropyl succinate, trimethylsilylethyl, methoxyethyl, methoxypropyl, sulfoethoxyethyl, and other groups is typical.

In general formula [1[], examples of the nitrogen-containing heterocyclic group necessary to form the cyanine dye represented by are shown below.

These basic nitrogen-containing heterocycles may be substituted with any substituent (
For example, alkyl groups such as methyl group and ethyl group, phenoxy group such as methoxy group and ethoxy group, furkylthio group such as methylthio group and ethylthio group, aryl group such as phenyl group and tolyl group, 7-aryloxy group such as phenoxy group, Heterocyclic groups such as chenyl group, benzothiazolyl group, pyridyl group, halogen atoms such as fluoro atom, chloro atom, bromine atom, amino groups such as N,N-diethylamino group, acetylamino group, methoxycarbonyl group, ethoxycarbonyl group, etc. alkoxycarbonyl group, cyano group, N, N-
dimethylcarbamoyl group, carbamoyl group, N,N-dimethylsulfamoyl group, sulfamoyl group, nitro group, trifluoromethyl group, hydroxy group, methylsulfonyl group, etc.
Synthesis and properties of cyanine and related dyes in heterocyclic compounds - Volume 30 (1977) [S ynt
hesis and properties of
CVanines and Re1ated Dyes
in Chemistry of Heterocyc
lic Compounds30 (1977)]
, 1-. M. Haraa, Cyanine Dice and Related Combines (1964, published by Inter Science Publishers), The Chemistry of Heterocyclic Combounds
It is selected from the known ones described in Volume 34 (3) (published by Inter Science 1 Publications) and the like.

In the formula, Ro represents a monovalent organic substituent, and an alkyl group (
For example, unsubstituted groups such as methyl, ethyl, and isobutyl; substituted groups such as methoxyethyl, hydroxyethyl, hydroxyethoxyethyl, carboxyethyl, and sulfamoylethyl; phenyl, p-sulfophenyl, etc.), heterocyclic groups (eg, 2'-pyridyl, 2-chenyl, 2-benzothiacylyl, etc.), allyl groups, benzyl groups, and hydrogen atoms.

Examples of the alkyl represented by R6 or Rlo include groups such as methyl, ethyl, and 70robyl; examples of aralkyl include groups such as benzyl, phenethyl; and examples of aryl such as phenyl; For example, each group such as chenyl or furyl can be used as an amino group, a substituted amino group such as dimethylamino or anilino can be used as an amino group, a methylthio group can be used as an alkylthio group, a phenylthio group can be used as an arylthio group, and an example can be used as an alkoxy group such as methoxy, ethoxy, etc. Examples of the aryloxy groups include phenoxy groups.

The alkyl group represented by R7, R8 or R9 includes, for example, methyl, ethyl, propyl, butyl, etc.; the aracyl group includes, for example, benzyl, phenethyl, etc.; and the halogen atom includes, for example, fluorine, chloro, etc. Examples of the amino group include substituted amino groups such as dimethylamino, tetramethyleneamino, and anilino; examples of the aryl group include phenyl; and examples of the heterocyclic group include chenyl and furyl; The alkylthio group includes, for example, a methylthio group, the arylthio group includes, for example, a phenylthio group, the alkoxy group includes, for example, methoxy and ethoxy groups, and the aryloxy group includes, for example, a phenoxy group.

The acidic nucleus represented by R7, Ra or R9 in the general formula [111 or E in the general formula [■j] may or may not be cyclic, and the following are exemplified. ).

If it is a geographical firearm, the blank space below is R'L, Rh, R, tFRcj, sotL.
-F is a substituent with a hydrogen atom, an alkyl group (e.g. methyl group, ethyl group, octyl group, dodecyl group, 5
ec-octyl group, etc.), nalaryl group (eg, p-tolyl group, phenyl group, etc.), or heterocyclic group (eg, benzofuryl group, etc.).

If j is a cyclic group, in the following margin 1 formula,
R is a monovalent substituent, such as a hydrogen atom, an unsubstituted alkyl group (e.g. methyl group, ethyl group, etc.), a substituted alkyl group (e.g. methoxyethyl group, hydroxyethyl group, carboxyethyl group, sulfoethyl group, carbamoyl group) ethyl group, etc.), aryl groups (eg, phenyl group 1), and heterocyclic groups (eg, pyridyl group, benzothiazolyl group, etc.). Further, the ring may have a substituent such as a methyl group or a phenyl group. ], etc.

R12% The alkyl group represented by R13 or R14 includes, for example, methyl, ethyl, propyl, etc., the aralkyl group includes, for example, benzyl, phenethyl, etc., and the aryl group includes, for example, phenyl, and cyano group. Examples of the alkoxy group include methoxy and ethoxy groups; examples of the aryloxy group include phenoxy; examples of the alkylthio group include methylthio; and examples of the arylthio group include phenylthio.

Y- representing the counter ion is a halogen atom (chloro,
Representative examples include anions such as bromine and iodine atoms) and sulfone M (methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, etc.).

In a preferred form, the cyanine dyes of the present invention satisfying the general formula [rlI] are represented by the following general formulas [IV], [V], [VI]
and [■].

Below are the blank general formula [■] General formula (V) General formula [■] Ra s R4s Rs s R11%
Re, R10% f's D and Y- have the same meanings as in the above general formula [1[], and the same ones are exemplified.

R17 is a hydrogen atom, an alkyl group (e.g., methyl, ethyl, butyl, butyl, etc.), an aralkyl group (e.g., benzyl, netyl, etc.), a halogen atom (e.g., fluorine, each atom), M-substituted amino group (for example, dimethylamino, tetramethyleneamino, anilino, etc.), aryl group (e.g. diphenyl group), heterocyclic group (
For example, groups such as chenyl and furyl), alkylthio groups (
For example, it represents a methylthio group), an arylthio group (for example, a phenylthio group), an alkoxy group (for example, methoxy, ethoxy, etc.), and an acidic nuclear group.

Examples of the acidic nucleus represented by R17 include malononitrile, alkylsulfonylacetonitrile, cyanomethyl benzofuranyl ketone or cyanomethyl phenyl ketone, 2-pyrazolin-5-one, pyrazolidine-3,5
-dione, imidacillin-5-one, hydantoin, 2
or 4-thiohydantoin, 2-iminooxazolin-''4-one, 2-oxazolin-5-one, 2-thioxazolidine-2,4-dione, isoxazoline-5
-one, 2-thiazolin-4-one, thiazolidine-4
-one, thiazolidine-2,4-dione, rhodanine,
Thiazolidine-2,4-dithione, isorhodanine, indan-1,3-dione, thiophen-3-one, thiophene-3-1,1-dioxide, indolin-2-one, indolin-3-one, indacillin-3- on,
2-oxoindacillinium, 3-oxoindacillinium, 5,7-thioxo6,7-dihydrothiazolo[
3,2-alpyrimidine, cyclohexane-1,3-dione, 3,4-dihydroisoquinolin-4-one, 1.
3-dioxane-4,6-dione, barbic acid, 2-
Possible karyotypes are thiobarbic acid, lyoman-2,4-dione, indacillin-2-one or pyrido[1,2-a]]pyrimidine-1,3-dio.

Rla and R19 each independently represent a hydrogen atom, alkoxy (e.g., methoxy, ethoxy, etc. groups), aryloxy (e.g., phenoxy group), alkylthio (e.g., methylthio group), and arylthio (e.g., phenylthio group). .

R20 and R21 each independently represent a hydrogen atom, a methyl group,
Represents an ethyl group.

Specific examples represented by the general formula [I] will be shown below.

Below margin (1-A) (1-B) (1-C) (1-D) ←1-E) (IF) (1-G) (1-I) (1-J) (1-K) (1-L) (1-M) (1-N) (IP) CI-Q) 02H.

(1-T) (1-U) (1-V) Below margin [3] (5) (11th (16 (17) etas (19) (25) (39) (43) N(C,)mu]3 (45) (49) CH.

■ Hs Ct) Mu P-s The dye of the general formula [I] in the following margin is, for example,
, 56-38936, and the sensitizing dye of the general formula [I[] or [111] of the present invention can be synthesized by referring to the following patent, Bunju.

British Patent No. 625,245, British Patent No. 654,690, British Patent No. 841.119, Color Circle Patent No. 151,161, U.S. Patent No. 1,846.302, British Patent No. 2,345,094
No. 2,369,646, No. 2, 378.783
@, No. 2,385,815, No. 2.478.366
No. 2,610.121, No. 2,238. ,231
No. 2,213,995, No. 2,503.776, and No. 2,734,900, JP-A-47-9
678, 6G-78445, Journal of the American Chemical Society
67 volumes, 1875-1889 (1945), F.
M. Harma, Cyanine Dice and Related Compounds (published by Inter Science Publishers, 1964) Pharmaceutical Journal, Volume 68, 191-19
4 (194B).

Next, a specific synthesis example of the sensitizing dye of general formula [I] will be shown, but other compounds represented by general formula [I] can also be synthesized according to the following synthesis method.

Synthesis Example-1 Bis-3,8-3', 10-trimethyleneteralucyanine iodo salt (Exemplary Compound No., 16>2.3-
4 g of trimethylene benzotellazolium iodo salt and 1.5 g of orthoformic acid ethyl ester were added to pyridine 30112.
added to.

Triethylamine was added, and the mixture was heated under reflux for 15 minutes and allowed to cool to crystallize.

The precipitate was collected by filtration and washed with ethanol to obtain crude product 1, Og.

It was purified by repeated recrystallization from methanol.

Yield @ 0.61J, melting point over 300℃.

Maximum absorption wavelength in methanol is 627 nm.

Synthesis Example-2 3-(2-[3-(5,6-sihydro28°4H-tellazolo(5,4,3-i,j)quinoline-2-ylidene-1-propenyl]-1-naphtho[1, 2-d
] Thiazolio) propanesulfonic acid inner salt (Exemplary Compound No., 28) 5.6-Sihydro-2-methyl-4-day-Terrazolo[5,4,3-i,j] Quinolinium chloride (3.2 g) is anhydrous. Suspended in 30ml of acetic acid,
Add 3.8 g of diphenylformamidine and heat under reflux for 10 minutes. After cooling, the mixture is diluted with isopropyl ether, and the precipitate is collected by filtration, washed with ethyl acetate, and dried. Yield @ 3.30° 2.3g of the crude product was dissolved in 11-cresol 20iJ2, and 1.6g of 3-[2-methyl-1-naphtho(1,2-d)thiazolio]propanesulfonic acid inner salt and Triethylamine2. Add Og and heat and stir at 110° C. for 20 minutes.

After cooling, dilute with isopropyl ether and discard the supernatant. Add acetone and stir to crystallize, collect the precipitate by filtration and wash with ethanol.

The crude product is purified by repeated recrystallization from chloroform-methanol (1:1).

Yield o, ssg, melting point 300°C or higher.

Maximum absorption wavelength in methanol solution: 607n■.

Synthesis Example-3 2-(5-2-[3-methyl-4-phenyl-2(3H
) tellurazoliden) ethylidene]-4-oxo2-thioxo-1,3-thiazolidin-3-yl)ethanesulfonic acid (exemplary compound NO634) 2-acetamidovinyl-3-methyl-4-phenyltellazolium trifluoromethanesulfonic acid 2.9g salt
and 1.2 g of 3-β-sulfoethyl O-danine were dissolved in 30*Q absolute ethanol, 2 g of triethylamine was added, and the mixture was heated under reflux for 15 minutes.

The reaction solution is allowed to cool, and then sufficiently cooled in a water bath to cause crystallization, and the precipitated crystals are collected by filtration. The crude product is purified by repeated recrystallization from methanol.

Yield 0.8IQ.

Maximum absorption wavelength in methanol solution is 548 nm.

Synthesis Example-4 2-(5-chloro-2-[3-(3-methyl-4-7enyl-2(3H)tellazolidene)-1-probenylidene]-3-penzooxazolio)ethanesulfonic acid inner salt (Exemplary Compound No. 39) 13.5111 of 2-methyl-4-phenyltetrazole was added to 80% of dichloromethane.
1Q, add 9.0 g of methyl trifluoromethanesulfonate, seal the solution, and leave it at room temperature for one week.

The precipitated crystals are collected by filtration and then suspended in 120 iQ of acetic anhydride. Add 19.6 g of diphenylformamidine to 1
Heat to reflux for 0 minutes. After cooling, dilute with isopropyl ether, filter the precipitate, wash with ethyl acetate, and dry. Yield 15. IQ.

2.9 g of the crude product was dissolved in l-cresol 2011,
1.4 g of 2-(5-chloro-2-methyl-3-penzooxazolio)ethanesulfonic acid inner salt and 1 g of triethylamine are added, and the mixture is heated and stirred at 110° C. for 15 minutes.

After cooling, dilute with isopropyl ether and discard the supernatant. Add acetone and stir to crystallize. The precipitate is collected by filtration and washed with ethanol.

It was purified by recrystallization from a mixed solvent of chloroform-methanol <1:2).

Yield 0.549° Maximum absorption wavelength in methanol solution: 601nl.

Synthesis Example-5 Anthro[]-3-(2-[3-(5-fluoro-3-
Methyl-2(3H)penzotellazolidene)-1-propenyl]-5-methoxy3-penzoselenazolio)propanesulfonic acid inner salt (Exemplary Compound No. 49) 5-Fluoro-2-methylbenzotella Sol 13゜1
Dissolve Q in 10011 dichloromethane, add 9.0 liters of methyl trifluoromethanesulfonate, seal tightly and leave at room temperature for 2 weeks.

The precipitated crystals are collected by filtration and then suspended in acetic anhydride 100112. Add 19.6 g of diphenylformamidine and heat under reflux for 10 minutes. After cooling, dilute with inpropyl ether, filter the precipitate, wash with ethyl acetate and dry. Yield: 8.3g.

2.89 of the crude product was dissolved in l-cresol 20-
1.7 g of -(5-methoxy-2-methyl-3-penzoselenazolio)propanesulfonic acid inner salt and 2 g of triethylamine are added, and the mixture is heated and stirred at 110° C. for 15 minutes.

After cooling, dilute with isobutylene ether and discard the supernatant. Add acetone and stir to crystallize. The precipitate is collected by filtration and washed with ethanol.

Purification was performed by recrystallization from a mixed solvent of chloroform-methanol (1:2).

Yield: 0.51.

Maximum absorption wavelength in methanol solution: 599nl.

Synthesis Example-6 5-(4-[3-ethyl-5-methyl-2(3H)tellazolidene]-2-methyl-2-butenylidene)-4-
Oxo-2-thioxo-1,3-thiazolidin-3-yl acetic acid (Exemplary compound No. 59) 2-(3-acetanilidemethylene-2-butenyl)-
5.9 g of 3-ethyl-5-methylbenzotellazolium iodo salt and 1.9 g of 3-carboxymethyl 0-danine
Add to ethanol 8011.

Add 3 g of triethylamine, heat under reflux for 30 minutes, cool on ice, and precipitate as acidic acetic acid.

The crude product was heated and dissolved in methanol containing triethylamine, cooled, and crystallized as acidified with acetic acid.

The product was collected by filtration and washed with ethanol to obtain 1.2 g of the target product.

Maximum absorption wavelength eoan■ in methanol solution.

Synthesis Example-7 5'-Chloro-3., 5.10-trimethyl-3'-sulfoprobylterazolium 7-carpocyanine intramolecular MA [Exemplary Compound (64)] 2.3.5-Trimethylbenzotellazolium-trifluoro O methanesulfonic acid MA 4.2Q and 3-[5-
Do-2-(2-methylthio-1-propenyl)-3
-Benzothiazolio]propanesulfonic acid molecule 1!
Add 3.8a to 30% of pyridine and add 2g of triethylamine.
and stir at 40'C.

The precipitated dye is collected by filtration and washed with methanol.

2.2.3.3-Recrystallization from a mixed solution of 3-tetrafluoropropanol and methanol was carried out to obtain the desired product at a concentration of 0.74
I got 9.

Maximum absorption wavelength in methanol solution: 595rv.

Synthesis Example-8 3-ethyl-5-methyl-3'-sulfobyl-9,
11-Neopentylene telluratio lupocyanine inner salt (exemplary compound 60) 3-ethyl-2-methyl-tellazolium trifluoromethanesulfonate 43.7
g and isophorone 16.6Q are mixed, heated and stirred in an external bath at 180° C. for 4 hours under nitrogen atmosphere, and dehydrated. After cooling, add 100 ij2 each of water and chloroform, stir, and extract.

The black chloroform solution is washed with water, and the chloroform phase is diluted by adding twice the amount of acetic acid ethyl ester and crystallized with stirring. 11. Filter and wash with ethyl acetate to obtain a dark brown powder.
I got IQ.

2.8 g of the crude reaction product and 1.9 g of 3-sulfopropyl-2-sulfopropylthiobenzothiazolium were suspended in 50 g of acetonitrile and stirred.

Subsequently, 2 g of triethylamine is added and stirred at room temperature.

After dissolution, the dye that develops color and precipitates is collected by filtration and washed with methanol.

The product was purified by recrystallization from a chloroform-methanol mixed solution to obtain 1.2 g of the desired product.

Maximum absorption wavelength in methanol solution: 66601.

Synthesis Example-9 2-(5-[2-(3-methyl-2(3H)cheno(2
, 3-d) tellrazoliden]ethylidene]-4-oxo-2-thioxo-1,3-thiazolidin-3-yl)
Ethanesulfonic acid (exemplified compound 61) 2-acetanilide vinyl-3-methyl-cheno[2,
3-d] Tellazolium trifluoromethanesulfone I salt 2.6Q and 3-β-sulfoethylrhodanine 1.
Dissolve 2 g in absolute ethanol 501Q, add 2 g of triethylamine, and heat under reflux for 15 minutes. The reaction solution is allowed to cool, and then sufficiently cooled in a water bath to cause crystallization, and the precipitated product is filtered. The crude product is purified by repeated recrystallization from methanol.

Yield 0.85Q.

Maximum absorption wavelength 562n1 synthesis example in methanol solution-1
0 5-(4-[IH-2,3-dihydropyrido(2,1-
b) Penzotelllazolyl]) Methylene-4-oxo-2
-thioxo-1,3-thiazolidin-3-yl acetic acid (exemplified compound 62) 4-acetanilide methylene-1,2
, 5.6 g of 3,4-tetrahydropyrido[2,1-b]penzotellazolium iodo salt and 1.9 g of 3-carboxymethylrhodanine were dissolved in 60 g of absolute ethanol, and 2 g of triethylamine was added to give 15 g. minutes.

The mixture was heated to reflux.

After cooling, the mixture was acidified with acetic acid to cause crystallization, and the precipitate was collected by filtration and washed with ethanol.

Purification was carried out by dissolving it in methanol containing triethylamine and acidifying it with acetic acid for crystallization.

Yield 1.4Q, melting point 300℃ or higher.

Maximum absorption wavelength in methanol solution: 556 nm.

Synthesis Example-11 4-(2-[5,6-sihydro28.4H-tellazolo(5,4,3-i,j)quinolin-2-ylidene]ethylidene)-5-oxo-2-thioxo-1, 3
-thiazolidin-1-yl acetic acid (exemplified compound 63) 2-7cetanilidovinyl-5,6-sihydro48-
Tellurazolo[5,4,3-i,j]quinolinium chloride 4.6g and 3-carboxymethylrhodanine 1
．． Dissolve 9 g in 50 mN of absolute ethanol, add 2 g of triethylamine, and heat under reflux for 15 minutes. The reaction solution is allowed to cool, and then sufficiently cooled in a water bath to cause crystallization, and the precipitated crystals are collected by filtration. The crude product is purified by recrystallization from methanol (repeatedly).

Yield: 1.4g.

Maximum absorption wavelength in methanol solution: 550 nm.

Synthesis Example-12 Anne and draw 3'-(2- and droxyethyl)-3-(
3-sulfopropyl)-naphtho[1,2-dl tellrazolothiacarboxyanine hydroxide [exemplified compound (6
5)] Anhydro-2-methyl-3-(3-sulfopropyl)
naphthoN, 2-d ] tellrazolium hydroxide 4.
2g and 2-(2-acetanilidevinyl)-3-(
4.7 g of 2-hydroxyethyl)-benzothiazolium iodide was added to dimethylformamide 251112, and further 2 g of trie and thylamine were added, and the mixture was stirred at about 60° C. for 1 FRWR.

After cooling to room temperature, the product was precipitated by addition of ether, isolated by filtration and recrystallized from methanol. Yield 1.2 (1.

””’ 607nm.

The sensitizing dye used in the present invention is added to the silver halide emulsion as an aqueous solution or a solution dissolved in a water-miscible organic solvent such as methanol, ethanol, methylcellosolve, pyridine, etc.

The sensitizing dye used in the present invention is U.S. Patent No. 3.485.6.
The melting may be carried out using ultrasonic vibration as described in No. 34. Other methods of dissolving or dispersing the sensitizing dye of the present invention and adding it to an emulsion include US Pat.
．． No. 981, No. 3.585.195, No. 3,469.
No. 987, No. 3,425,835, No. 3.342
．． No. 605, No. 1.121,174, U.S. Patent No. 3.6
The methods described in No. 60.101 and No. 3,658.546 can be used.

The sensitizing dye of the present invention represented by the general formula [I], [II] or [vi] has a content of 1 x 10-8 mol-5 per mol of silver halide used in the silver halide emulsion.
X10-3 mol, preferably 1X10-6 mol-2,5
X 10-3 mol, particularly preferably from 5X10-6 mol
IX is used in a proportion of 10-3 mol. General formula [I
The molar ratio of the dye of general formula [IN to the dye of general formula [IN] is preferably 1:20 to 20:1.

The silver halide emulsions used in the photographic elements of this invention include:
Any silver halide used in conventional silver halide emulsions can be used, such as silver bromide, silver iodobromide, silver iodochloride, silver chlorobromide, and silver chloride.

The silver halide grains used in the silver halide emulsion are:
It may be obtained by any of the acidic method, neutral method and ammonia method. The particles may be grown all at once, or may be grown after seed particles are created. The method of creating and growing the seed particles may be the same or different.

In the silver halide emulsion, halide ions and silver ions may be mixed simultaneously, or one may be mixed in a liquid in which the other is present. Alternatively, halide ions and silver ions may be generated by sequentially and simultaneously adding the halide ions and silver ions while controlling the pHloAg in the mixing pot, taking into consideration the critical growth rate of silver halide crystals. Go,
By this method, the grain size, grain shape, grain size distribution, and grain growth rate of silver halide grains are controlled using a silver halide solvent depending on the halogen whose crystal form is regular and grain size is nearly uniform. be able to.

The silver halide grains contain cadmium salts, zinc salts, lead salts, thallium salts, iridium salts (complex salts containing), rhodium salts (complex salts containing), and iron salts in the process of forming and/or growing the grains. By adding metal ions using at least one kind selected from (complex salts containing), these metal elements can be contained inside the particles and/or on the particle surfaces, and by placing them in an appropriate reducing atmosphere. , reduction sensitizing nuclei can be provided inside the particles and/or on the particle surfaces.

Unnecessary soluble salts may be removed from the silver halide emulsion after the growth of silver halide grains is completed, or the salts may be left in the silver halide emulsion. When removing the salts, please refer to Research Disclosure (Re5earch D).
1 closure) can be carried out based on the method described in No. 17643.

The silver halide grains used in the silver halide emulsion are:
The grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside of the grain and the surface layer.

The silver halide grains used in the silver halide emulsion are:
It may be a particle in which a latent image is mainly formed on the surface, or it may be a particle in which a latent image is mainly formed inside the particle.

The silver halide grains used in the silver halide emulsion are:
It may have a regular crystal shape such as a cube, octahedron, or dodecahedron, or it may have an irregular crystal shape such as a sphere or a plate. In these particles, (10G
) plane and (111) plane, any ratio can be used.

Further, the particles may have a composite form of these crystal forms, or particles of various crystal forms may be mixed.

The average grain size of the silver halide grains (grain size represents the diameter of a circle with an area equal to the projected area) is preferably 5 .mu.l or less, and particularly preferably 3 .mu.- or less.

The silver halide emulsion of the present invention may have any grain size distribution. Emulsions with a wide grain size distribution may be used, or emulsions with a narrow grain size distribution may be used alone or in combination.

The silver halide emulsion may be a mixture of two or more silver halide emulsions that have been separately formed.

Silver halide emulsions can be chemically sensitized by conventional methods. That is, sulfur sensitization method, selenium sensitization method, reduction sensitization method,
A noble metal sensitization method using gold or other noble metal compounds can be used alone or in combination.

The silver halide emulsion of the present invention includes steps for producing light-sensitive materials,
During chemical ripening, at the end of chemical ripening, and/or after chemical ripening, until silver halide emulsion is applied, for the purpose of preventing fog during storage or photographic processing, or to maintain stable photographic performance. In addition, compounds known in the photographic industry as antifoggants or stabilizers can be added.

It is advantageous to use gelatin as a binder (or protective colloid) for silver halide emulsions, but gelatin derivatives, graft polymers of gelatin and other polymers, other proteins, sugar derivatives, cellulose derivatives, single Alternatively, hydrophilic colloids such as synthetic hydrophilic polymeric substances such as copolymers can also be used.

When gelatin is used as a binder for a silver halide emulsion, the jelly strength of the gelatin is not limited, but it is preferably a jelly strength of 2509 or more (value measured by the baggy method).

The photographic emulsion layer or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention contains one or more hardeners that crosslink binder (or protective colloid) molecules and increase film strength. It can be used to harden the membrane. A hardening agent can be added in an amount that can harden the photosensitive material to the extent that there is no need to add a hardening agent to the processing solution.
It is also possible to add a hardening agent to the processing solution.

A plasticizer can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of a light-sensitive material using the silver halide emulsion of the present invention for the purpose of increasing flexibility.

A dispersion (latex) of a water-insoluble or poorly soluble synthetic polymer is added to the photographic emulsion layer and other hydrophilic colloid layers of the light-sensitive material using the silver halide emulsion of the present invention for the purpose of improving dimensional stability. It can be included.

The emulsion layer of the light-sensitive material of the present invention undergoes a coupling reaction with an oxidized form of an aromatic primary amine developer (for example, p-phenylenediamine derivatives, aminophenol derivatives, etc.) during color development processing to form a dye. A dye-forming coupler is used.

The dye-forming couplers are typically selected for each emulsion layer such that a dye is formed that absorbs light in the light-sensitive spectrum of the emulsion layer, with a yellow dye-forming coupler for the blue-sensitive emulsion layer and a dye for the green-sensitive emulsion layer. A magenta dye-forming coupler is used in the sensitive emulsion layer and a cyan dye-forming coupler is used in the red-sensitive emulsion layer. However, depending on the purpose, silver halide color photographic materials may be produced using different combinations from the above.

These dye-forming couplers preferably have a group called a ballast group in the molecule, which makes the coupler non-diffusive and has 8 or more carbon atoms. In addition, even if these dye-forming couplers are 4-equivalent, in which 4 molecules of silver ions need to be reduced to form one dye, only 2 silver ions need to be reduced. Either equivalence is fine. Dye-forming couplers can be used as development accelerators, bleach accelerators, developers, silver halide solvents, toning agents, hardeners, capric agents, anti-capri agents, and chemical sensitizers by coupling with oxidized forms of developing agents. Compounds that release photographically useful fragments, such as agents and desensitizers, can be included. These dye-forming couplers may be used in combination with colored couplers that have a color correction effect or DIR couplers that release a development inhibitor during development and improve image sharpness and image graininess. In this case, it is preferable that the dye formed from the DIR coupler is of the same type as the dye formed from the dye-forming coupler used in the same emulsion layer, but if the color turbidity is not noticeable, a different type of dye may be used. It may also be one that forms a pigment. Instead of the DIR coupler, a DIR compound may be used which, when used with or in combination with the coupler, undergoes a coupling reaction with the oxidized form of the developing agent to produce a colorless compound and at the same time release a development inhibitor.

A colorless coupler that undergoes a coupling reaction with an oxidized aromatic primary amine developer, but does not form a dye, can also be used in combination with a dye-forming coupler.

Dye-forming couplers, colored couplers, DIR couplers, DIR that do not need to be adsorbed on the silver halide crystal surface
compounds, image stabilizers, color antifoggants, ultraviolet absorbers,
Among fluorescent brighteners, hydrophobic compounds can be prepared using various methods such as solid dispersion method, latex dispersion method, and oil-in-water emulsion dispersion method. It can be selected as appropriate. The oil-in-water emulsion dispersion method can be applied by dispersing hydrophobic additives such as couplers, and usually a high boiling point organic solvent with a boiling point of about 150°C or higher is mixed with a low boiling point and/or water-soluble organic solvent as necessary. and then emulsified and dispersed in a hydrophilic binder such as an aqueous gelatin solution using a surfactant using a dispersion means such as a stirrer, homogenizer, colloid mill, 70-jit mixer, or ultrasonic device. , may be added to the desired hydrophilic colloid layer. A step of removing the low-boiling organic solvent simultaneously with the dispersion or dispersion may be included.

When the dye-forming coupler, DIR coupler, colored coupler, DIR compound, image stabilizer, color capri-preventing agent, ultraviolet absorber, optical brightener, etc. has an acid group such as carboxylic acid or sulfonic acid, it can be used as an alkaline aqueous solution. They can also be incorporated into hydrophilic colloids.

Anionic surfactants, nonionic surfactants, Cationic surfactants can be used.

In the emulsion layer fin (between the same color-sensitive layers and/or between different color-sensitive layers) of the light-sensitive material of the present invention, the oxidized form of the developing agent or the electron transfer agent may migrate, causing color turbidity or reducing sharpness. A color anticapri agent can be used to prevent deterioration and noticeable graininess.

The color antifoggant may be contained in the emulsion layer itself, or
An interlayer may be provided between adjacent emulsion layers and contained in the interlayer.

The light-sensitive material of the present invention can contain an image stabilizer that prevents deterioration of dye images.

The hydrophilic colloid layers such as the protective layer and intermediate layer of the photosensitive material of the present invention contain an ultraviolet absorber to prevent capri due to discharge caused by charging of the photosensitive material due to friction, etc., and to prevent image deterioration due to UV light. May contain.

A formalin scavenger can be used to prevent deterioration of magenta dye-forming couplers and the like due to formalin during storage of light-sensitive materials.

In the photographic material of the present invention, when dyes, ultraviolet absorbers, etc. are contained in the hydrophilic colloid layer, they may be mordanted with a mordant such as a cationic polymer.

Compounds that change the developability, such as development accelerators and development retardants, and bleaching accelerators can be added to the silver halide emulsion layer and/or other hydrophilic colloid layers of the light-sensitive material of the present invention. Compounds that can be preferably used as development accelerators are listed in Research Disclosure (Research4'ID).
1sclosure) A compound described in Section XXI B to D of No. 17463, and the development retardant is a compound described in No. 17463.
This is a compound described in Section XXI, Section E of No. 3.

A black and white developing agent and/or its precursor may be used to accelerate development or for other purposes.

The photographic emulsion layer of the light-sensitive material of the present invention contains polyalkylene oxide or its derivatives such as ethers, esters, and amines, thioether compounds, thiomorpholines, quaternary ammonium compounds, etc. for the purpose of increasing sensitivity, increasing contrast, or promoting development. It may also contain urethane derivatives, urea derivatives, imidazole derivatives, and the like.

In the light-sensitive material of the present invention, a fluorescent whitening agent can be used for the purpose of emphasizing the whiteness of the white background and making the coloring of the white background less noticeable.

The photosensitive material of the present invention can be provided with auxiliary layers such as a filter layer, an antihalation layer, and/or an antiirradiation layer. These layers and/or the emulsion layer may contain dyes that are washed out or bleached from the light-sensitive material during the development process.

A matting agent can be added to the silver halide emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention for the purpose of reducing the gloss of the light-sensitive material, improving the ease of writing, and preventing the light-sensitive materials from sticking together.

A lubricant can be added to reduce the sliding friction of the photosensitive material.

An antistatic agent for the purpose of preventing static electricity can be added to the photosensitive material of the present invention. The antistatic agent may be used in the antistatic layer on the side of the support where the emulsion is not formed as the fs layer, and may be used as a protective colloid in the emulsion layer and/or the emulsion layer on the side where the emulsion layer is laminated with respect to the support. It may be used in layers.

The photographic emulsion layer and/or other hydrophilic colloid layer of the light-sensitive material of the present invention includes improved coating properties, antistatic properties, improved slipperiness,
Various surfactants can be used for the purpose of emulsification dispersion, prevention of adhesion, and improvement of photographic properties (development acceleration, film hardening, sensitization, etc.).

Supports used in the photosensitive material of the present invention include films made of semi-synthetic or synthetic polymers such as cellulose acetate, cellulose nitrate, polystyrene, polyvinyl chloride, polyethylene terephthalate, polycarbonate, and polyamide, and reflective layers on these films. Includes flexible supports, glass, metal, ceramics, etc.

The photosensitive material of the present invention can be used directly or after subjecting the support surface to corona discharge, ultraviolet irradiation, flame treatment, etc., as necessary, or to improve the adhesion, antistatic property, dimensional stability, abrasion resistance, etc. of the support surface. It may be applied through one or more subbing layers to improve hardness, antihalation, frictional properties, and/or other properties.

When coating the photosensitive material of the present invention, a thickener may be used to improve coating properties. Also, for example, as a hardening agent,
For substances that have a fast reactivity and may cause gelation before coating if added to the coating solution in advance, it is preferable to mix them using a static mixer or the like immediately before coating.

In preparing the light-sensitive material of the present invention, the silver halide emulsion layer and other protective colloid layers were prepared using a research disc 0-dit-(Research [) 1sclos
It can be applied by the method described in XV-A of No. 17463 and dried on the same day by the method described.

The light-sensitive material of the present invention can be exposed using electromagnetic waves in a spectral region to which the emulsion layer constituting the material is sensitive. Light sources include natural light (sunlight), tungsten electric lamps, fluorescent lamps,
Light emitted from phosphors excited by mercury lamps, xenon arc lamps, carbon arc lamps, xenon flash lamps, cathode ray tube flying spots, various laser lights, light emitting diode lights, electron beams, X-rays, gamma rays, alpha rays, etc. , any known light source can be used.

The exposure time is usually 1 millisecond to 1 second exposure FI# used in a camera, of course, and exposure shorter than 1 microsecond, for example 100 nanoseconds to 100 nanoseconds using a cathode ray tube or xenon flash lamp.
Exposures of 1 microsecond can be used, or exposures longer than 1 second are possible. The exposure may be performed continuously or intermittently.

Any known method can be used for developing the photosensitive material of the present invention. This development process may be either a process for forming a silver image (black and white development process) or a process for forming a color image, depending on the purpose. If an image is to be produced by the reversal method, a black and white negative development step is first carried out, and then a color development process is carried out by applying white exposure or processing with a bath containing a fogging agent. Alternatively, silver dye bleaching may be used, in which a dye is contained in the photosensitive material, a black and white development process is performed after exposure to form a silver image, and the dye is bleached using this as a bleaching catalyst.

Each processing step is usually carried out by immersing the photosensitive material in a processing solution, but other methods, such as a spray method in which the processing solution is supplied in the form of a spray, or contact with a carrier impregnated with the processing solution, are also used. A web method, a method of viscous development processing, etc. may be used.

The black and white development process includes, for example, a development process, a fixing process, and a water washing process. Further, the developing agent or its precursor may be incorporated into the sensitive material and the developing step may be carried out using only an alkaline solution, or the developing step may be carried out using a lithium developer as the developing solution.

The color development process includes a color development process, a bleaching process, a fixing process, and if necessary, a water washing process, or a stabilization process accompanied by water washing. Instead of the treatment step using 1
A bleach-fixing process can be carried out using a bath bleach-fix solution, or a monobath process can be carried out using a one-bath development, bleach-fixing solution that allows color development, bleaching and fixing to be carried out in one bath. You can also do it.

In combination with these processing steps, a pre-hardening process, its neutralization process, a stop-fixing process, a post-hardening process, etc. may be performed. In these treatments, instead of the color development process, an activator treatment process may be performed in which a color developing agent or its precursor is contained in the material and the development process is performed with an activator solution, or instead of monobath treatment. Activator treatment, bleaching, and fixing treatment may be performed at the same time. Typical treatments during these treatments are shown below. Processing process Constant fixation treatment process/Color development treatment process - Bleach fixing treatment process/Pre-hardening treatment process - Neutralization treatment process - Color development treatment process - Stopping constant treatment process - Water washing treatment process - Bleach treatment process Constant fixation treatment process - Water washing process - Post-hardening process - Color development process - Water washing process - Supplementary color development process - Stopping process - Bleaching process Constant fixation process - Monobath process - Activator process - Ring whitening Fixing treatment process/Activator treatment process - Bleaching treatment process Constant fixation treatment process In addition to these treatments, there is a method in which the developed silver produced by color development is bleached and then color development is performed again, and JP-A-1988-1 Processing may be performed using a developing method that increases the number of dyes produced, such as various intensification processing (amplification processing) described in the specification of No. 154839.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Silver halide grains were precipitated by a double jet method, physically ripened by a conventional method, desalted, and further chemically ripened by a total sensitization method and a sulfur sensitization method to obtain 6 mol% silver iodide. A silver iodobromide emulsion containing . The average diameter of the silver halide grains contained in this emulsion was 0.7 μm.

This emulsion I ko contains 0.60 mol of silver halide and 880 g of gelatin binder.

Each 1 kO of this emulsion was weighed into a pot and heated to 40°C to dissolve. Then, predetermined amounts of methanol solutions of the sensitizing dye according to the present invention and the comparative sensitizing dye were added and mixed and stirred.

Furthermore, 4-hydroxy-6-methyl-1,3°38.7-
20- of a 1.0% aqueous solution of citrazaindene was added, 101 g of a 1% aqueous solution of 1-hydroxy-3,5-dichlorotriazine sodium salt was added, and then a 1.0% aqueous solution of dodecylbenzenesulfonic acid sodium salt was added. 101 g of was added and stirred. This finished emulsion was applied to a cellulose triacetate film base with a dry film thickness of 6 μ-
A sample of the photosensitive material was obtained by coating and drying to obtain a photosensitive material sample. Each sample was cut into strips using a photosensitive needle with a light source with a color temperature of 540 G''K, and a blue filter (Wratten No. 47B) or yellow filter (Wratten No. 47B) manufactured by Eastman Kodak Co., Ltd. was used for the light source. SC-50) was attached and exposed to light.

After exposure, development was performed at 20°C for 3 minutes using a developer with the following composition, stopped, fixed, washed with water, and dried to obtain blue filter sensitivity (SB) and yellow filter sensitivity (S), respectively.
Y) and Capri were obtained. Note that the optical density standard for determining sensitivity was [Capri + 0.23].

Developer composition Metol 2g Anhydrous sodium sulfite 40g Hydroquinone 4g Sodium carbonate monohydrate 28Q Potassium bromide 11) Add water 11
Let it be L.

The results obtained are shown in Table 1 as relative sensitivities.

Table 1: Exemplary Compound A (Comparison) It has been found that the combination of dyes of the present invention provides a remarkable supersensitizing effect without generating capri.

In addition, after leaving each of these photosensitive materials at 40°C and 65% relative humidity for 3 weeks, they were subjected to exposure, development, and sensitivity measurement using the same method as above, and in comparison, capri occurred and the sensitivity decreased. On the other hand, it was found that the light-sensitive material sensitized by the combination of dyes of the present invention had a small decrease in yellow filter sensitivity and was excellent in stability over time.

Example 2 A silver iodobromide emulsion containing 6 mol % of silver iodide was chemically ripened by a conventional method, and the average grain size was 0.9μ tin, and the amount of silver was 0.
．． Emulsions of 60 mol/ka emulsion and gelatin 70 a/ka emulsion were obtained. This emulsion 1 kQ was heated to 40° C., and 450 g of an emulsion of cyan coupler A described below was added thereto. The emulsion of coupler A is prepared by adding 300 g of ethyl acetate and 1001 g of dibutyl phthalate to the coupler A100II+, dissolving it, adding sodium dodecylbenzenesulfonate,
The material obtained was emulsified and dispersed in a 10% gelatin aqueous solution Ika using a homogenizer. To this emulsion were added predetermined amounts of methanol solutions of the sensitizing dye according to the present invention and the comparative sensitizing dye, and the mixture was mixed and stirred.

Furthermore, 4-hydroxy-6-methyl-1,3°38.7-
Add 20% of a 1.0% aqueous solution of citrazaindene, add 20% of a 1% aqueous solution of 1-human oxygen 3.5-dichlorotriazine sodium salt, and then add 1.0% of a 1% aqueous solution of dodecylbenzenesulfonic acid sodium salt. A wt % aqueous solution of 10- was added and stirred. This finished emulsion was coated on a cellulose triacetate film base at a silver weight of 6 (J
/f and dried to obtain a sample. This film sample was measured using a sensitometer with a light source with a color temperature of 5400'K, and a blue filter (Wratten No. 47B) or a yellow filter (S) manufactured by Eastman Kodak was used as the light source.
C-50) and exposed to light.

After exposure, the following formulation was developed, bleached, fixed and dried, and the density of the developed cyan image was measured.

The optical density reference point that determined the sensitivity was fog +0.20.
This was the point. Immediately after coating, the blue filter sensitivity (SB), yellow filter sensitivity (SY) and capri of each sample obtained by color development were obtained. The optical density standard for determining sensitivity is E fog. 2].

The results obtained are shown in Table 2 as relative sensitivities.

Coupler A Development processing recipe 1, color development 3 minutes 15 seconds (38℃) 2, bleaching
White 6 minutes 30 seconds 3, water washing 3 minutes 15 seconds 4, fixation 6 minutes 30 seconds 5, water washing 3 minutes 15 seconds 6, stability 3 minutes 15 seconds The composition of the processing solution used in each step is as follows. be.

Color Developer Bleach Fixer Stabilizer Below Margin Table 2 It has been found that the combination of dyes of the present invention provides a remarkable supersensitizing effect without causing fogging.

In addition, after leaving each of these samples at 40°C and 65% relative humidity for 3 weeks, they were subjected to exposure, development, and sensitivity measurement using the same method as above. As a result, fogging occurred and the sensitivity decreased in comparison. On the other hand, it was found that the light-sensitive material sensitized by the combination of dyes of the present invention had a small decrease in yellow filter sensitivity and was also excellent in stability over time.

The following compounds were used as comparative examples.

Comparative example compound

Claims (1)

[Scope of Claims] A light-sensitive material having at least one silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains at least one sensitizing dye represented by the following general formula [I], A silver halide photographic light-sensitive material characterized by containing a combination of at least one sensitizing dye represented by the general formula [II] or [III]. General formula [I] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, Z_1 and Z_2 are pyrroline nucleus, pyridine nucleus, indolenine nucleus, benzimidazole nucleus, oxazole nucleus, benzoxazole nucleus, naphthoxazole nucleus, naphtho, respectively. Represents the atomic group necessary to complete the oxazole nucleus, thiazoline nucleus, thiazole nucleus, benzothiazole nucleus, naphthothiazole nucleus, selenazole nucleus, benzoselenazole nucleus or naphthoselenazole nucleus, R_1,
R_2 is an aliphatic group which may be substituted and whose carbon chain may be interrupted by an oxygen atom or a sulfur atom, and at least one of R_1 and R_2 is a hydroxy group,
represents the aliphatic group having either a carboxyl group or a sulfo group, X_(_1_)^■ represents an acid anion, and n represents 1 or 2; however, when the dye forms an inner salt, n represents It is 1. ] General formula [II] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_3 and R_4 are each a hydrogen atom or a monovalent group that may be substituted, and at least one is and preferably each is a hydrogen atom or an alkyl group or aryl group, each of which may be substituted, and at least one of them is an alkyl group or aryl group, each of which may be substituted. or (ii) a group of atoms that together complete a ring that is fused to a ring containing tellurium and nitrogen, preferably an aromatic ring that is fused directly to a ring containing tellurium and nitrogen, or A group of atoms completing an aromatic ring fused to a non-aromatic ring fused to a ring. R_5 and R_1_1 independently represent quaternized substituents, and R_5 may join with R_4 to complete a fused heterocycle. Also, R_6 may cooperate with R_5 to complete a fused heterocycle. R_7, R_8 and R_9 are each a hydrogen atom, a halogen atom, an alkyl, an aralkyl, an aryl, a heterocycle,
Represents a cyano, amino, alkylthio, arylthio, alkoxy, aryloxy group or an acidic nucleus. R_6 and R_1_0 are each a hydrogen atom, alkyl, aralkyl, aryl, heterocycle, amino, cyano,
Represents alkylthio, arylthio, alkoxy, and aryloxy groups. R_6 and R_1_0 (however, m=0
) or R_7 and R_9 may jointly form a ring, and R_1_1 may jointly form a fused heterocycle with R_1_0. Q represents the atomic group that completes the nucleus of the nitrogen-containing heterocycle, and Y^
- represents a counter anion, and p represents 0 or a positive integer for combining ion charges. l and m each represent 0 or 1, and n represents 0, 1 or 2. ] General formula [III] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R_3, R_4, R_5 and R_6 have the same meaning as the general formula [II]. R_1_2, R_1_3 and R_1_4 each represent a hydrogen atom, an alkyl, aralkyl, aryl, alkylthio, cyano, arylthio, alkoxy, or aryloxy group. R_1_2 and R_1_4 may jointly form a ring. q represents 0 or 1, and E represents an acidic nucleus. ]