JP2002357879A - Silver halide emulsion and iridium complex useful for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a high contrast silver halide emulsion having high sensitivity and free of reciprocity law failure over a wide illumination range of exposure. SOLUTION: The silver halide emulsion contains an iridium complex having at least one bromide ion as a ligand represented by the formula [IrBrn Lm ]<1> wherein L is an inorganic ligand other than Br and may coordinate as any of mono-and multidentate ligands with iridium as a central metal, (n) is an integer of 1-5; (m) is an integer of 1-5, and (1) is an integer of +3 to -8.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material. In particular, the present invention relates to a silver halide photographic material having high sensitivity, high gradation and no reciprocity failure using a dopant technique, an iridium complex used as a dopant thereof, and a method for producing the same.

[0002]

2. Description of the Related Art As one of the techniques for modifying silver halide grains to improve the performance of the silver halide photographic light-sensitive material as expected, a technique of incorporating a substance (dopant) other than silver ions and halide ions. (Dope technology).
In particular, much research has been made on the doping technology of transition metal ions. It is generally accepted that transition metal ions effectively change photographic performance when they are introduced into silver halide grains as dopants, even if the added amount is very small.

In order to more effectively improve the photographic characteristics of silver halide emulsions, there has been known a technique of doping not only transition metal ions but also transition metal complexes into silver halide grains. As a complex to be doped, a cyanide ion is used as a ligand for the purpose of obtaining a sensitized emulsion.VIII
Most disclosed examples are emulsions doped with group III metal complexes. JP-A-2-20854 and JP-B-7-113743 disclose dopants containing four or more cyanide ions, and most of these and other disclosed examples use iron or ruthenium as a central metal. Hexacyano complex is used. Further, as disclosed in JP-A-2-20853, there is an example in which a silver halide emulsion having high sensitivity is obtained with a cyano complex of rhenium, osmium and iridium.

Gradation is one of the important characteristics in the photographic characteristics of a silver halide emulsion, and a doping technique is also used to obtain a high gradation emulsion. In order to obtain a high gradation, that is, a high contrast emulsion, EP033642 and EP063642.
There is a technique using nitrosyl or thionitrosyl as a ligand of a transition metal complex as disclosed in Japanese Patent Nos. 06895 and 0610670. At this time, ruthenium osmium is mainly used as the central metal. In order to obtain a high-contrast emulsion, it is effective not only to use nitrosyl or thionitrosyl but also to use hexachlororuthenium, hexachlororhodium and hexachlororhenium. No. 2-20852, No. 2-
No. 20,855.

In order to improve reciprocity failure, in particular, high illuminance reciprocity failure, an iridium complex is used. Examples of doping silver halide grains with an iridium complex are described in JP-A-1-285941 and JP-A-3-118585.
Nos. 4-213449, 4-278940, 5-66511, 5-313277, 6-82
Nos. 947, 6-235959 and 7-72569
Nos. 7-72576, 11-202440, 11-2955841, and the like. As ligands for iridium complexes, fluoride ions, chloride ions, bromide ions, H ₂ O, Cyano, nitrosyl and thionitrosyl have been used.

In recent years, a technique has been disclosed in which a complex having an organic compound as a ligand is doped into silver halide grains to change the properties of the emulsion. US Patent 5,3
Nos. 60,712, 5,457,021, 5,46
Nos. 2,849, EP 0709724,
JP-7-72569, and examples same 8-179452 Each publication is complex to many organic compounds and ligands used are shown, in particular _{[(NC) 5 Fe (m} -4,4'-bi
pyridine) Fe (CN) ₅ ] ^6- is described to have a large effect of sensitization, and furthermore, doping with [IrCl ₅ (thia)] ^2- (thia = thiazole) causes a high illuminance failure. It is described that can be effectively improved. JP-A-11-24194 discloses [Fe (CO) ₄ (P (Ph) ₃ )] ⁰ , [Fe
By doping (CO) ₃ (P (Ph) ₂ )] ⁰ , an emulsion having high sensitivity and improved reciprocity failure is obtained.

Japanese Patent Application Laid-Open No. 11-102442 discloses [M (CN) ₅ L] ^3- (M = Fe ²⁺ , Ru ²⁺ , I
r ³⁺ ), [Fe (CO) ₄ L] ⁰ , [M ′ (CN)
₃ L] ^- (M '= Pd ²⁺ , Pt ²⁺ ), [IrCl ₅ L]
^{In a 2-} type complex, L is 2-mercaptoben
zimidazole, 5-methyl-s-tri
azolo (1.5-A) pyrimidine-7-
ol, 2-mercapto-1,3,4-oxadi
A high-sensitivity emulsion was obtained when using azole.
Further, JP-A-10-293377 discloses [RuCl ₅
L ′] ^2- (L ′ = imidazole, benzimidazole and its derivatives) -doped emulsion shows remarkable hardening, and the sensitivity at that time is much higher than the emulsion using the conventional desensitizing hardening dopant. It is shown.

As in these examples, many iridium complexes are used to improve reciprocity failure with high illuminance, but most of them are complexes using chloride ions as a majority ligand. Few examples have been known in which an iridium complex having bromide ions as a majority ligand is used in addition to IrBr ₆ ] ^3- and [IrBr ₆ ] ^2- .

[0009]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic light-sensitive material which has higher sensitivity, has no reciprocity failure over a wide range of exposure illuminance, and has higher contrast. A second object is to stably obtain an iridium complex which can achieve the above object in high purity and high yield.

[0010]

Means for Solving the Problems As a result of intensive studies, the present inventors have attained the above objects by the following (1) to (9). (1) A silver halide emulsion containing an iridium complex having at least one bromide ion represented by the following general formula as a ligand. In the general formula I [IrBr _n L _m ] ^l , L represents an inorganic ligand other than Br, and may be monodentate or polydentate with iridium as the central metal. n represents an integer of 1 to 5, and m represents an integer of 1 to 5. l represents an integer from +3 to -8. In the above general formula, n is 2
And m is preferably an integer of 1 to 4.

(2) In the iridium complex, n is 3, 4 or 5, m is 1, 2 or 3, and l is from +1 to-
The silver halide emulsion according to (1), which is an integer up to 3. It is preferable that not all of L be Cl.

(3) The silver halide emulsion according to (1), wherein the iridium complex contained in the silver halide grains contained in the emulsion is represented by the following general formula II. Formula _{II [IrBr x L '(6} -x)] ^y in formula, L' represents a fluoride ion, a chloride ion. x
Represents an integer from 1 to 5, and y represents -2 or -3. In the general formula II, x is preferably an integer of 2 to 5.

(4) The silver halide emulsion according to (1), wherein the iridium complex contained in the silver halide grains contained in the emulsion is represented by the following general formula III. General formula III [IrBr _a Cl _(ba) L ″ _c ] ^{d In the} formula, L ″ represents an arbitrary inorganic ligand, and can be monodentate or polydentate with iridium as a central metal. Is also good.
a is an integer from 1 to 4; b is 4 or 5;
b and c represent 1 or 2. d represents an integer from +1 to -3.

(5) The silver halide emulsion according to any one of (1) to (4), wherein the iridium contained in the silver halide grains contained in the emulsion is trivalent.

(6) The time required for electrons trapped in the center of iridium to be released from the iridium is 10 seconds to 1 second.
The silver halide emulsion according to any one of (1) to (5), which provides an emulsion having 0 to ⁴ seconds.

(7) A silver halide emulsion containing an iridium complex having at least one bromide ion represented by the following general formula IV as a ligand. In the general formula ^{_{IV [IrBr 6-p L 1}} p] r formula, L ¹ is pyrrole, thiophene, pyrazoles, isoxazoles include, isothiazoles, imidazoles, oxazoles, furazan compound, or a nitrogen atom, an oxygen Contains at least three atoms selected from atoms and sulfur atoms, has five or less carbon atoms, and may contain other atoms, and may further contain (number of carbon atoms) / (number of nitrogen atoms + number of oxygen atoms + sulfur atom Number) is less than 0.5. The central metal, iridium, may be monodentate or polydentate. p represents an integer of 1 to 3. r is 0
Represents an integer from to -3.

(8) A metal complex represented by the following general formula V: Formula V N _k [IrBr _{6-p ′} L ² _{p ′} ] (wherein N represents a counter cation. _K represents the number of counter cations required for neutralizing the charge of the complex salt. L ² represents a nitrogen atom, oxygen It contains three or more atoms selected from atoms or sulfur atoms, has five or less carbon atoms, may contain other atoms, and may further contain (number of carbon atoms) / (number of nitrogen atoms + number of oxygen atoms + sulfur atom Number) is less than 0.5, and p ′ represents an integer of 1 or 2.)

(9) The method for producing a metal complex according to the above (1), (7) or (8), wherein the metal complex represented by the general formula A is used as a raw material. General formula A N ¹ _{k ′} [IrBr _6-q (H ₂ O) _q ] (wherein N ¹ represents a counter cation. K ′ represents the number of counter cations necessary for neutralizing the charge of the complex salt. 1
Or an integer of 2. )

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The high illuminance reciprocity failure of a silver halide photographic emulsion is caused by the generation of a large amount of photoelectrons in silver halide grains at the time of high illuminance exposure and dispersion of a latent image. Therefore, high-illuminance failure is improved by temporarily evacuating a large amount of photoelectrons generated by high-illumination exposure from the conduction band, and having the function of releasing it into the conduction band after staying for a certain time in the silver halide grains. You can do it. This corresponds to recreating the situation in the silver halide grains during high illuminance exposure to the same situation as during low illuminance exposure. The function of temporarily evacuating the photoelectrons, that is, the function of temporarily capturing the photoelectrons, can be realized by doping a transition metal complex. Called dopant). Hexachloroiridium has been used as a transition metal complex to improve high-illuminance reciprocity failure. When hexachloroiridium is used, photoelectrons generated by exposure are captured in the lowest free orbit of iridium, which is the central metal, and stay in this orbit for a certain period of time, and then emit again into the conduction band. The average time from the exposure to the re-emission of the captured electrons is defined as the sustained electron release time.

On the other hand, the time until the sustained release of electrons is completed
Long exposure improves high light failure, but from exposure to development
Time-dependent increase in sensitivity (latent image sensitization)
Noh becomes unstable. Therefore, the improvement of high illumination reciprocity failure is
Must be performed on the assumption that latent image sensitization does not occur
Is IrCl₆ In the high illuminance phase as long as no latent image sensitization occurs
It is not possible to sufficiently improve foul failure. Listed above
IrCl in disclosed examples_Five (H _Two O) or IrCl_Five (Thi
In a), reciprocity failure can be improved without causing latent image sensitization
However, the ideal reciprocity law is because the electron sustained release time is slightly too short
The effect is not enough to obtain.

If the exposure light source is constant, the electron sustained release time may be set only for a certain exposure illuminance. It is necessary to introduce a dopant having an appropriate electron sustained release time corresponding to the illuminance of the exposure light source into the silver halide grains.

One of the factors governing the electron sustained release time is the "depth" of the electron trapping level from the bottom of the conduction band in the silver halide grains. It is thought that the longer the time is, the shorter the release time becomes. In IrCl ₅ (H ₂ O) and IrCl ₅ (thia), the depth of the electron trap level can be increased by replacing chloride ion, which is a ligand, with bromide ion, and has an ideal sustained release time. It is expected that the complex can be doped.

In the present invention, silver halide grains are formed.
And / or during the growth process, inside and outside of silver halide grains.
And / or preferably incorporated into surfaces
Examples of the iridium metal complex are as follows. The above general formula I
And L or L ″ of the general formula III is preferably A
10_Two ^-, B^3-, B_Two ^3-, B₆ ^2-, BBr_Three, BCl_Three, BF, B
N, BN (SiH_Three)_Two , BNH_Two, BO, BO_Two ^-, BO_Three ^-, B
O_Three ^3-, B_TwoO_Three, B_FourO₇ ^2-, B_FiveO ₈ ^-, Br_Three ^-, BrC
l_Two ^-, BrO_Three ^-, C^-, CF_ThreeSO_TwoNH_Two, CF_ThreeSO_Three ^-, Cl
O^-, ClO_Two ^-, ClO_Three ^-, ClO_Four ^-, CN^-, CN_Two ^-,
CNO^-, CO, CO_Two, CO_Three ^-, CS_Two, CS_Three ^2-,
H^-, H_TwoO, I^-, I_Three ^-, IBr_Two ^-, ICl_Two ^-, I
O_Three ^-, IO_Four ^-, Si^-, N_Three ^-, N_Two, N_Two ^3-, N_Three ^-, NC
Cl, NCO^-, NCS^-, NCSe^-, NCS_ThreeCN, N
CTe^-, NH_Two ^-, NH_TwoNH_Two, NH_TwoOH, NH_TwoOS
O_ThreeH, NH_TwoSO_TwoNH_Two, NH_TwoSO_ThreeH, NH_Three, NO
^{+ / 0}, NO_Two ^-, NO_Three ^-, NS, NSF, NSF_Two, NSF
_Three, NSO, O^2-, O_Two ^-, O_Two ^2-, O_Three ^2-, OCN^-, O
H^-, P^3-, PBr_Three, PCl_Three, PF_Three, PH_Three ^-, PO
(NCO)_Three, PO_TwoH_Two ^-, PO_Three ^-, PO_Three ^3-, PO_Four ^3-,
P_TwoO₇ ^Four-, HPO_Four ^2-, H_TwoPO_Four ^-, PHO_Three ^2-, PH_Two
O_Two ^2-, POF_Three, S^2-, S (NSO)_Two, S_Three ^2-, SO,
SO_Two, SO_Three, SO_Three ^2-, SO_ThreeF^-, SO_Four ^2-, S_TwoO,
S_TwoO_Two, S_TwoO_Three ^2-, S_TwoO_Four ^2-, S_TwoO_Five ^2-, S_TwoO₆ ^2-, S
_TwoO₇ ^2-, S_TwoO₈ ^2-, S_ThreeO₇ ^2-, S_FourO₆ ^2-, S_FiveO₆ ^2-,
Sb^3-, SCN-, Se^2-, SeCN^-, SeO_Three ^2-, S
eO_Four ^2-, SH^-, Si^-, Si_FourO₉ ^2-, SiCl_Three ^-, S
iCl_Four, SiH_Four, SiO, SiO_Two, SiO_Three ^2-, Si
O_Four ^2-, SnCl_Two, SnCl_Three ^-, SnS_Three ^2-, Te^2-,
TeCN^-, TeO_Three ^2-, TeO _Four ^2-, TiO_Three ^2-, Mg
O_Four ^6-, VO_Three ^-, VO_Four ^3-, V_TwoO₇ ^Four-, CrO_Four ^2-, Cr
O ₈ ^3-, Cr_TwoO₇ ^Two-, MnO_Four ^2-, MnO_Four ^-, FeO_Three ^-,
FeO_Four ^{2- / 3-}, NiO_Four ^6-, ZnO_Four ^6-, MoO_Four ^2-, W
O_Four ^2-Or ReO^-But preferably
H^-, N_Three ^-, O^2-, O_Two ^-, O_Two ^2-, I^-, BO_Two ^-, C
O_Three ^-, SiO_Three ^2-, SiO _Four ^2-, SnCl_Three ^-, NH_Two ^-, N
H_Three, NH_TwoOH, NO_Two ^-, NO_Three ^-, NCO^-, SCN^-,
PH_Three ^-, PO_Three ^-, PO_Four ^Three-, PHO_Three ^2-, PH_TwoO_Two ^2-, O
H^-, H_TwoO, SH^-, SO_Three ^2-, SO_ThreeF^-, SO_Four ^2-, C
10^-, ClO_Two ^-, ClO_Three ^-, ClO_Four ^-, Br_Three ^-,Also
Is I_Three ^-And most preferably H^-, N_Three ^-, O^2-,
I^-, NH_Three, NO_Two ^-, NO_Three ^-, NH_TwoOH, NCO^-, S
CN^-, NCS^-, PH_Three, OH^-, H_TwoO or SH^-
It is. Complexes preferably represented by the general formula I
As [IrBr_Five(H_TwoO)]^2-, [IrBr_Five(O
H)]^3-, [IrBr_Five(O)] ^Four-, [IrBr_Five(C
N)]^3-, [IrBr_Five(CO)]^2-, [IrBr_Five(N
H_Three)]^2-, [IrBr_Five(NO_Two)]^3-, [IrBr
_Five(CNO)]^3-, [IrBr_Five(SCN)]^3-, [Ir
Br_Five (PH_Three )]^3-, [IrBr_Five(PH
_TwoO_Two)]^3-, [IrBr_Five(SnCl_Three )]^3-, [Ir
Br_Four(H_TwoO)_Two]^-, [IrBr_Four(OH)_Two]^3-, [I
rBr_Four(O)_Two]^Five-, [IrBr_Four(CN)_Two]_3-, [I
rBr_Four(CO)_Two]^-, [IrBr_Four(NH_Three)_Two]^-,
[IrBr_Four(NO_Two)_Two]^3-, [IrBr_Four(CN
O)_Two]^3-, [IrBr_Four(SCN)_Two]^3-, [IrBr_Four
(PH_Three)_Two]^3-Or [IrBr_Four(SnC
l_Three)_Two]^3-And the complex represented by the general formula II is
[IrBr_FiveF]^3-, [IrBr_FourF_Two]^3-, [IrBr_Three
 F_Three] _3-Or [IrBr_TwoF_Four]^3-It is. General formula
Preferably, the complex represented by III is [IrBr_FourC
l (H_TwoO)]^2-, [IrBr_ThreeCl_Two(H_Two O)]^2-,
[IrBr_TwoCl_Three(H_TwoO)]^2-, [IrBrCl_Four(H
_TwoO)]^2-, [IrBr_FourCl (OH)]^3-, [IrBr
_ThreeCl_Two(OH)]^3-, [IrBr_TwoCl_Three(OH)] ^3-,
[IrBrCl_Four(OH)]^3-, [IrBr_FourCl
(O)]^Four-, [IrBr_ThreeCl_Two(O)]^Four-, [IrBr
_TwoCl_Three(O)]^Four-, [IrBrCl_Four(O)]^Four-, [I
rBr_FourCl (OCN)]^3-, [IrBr_Three Cl_Two(OC
N)]^3-, [IrBr_TwoCl_Three(OCN)]^3-, [IrB
rCl_Four (OCN)]^3-, [IrBr_FourCl (CN)]
^3-, [IrBr_ThreeCl_Two(CN)]^3-, [IrBr_TwoCl_Three
(CN)]^3-, [IrBrCl_Four(CN)]^3-, [Ir
Br_FourCl (SCN)]^2-, [IrBr _ThreeCl_Two(SC
N)]^2-, [IrBr_TwoCl_Three(SCN)]^2-, [IrB
rCl_Four(SCN)]^2-, [IrBr_FourCl (C
O)]^2-, [IrBr_ThreeCl_Two(CO)]^2-, [IrBr
_TwoCl_Three(CO)]^2-, [IrBrCl_Four(CO)]^2-,
[IrBr_FourCl (NO_Two)]^3-, [IrBr_ThreeCl_Two(N
O_Two)]^3-, [IrBr_TwoCl_Three(NO _Two )]^3-, [Ir
BrCl_Four(NO_Two)]^3-, [IrBr_FourCl (PH_Three)]
^3-, [IrBr_ThreeCl_Two(PH_Three)]^3-, [IrBr_TwoCl
_Three(PH_Three)]^3-, [IrBrCl_Four(PH_Three)]^3-, [I
rBr_FourCl (PH_TwoO_Two)]^3-, [IrBr_ThreeCl_Two(P
H_TwoO_Two)]^3-, [IrBr_TwoCl_Three(PH_TwoO_Two)]^3-Ma
Or [IrBrCl_Four(PH_TwoO_Two)]^3-It is.

The ligand represented by L ¹ in the general formula (IV) includes pyrroles, thiophenes, pyrazoles, isoxazoles, isothiazoles, imidazoles,
A compound selected from oxazoles and furazanes, or containing at least three or more atoms selected from a nitrogen atom, an oxygen atom, and a sulfur atom alone or in combination, having five or less carbon atoms, and other atoms And a compound in which (number of carbon atoms) / (number of nitrogen atoms + number of oxygen atoms + number of sulfur atoms) is less than 0.5.

[0026] pyrroles represented by L ^1, thiophenes, pyrazoles, isoxazoles include, isothiazoles, imidazoles, oxazoles, a compound selected from the furazan compound may have a substituent. Examples of the substituent that may be present include a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an alkyl group [linear,
Represents a branched or cyclic substituted or unsubstituted alkyl group.
They include an alkyl group (preferably an alkyl group having 1 to 10 carbon atoms, for example, methyl, ethyl, n-propyl, isopropyl, t-butyl)], a heterocyclic group (preferably a 5- or 6-membered substituted or unsubstituted, A monovalent group obtained by removing one hydrogen atom from an aromatic or non-aromatic heterocyclic compound, and more preferably a 5- or 6-membered aromatic heterocyclic group having 3 to 20 carbon atoms. 2
-Furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxyl group, alkoxy group (preferably substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, for example, methoxy Ethoxy, isopropoxy, t-butoxy, n-octyloxy, 2-methoxyethoxy), acyloxy group (preferably formyloxy group, carbon number 2)
To 10 substituted or unsubstituted alkylcarbonyloxy groups), a carbamoyloxy group (preferably a substituted or unsubstituted carbamoyloxy group having 1 to 10 carbon atoms such as N, N-dimethylcarbamoyloxy, N,
N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyloxy), alkoxycarbonyloxy group (preferably substituted or unsubstituted having 2 to 10 carbon atoms) Alkoxycarbonyloxy group, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy), amino group (preferably amino group, substituted or unsubstituted alkylamino group having 1 to 10 carbon atoms) ), An acylamino group (preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 10 carbon atoms), an aminocarbonylamino group (preferably a substituted or unsubstituted aminocarboxy group having 1 to 10 carbon atoms) Arylamino, such as carbamoylamino, N, N-dimethylaminocarbonyl amino, N, N
-Diethylaminocarbonylamino, morpholinocarbonylamino), alkoxycarbonylamino group (preferably substituted or unsubstituted alkoxycarbonylamino group having 2 to 10 carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n- Octadecyloxycarbonylamino,
N-methyl-methoxycarbonylamino), a sulfamoylamino group (preferably a substituted or unsubstituted sulfamoylamino group having 0 to 10 carbon atoms, for example, sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino), alkyl and arylsulfonylamino groups (preferably substituted or unsubstituted alkylsulfonylamino having 1 to 10 carbon atoms), mercapto groups, alkylthio groups (preferably having 1 to 10 carbon atoms) A substituted or unsubstituted alkylthio group, for example, methylthio, ethylthio, n-hexadecylthio), a sulfamoyl group (preferably having no carbon atoms)
To 10 substituted or unsubstituted sulfamoyl groups such as N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl), sulfo group, Alkyl and arylsulfinyl groups (preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 10 carbon atoms), alkyl and arylsulfonyl groups (preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 10 carbon atoms), An acyl group (preferably a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 10 carbon atoms, for example, methoxycarbonyl, ethoxy Carbonyl, t-butoxyca Boniru, n- octadecyloxycarbonyl), carbamoyl groups (preferably a substituted or unsubstituted carbamoyl having 1 to 10 carbon atoms,
For example, carbamoyl, N-methylcarbamoyl, N, N
-Dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl), imide group (preferably N-succinimide, N-
Phthalimide), a phosphino group (preferably a substituted or unsubstituted phosphino group having 2 to 10 carbon atoms, such as dimethylphosphino, diphenylphosphino, methylphenoxyphosphino), a phosphinyl group (preferably having 2 to 10 carbon atoms). Or a substituted or unsubstituted phosphinyl group such as phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl) and a phosphinyloxy group (preferably substituted or unsubstituted phosphinyloxy having 2 to 10 carbon atoms) Groups such as diphenoxyphosphinyloxy, dioctyloxyphosphinyloxy), phosphinylamino groups (preferably substituted or unsubstituted phosphinylamino groups having 2 to 10 carbon atoms,
For example, dimethoxyphosphinylamino, dimethylaminophosphinylamino), a silyl group (preferably a substituted or unsubstituted silyl group having 3 to 10 carbon atoms, such as trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl). Can be Hereinafter, these substituents are referred to as substituent V. Substituent V may be further substituted.

The ligand represented by L ¹ preferably contains three or more atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom alone or in combination, and has 5 or less carbon atoms. Other atoms may be contained, and (number of carbon atoms) / (number of nitrogen atoms + number of oxygen atoms + number of sulfur atoms)
Compounds that are less than 0.5. More preferably, a ligand represented by the following general formula B or a 5- or 6-membered heterocyclic ring containing three or more atoms selected from a nitrogen atom, an oxygen atom or a sulfur atom, and having three or less carbon atoms A ligand,
In addition, other atoms may be contained, and (number of carbon atoms) / (number of nitrogen atoms + number of oxygen atoms + number of sulfur atoms) is 0.5.
Less than. General formula B

[0028]

Embedded image

Wherein E is N-, NH, C = O, C = S, C = Se, C
= Te, C = NH, S, S = O, P, P = O, P = S, P = Se, P = Te or P-
Represents S-. R has not more than 2 carbon atoms and (number of carbon atoms) / (number of nitrogen atoms + number of oxygen atoms + number of sulfur atoms) is 0.5
The following groups are represented. t represents an integer of 2 or 3. R
May be the same or different. It is more preferable that the ligand represented by L ¹ is a compound represented by the general formula (B-1), (B-2), (B-3), (B-4), or (B-
5) A ligand represented by 5) or a 5-membered heterocyclic ring which contains three or more atoms selected from nitrogen or sulfur atoms in the ring. Particularly preferred is a ligand which is a 5-membered heterocyclic ring and contains three or more atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom in the ring.

[0030]

Embedded image

(Wherein T ^{1 to} T ⁶ each represent a hydrogen atom, an alkyl group, a hydroxyl group, an amino group, a cyano group, or a sulfonyl group. These groups may have a substituent. When there are plural in the molecule, they may be the same or different.)

E in the general formula B is N-, NH, C = O, C =
S, C = Se, C = Te, C = NH, S, S = O, P, P = O, P = S, P = Se, P
= Te or PS-, preferably N-, NH, C = O, C =
S, C = NH, P = O, or P = S, more preferably N-,
C = S, C = NH or P = S, particularly preferably N-.

The group represented by R in the general formula B is a group having 2 or less carbon atoms and having (carbon atom number) / (nitrogen atom number + oxygen atom number + sulfur atom number) of 0.5 or less. It is. Examples thereof include a hydrogen atom, an alkyl group, a hydroxyl group, an amino group, a cyano group, a sulfonyl group, a nitro group, a formyl group, a carboxyl group, a sulfinyl group, a sulfamoyl group, an alkyloxycarbonyl group, and an acylmercapto group. Preferably CF ₃ , CCl ₃ , CN, CHO, CO
₂ H, CO ₂ CH ₃ , NO ₂ , S (O) CH ₃ , S (O ₂ ) CH ₃ , SO ₂ NH ₂ , SCOC
H ₃ and more preferably CF ₃ , CCl ₃ , CN, CHO, C
O ₂ H, CO ₂ CH ₃ , S (O ₂ ) CH ₃ , SO ₂ NH ₂ and SCOCH ₃ , and particularly preferably CN.

In the general formula B, t represents an integer of 2 or 3. t is preferably 2. General formula (B-1)
T ^{1 to} T ⁶ in (B-5) each represent a hydrogen atom, an alkyl group, a hydroxyl group, an amino group, a cyano group, or a sulfonyl group. As the alkyl group, for example, having 1 to 2 carbon atoms
Alkyl group. For example, a methyl group, an ethyl group, and a trifluoromethyl group. These substituents may further have a substituent.

The 5- or 6-membered heterocyclic ring represented by L ¹ contains three or more of any one of a nitrogen atom, an oxygen atom and a sulfur atom, alone or in combination, and has (number of carbon atoms) /
It is a compound having (number of nitrogen atoms + number of oxygen atoms + number of sulfur atoms) less than 0.5. Preferred is a 5-membered heterocyclic ring. More preferably, it is a 5-membered ring compound having three or more atoms selected from nitrogen or sulfur atoms. Specifically, for example, thiadiazoles (eg, 1,2,4-thiadiazole, 1,
3,4-thiadiazole, 2,5-dichloro- [1,
3,4] -thiadiazole, 2,5-difluoro- [1,
3,4] -thiadiazole, 2-chloro-5-fluoro- [1,3,4] -thiadiazole, 3,5-difluoro- [1,2,4] -thiadiazole, 1,2,3-thiadiazole), Triazoles (e.g., 1,2,4-triazole, 3,5-dichloro-4H- [1,2,4] -triazole) and tetrazoles (e.g., 1H-tetrazole, 1H-tetrazole-5-thiol). Are preferably thiadiazoles and triazoles, more preferably thiadiazoles.

The ligand represented by L ² in the general formula V contains at least three or more atoms selected from a nitrogen atom, an oxygen atom and a sulfur atom alone or in combination, and has 5 or less carbon atoms. And may contain other atoms, and furthermore, a compound in which (number of carbon atoms) / (number of nitrogen atoms + number of oxygen atoms + number of sulfur atoms) is less than 0.5. These include at least three or more of atoms selected from nitrogen, oxygen, and sulfur represented by L ¹ in the general formula IV, alone or in combination, and the number of carbon atoms is five or less. May be further contained, and (the number of carbon atoms) / (the number of nitrogen atoms + the number of oxygen atoms + the number of sulfur atoms) is equal to or less than 0.1.
It has the same meaning as the compound having a value of less than 5, and the preferred range is also the same.

In the general formula IV, r represents an integer of 0 to -3, preferably -1 to -3, and more preferably-
2-3. P in the general formula IV represents an integer of 1 to 3, preferably 1 to 2, and more preferably 1. P ′ in the general formula V represents an integer of 1 or 2, and is preferably 1. Q in the general formula A represents an integer of 1 or 2. q is preferably 1.

The iridium ion in the general formulas IV, V and A can generally be monovalent to tetravalent in a complex state.
It is preferably trivalent or tetravalent, and more preferably trivalent. Iridium hexachloride, which has been used for photography, is tetravalent (eg, K ₂ [IrC
l ₆ ] and Na ₂ [IrCl ₆ ]) have been considered preferable, but since the complex of the present invention is stable even in an aqueous solution, it is preferable that the complex is actually a trivalent state which is actually doped.

N in the general formula V and in the general formula A
Examples of the counter cation represented by N ¹ include alkali metal ions (eg, lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion), and alkaline earth metals (eg, magnesium ion, calcium ion, strontium ion, barium ion) And the like, and onium salts (eg, ammonium salts, pyridinium salts, etc.). N in the general formula V is preferably an alkali metal ion or an alkaline earth metal ion, and more preferably an alkali metal ion. The alkali metal ion is preferably a sodium ion, a potassium ion, a rubidium ion or a cesium ion, and more preferably a potassium ion or a cesium ion. N ¹ in the general formula A is preferably an alkali metal ion, more preferably a rubidium ion or a cesium ion, and particularly preferably a cesium ion.

The charge of Ir can be both trivalent and tetravalent.
And when trivalent is oxidized to tetravalent, the complex counter
-One cation is removed. In general formula IV below
A compound having a ligand represented by the general formula V
Preferred specific examples of (including the metal complex represented) are shown below,
The scope of the present invention is not limited to these. K_Two[I
rBr_Five(S = P (NH_Two)_Three)], Rb_Two[IrBr_Five(O = P (NH_Two)_Three)], Cs_Two[IrBr_Five
 (Se = P (NH_Two)_Three)], K_Two[IrBr_Five(S = P (NH_Two)_Two(OH))], K_Two[IrBr_Five
(S = P (NH_Two) (OH)_Two)], K_Two[IrBr_Five(S = P (OH)_Three)], K_Two[IrBr_Five(S
= P (CN)_Three)], Na_Two[I rBr_Five(NH_TwoC (= S) NH_Two)], K_Two[IrBr_Five(NH_TwoC
(= S) NH_Two)], Cs_Two[IrBr_Five(N H_TwoC (= S) NH_Two)], K [IrBr_Four(NH_TwoC
(= S) NH_Two)_Two], K_Two[IrBr_Five(NH_TwoC (= NH) SCH_Three)], Na_Two[IrBr_Five(NH
_TwoC (= NH) SCH_Three)], K_Two[IrBr_Five(CH_ThreeNC (= S) NHCH_Three)], K_Three[IrBr_Five
(N (NC)_Two)], Cs_Three[IrBr_Five(N (NC)_Two)], K_Three[IrBr_Four(N (N
C)_Two)_Two], K_Two[IrBr_Five(S (NC)_Two)], K_Three[IrBr_Five(N (SO_TwoCF_Three)_Two)],
K_Three[IrBr_Five(N (CN) (SO_TwoCF_Three))], K_Two[IrBr_Five(Super)], K_Two[IrB
r_Five(Hypersol)], K_Two[IrBr_Five(Isoxazole)], K_Two[IrBr_Five( I
Sothia Sole)], K [IrBr_Four(Isothiazole) _Two], IrBr_Three(Isothiazole)
_Three, K_Two[IrBr_Five(Imitation)), K_Two[IrBr_Five(Oxazole)], K_Two[I
rBr_Five(Furassan)], K_Two[IrBr_Five(1,2,4-triazole)], K_Two[IrBr_Five
(Tetrasole)], K_Two[IrBr_Five(5-chloro- [1,2,3,4] -thiatriazole
Le)], K_Two[IrBr_Five(5-mercapht-[1,2,3,4] -thiatriazole)], K
_Two[IrBr_Five([1,3,4] -oxadazole)], K_Two[IrBr_Five([1,2,3] -H
Asia))], K_Two[IrBr_Five([1,3,4] -thiashiasole)], K_Two[Ir
Br_Five(2,5-dichloro- [1,3,4] -thiadiazole)], K_Two[IrBr_Five(2-k
Loro-5-fluoro- [1,3,4] -thiazazole)), K_Two[IrBr_Five(2,5-shiff
Ruoro-[1,3,4] -thiazazole)), K [IrBr_Four(2,5-difluoro-
[1,3,4] -thiadiazole) (NH_Three)], K_Three[IrBr_Five(2,5-mercaphate
-[1,3,4]-thiashiasole)], K_Three[IrBr_Five(2,5-cisulfamoyl-
[1,3,4] -thiashiasole)], K_Three[IrBr_Five(2-amino-5-sulfamoyl-
[1,3,4] -thiashiasole)], K_Three[IrBr_Five(2-Fluoro-5-sulfamoyl-
[1,3,4] -thiashiasole)], K_Two[IrBr_Five([1,2,4]-Chia assole
 )], K_Two[IrBr_Five(3,5-dichloro- [1,2,4] -thiadiazole).

The complexes of the general formulas I, II and III are described, for example, in Gmelin Handbuch der Anorganischen
It can be synthesized with reference to Chemie, Iridium, Erganzungsband2. Specific synthesis examples are shown below, but are not limited to these methods. (Synthesis of K ₃ [IrBr ₅ SH]) Place 300 mg (3.8 × 10 ⁻⁴ mol) of K ₃ [IrBr ₆ ] and 100 mg (1.2 × 10 ⁻³ mol) of NaSH · nH ₂ O (70%) in an eggplant flask. 3 mL of water was added. Reaction solution at 25 ° C for 5 hours
, And the precipitated solid was collected by filtration, washed with water and air-dried. 200 mg (yield 71%) of K ₃ [IrBr ₅ SH] was obtained. (Synthesis of K ₄ [IrBr ₅ (S ₂ O ₅ )]) K ₃ [IrBr ₆ ] 300 mg (3.8 × 10
^-4 mol) and 70 mg (1.2 × 10 ⁻³ mol) of K ₂ S ₂ O _{5 2} were placed in an eggplant-shaped flask, and 3 mL of water was added. The reaction solution was kept at 25 ° C. for 3 hours, and the precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. 150 mg (44% yield) of K ₄ [IrBr ₅ (S ₂ O ₅ )] was obtained.

(Synthesis of Cs ₅ [IrBr ₅ (OPO ₂ )]) K ₃ [IrBr ₆ ] 30
0 mg (3.8 × 10 ^-4 mol) and 175 mg of H ₃ PO ₃ (2.1 × 10 ^-3 mol)
Was placed in an eggplant-shaped flask, and 3 mL of water was added. Reaction solution 30
After keeping at 25 ° C. for an hour, CsCl (100 mg) and EtOH (3 mL) were added. The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. 70 mg (14% yield) of Cs ₅ [IrBr ₅ (OPO ₂ )] was obtained. (Synthesis of Cs ₅ [IrBr ₅ (OBO ₂ )]) K ₃ [IrBr ₆ ] 300 mg (3.8 × 10
⁻⁴ mol) and 84 mg (1.4 × 10 ⁻³ mol) of H ₃ BO ₃ were placed in an eggplant flask, and 3 mL of water was added. After keeping the reaction solution at 50 ° C. for 30 hours, CsCl (100 mg) and EtOH (3 mL) were added. The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. Cs ₅
5 mg (1% yield) of [IrBr ₅ (OBO ₂ )] was obtained. (Synthesis of Cs ₃ [IrBr ₅ (OSO ₂ NH ₂ )]) K ₃ [IrBr ₆ ] 300 mg (3.8
× 10 ⁻⁴ mol) and 130 mg (1.3 × 10 ⁻³ mol) of HOSO ₂ NH ₂ were placed in an eggplant-shaped flask, and 3 mL of water was added. Reaction solution at 50 ° C for 5 hours
After addition, CsCl (100 mg) and EtOH (3 mL) were added. The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. 50 mg (yield 12%) of Cs ₃ [IrBr ₅ (OSO ₂ NH ₂ )] was obtained. (Synthesis of Cs ₄ [IrBr ₅ (B ₄ O ₇ )]) K ₃ [IrBr ₆ ] 300 mg (3.8 × 10
^-4 mol) and 460 mg (1.3 × 10 ⁻³ mol) of Na ₂ B ₄ O ₇ · 10H ₂ O were placed in an eggplant flask, and 3 mL of water was added. Reaction solution for 3 days
After keeping at 25 ° C., CsCl (100 mg) and EtOH (3 mL) were added.
The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. The obtained crude crystals were dissolved in 1N HCl, and then precipitated by adding 1N NaOH. The solid was collected by filtration, washed with water and EtOH, and air-dried. 10 mg (2% yield) of Cs ₄ [IrBr ₅ (B ₄ O ₇ )] was obtained.

(Synthesis of Cs ₄ [IrBr ₅ (S ₂ O ₃ )]) K ₃ [IrBr ₆ ] 30
0mg (3.8 × 10 ^-4 mol) and _{Na 2 S 2 O 3 · 5H} 2 O 300mg (1.2 × 10
^-3 mol) was placed in an eggplant flask, and 3 mL of water was added. After keeping the reaction solution at 25 ° C for 24 hours, CsCl (100 mg) and EtOH (3m
L) was added. The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. 10 mg of Cs ₄ [IrBr ₅ (S ₂ O ₃ )] (yield 2
%) Obtained. (Synthesis of [IrBr ₃ (H ₂ NNH ₂ ) ₃ ]) K ₃ [IrBr ₆ ] 300 mg (3.8 × 10
^-4 moles) and was _{H 2 NNH 2 · H 2 O} 0.5mL of (1.0 × 10 ^-2 mol) was dissolved in putting water 2.5mL in a recovery flask. Reaction solution for 2 hours
The mixture was kept at 25 ° C., and the precipitated solid was collected by filtration, washed with water, and air-dried. 80 mg (40% yield) of [IrBr ₃ (H ₂ NNH ₂ ) ₃ ] was obtained. (Synthesis of Cs ₂ [IrBr ₅ (H ₂ NSO ₂ NH ₂ )]) K ₃ [IrBr ₆ ] 300 mg (3.
8 × 10 ⁻⁴ mol) and 420 mg (4.4 × 10 ⁻³ mol) of H ₂ NSO ₂ NH ₂ were placed in an eggplant flask and dissolved in 3 mL of water. After keeping the reaction solution at 25 ° C. for 24 hours, CsCl (100 mg) and EtOH (3 mL) were added. The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. 150 mg (41% yield) of Cs ₂ [IrBr ₅ (H ₂ NSO ₂ NH ₂ )] was obtained. (Synthesis of K ₂ [IrBr ₅ (NH ₃ )]) K ₃ [IrBr ₆ ] 1.8 g (2.3 × 10 ^-3
Mol) and NaNO ₂ 300 mg of (4.3 × 10 ^-3 mol) was dissolved in putting water 30mL egg plant flask. After refluxing the reaction solution for 8 hours, it was concentrated under reduced pressure until the amount of the solvent was reduced to half. This is rich HC
1 (45 mL) was added, the mixture was kept at 100 ° C for 30 minutes, and then cooled to 5 ° C.
The precipitated solid was collected by filtration, washed with EtOH, and air-dried. 890 mg (59% yield) of K [IrBr ₅ (NO)] was obtained. ₃ mL of a 25% NH ₃ aqueous solution was placed in an eggplant flask, and 100 mg of K [IrBr ₅ (NO)] (1.5
× 10 ^-4 mol) was added little by little. EtOH (3m
L) was added, and the precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. 50 mg (yield 48%) of K ₂ [IrBr ₅ (NH ₃ )] was obtained.

(K_Two[IrBr_Five(NH_TwoOH)]) K_Three[IrBr₆] Ten
0 mg (1.3 × 10^-FourMol) and (NH_ThreeOH)_TwoSO_Four 400 mg (2.4 × 10
^-3Mol) was placed in an eggplant flask, and 10 mL of water was added. reaction
After stirring the solution at 25 ° C. for 3 days, CsCl (50 mg) was added.
The precipitated solid was collected by filtration, washed with water and air-dried.
Cs _Two[IrBr_Five(NH_TwoOH)] was obtained in an amount of 50 mg (44% yield). (Cs_Three[IrBr_Five(PO_TwoH_TwoSynthesis of)]) K_Three[IrBr₆] 272mg (3.4 × 1
0^-FourMol) and NaPO_TwoH_Two・ H_TwoO 300mg (2.8 × 10^-3Mol)
In an eggplant flask, 10 mL of water was added. 25 reaction solution
After stirring at 24 ° C for 24 hours, CsCl (150 mg) and EtOH (10 mL) were added.
I got it. The precipitated solid is collected by filtration, washed with EtOH,
Dried. Cs_Three[IrBr_Five(PO_TwoH_Two)] Was obtained in an amount of 10 mg (yield 3%). (Ba_Two[IrBr_Five(NCO)]_ThreeSynthesis) K_Three[IrBr₆] 300mg (3.8 × 10
^-FourMol) and KNCO 300mg (3.7 × 10^-3Mol) dissolved in 10 mL of water
Understand. The reaction solution was stirred in the dark at 25 ° C. for 3 days
Later, BaCl_Two 50mg (2.4 × 10^-FourMol) and 10 mL of EtOH
Was. The precipitated solid is collected by filtration, washed with EtOH and air-dried.
did. Ba_Two[IrBr_Five(NCO)]_ThreeWas obtained (yield 5%). (Cs_Three[IrBr_Five(BO_ThreeSynthesis of)]) K_Three[IrBr₆] 150mg (1.9 × 10
^-FourMol) and NaBO_Three・ H_TwoO 150mg (1.5 × 10^-3Mol) eggplant
The flask was charged and 5 mL of water was added. Reaction solution at 25 ° C
After stirring for 4 hours, CsCl (50 mg) and EtOH (10 mL) were added.
The precipitated solid was collected by filtration, washed with EtOH, and air-dried.
Was. Cs_Three[IrBr_Five(BO_Three)] Was obtained in an amount of 50 mg (yield 25%). (K_Two[IrBr_Five(H_TwoNNH_TwoSynthesis of)]) K_Three[IrBr₆] 300mg (3.8 × 1
0^-FourMol) and H_TwoNNH_Two・ 320mg of HCl (4.7 × 10^-3Mol) eggplant
The flask was charged and 3 mL of water was added. Reaction solution at 80 ° C 3
After stirring for 0 minutes, the mixture was cooled to 0 ° C. The precipitated solid is collected by filtration.
The mixture was washed with EtOH and air-dried. K_Two[IrBr _Five(H_TwoNN
H_Two)] Was obtained in an amount of 200 mg (75% yield).

(Synthesis of K ₄ [IrBr ₅ (SiO ₃ )]) K ₃ [IrBr ₆ ] 300
mg (3.8 × 10 ^-4 mol) and _{Na 2 SiO 3 · 9H 2 O} 340mg (1.2 × 10
^-3 mol) was placed in an eggplant flask, and 3 mL of water was added. The reaction solution was stirred at 25 ° C for 3 days, and then cooled to 0 ° C. The precipitated solid was collected by filtration, washed with EtOH, and air-dried.
250 mg (80% yield) of K ₄ [IrBr ₅ (SiO ₃ )] was obtained. (Synthesis of Cs ₃ [IrCl ₅ (NCO)] · H ₂ O) Cs ₂ [IrCl ₅ (H ₂ O)] 2.0 g
(2.9 × 10 ^-3 mol), 2.0 g (2.5 × 10 ^-2 mol) of KCNO and water
40 mL was placed in an eggplant flask and dissolved while heating. The reaction solution was kept at 30 ° C. for 4 days, and the precipitated solid was collected by filtration. After washing with water, it was air-dried. Cs ₃ [IrCl ₅ (NCO)]
560 mg (22%) of H ₂ O was obtained. (Synthesis of Cs ₂ [IrCl ₅ (NH ₂ OH)]) 250 mg of Cs ₂ [IrCl ₅ (H ₂ O)]
(3.8 × 10 ^-4 mol) and NH ₂ OH · HCl 1.3 g (1.9 × 10 ^-2 mol)
Was placed in an eggplant flask, and 10 mL of water was added. Reaction solution
The mixture was kept at 25 ° C. for 3 days, and the precipitated solid was collected by filtration. After washing with water, it was air-dried. 50 mg of Cs ₂ [IrCl ₅ (NH ₂ OH)] (20
%)Obtained.

When these complexes are incorporated into silver halide grains, it is preferable that they are uniformly present inside the grains.
No. 5, as disclosed in JP-A-3-18837, it is also preferable that the compound is present only in the particle surface layer.
It is also preferred that the complex be present only inside the particle and a layer containing no complex be added to the particle surface. Further, as disclosed in US Pat. Nos. 5,252,451 and 5,256,530, it is also possible to modify the particle surface phase by physical ripening with fine particles having a complex incorporated therein. preferable. Further, these methods can be used in combination, and plural kinds of complexes may be incorporated in one silver halide grain. There is no particular limitation on the halogen composition at the position where the above-described complex is contained, and the complex may be contained in any of a silver chloride layer, a silver chlorobromide layer, a silver bromide layer, a silver iodochloride layer, and a silver iodobromide layer. Is also preferred.

[0047] In the present invention the complex of silver per mole 1 × 10 ^-10 mol 1 × 10 ^{- 4} mol amount that is can be used preferably added, more preferably 1 mol of silver per 1 × 10 ^-9 It is from 1 mol to 1 × 10 ^-5 mol. These complexes are added directly to the reaction solution when forming silver halide grains, or in an aqueous halide solution for forming silver halide grains, or in other solutions, and added to the grain formation reaction solution. Thus, it is preferable to incorporate them into silver halide grains. Further, it is also preferable to incorporate these methods into silver halide grains in combination. The iridium ion which is the central metal has III
Either a valence or a IV valence may be used, but a valence is preferably III. An iridium III-valent complex having a bromide ion as a ligand is easily oxidized, and it is preferable to add an oxidizing agent to a solution added to the emulsion. Preferably as an oxidizing agent to be added, reductones, hydrazines, hydroxylamines, hydroxysemicarbazides, hydroxyurethanes, hydroxyureas, hydroxamic acids, compounds having a vitamin E-like skeleton, phenylenediamines, phenidones, hydrazides, Or phenols. Most preferred are reductones.

The silver halide grains in the silver halide emulsion used in the present invention are preferably cubic or tetradecahedral crystal grains having substantially {100} planes (these are rounded at the apex of the grains and higher in height). May have the following planes) or octahedral crystal grains, or 50% of the total projected area
Tabular grains having an aspect ratio of 2 or more and composed of {100} planes or {111} planes are preferred. The aspect ratio is a value obtained by dividing the diameter of a circle corresponding to the projected area by the thickness of a particle. In the present invention, a cubic or tabular grain having a {100} plane as a principal plane or a tabular grain having a {111} plane as a principal plane is preferably applied.

As the silver halide emulsion used in the present invention, silver chloride, silver bromide, silver iodobromide, silver chloro (iodo) bromide emulsion and the like can be used. A silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide emulsion having a content of 95 mol% or more is preferable.
8 mol% or more of silver chloride, silver chlorobromide, silver chloroiodide, or silver chlorobromoiodide emulsion is preferred. Among such silver halide emulsions, 0.01 to 0.50 mol%, preferably 0.0
Those having a silver iodochloride phase of 5 to 0.40 mol% are also preferable because they can provide high sensitivity and are excellent in high illuminance exposure suitability. Further, the surface of the silver halide grains has a surface area of 0.2 to
Those having a silver bromide localized phase of 5 mol%, more preferably 0.5 to 3 mol% are particularly preferable because high sensitivity can be obtained and photographic performance can be stabilized.

When the emulsion of the present invention contains silver iodide, iodide ions can be introduced by adding an iodide salt solution alone or by adding iodide salt solution together with silver salt solution and high chloride salt solution. A chloride salt solution may be added. In the latter case, the iodide salt solution and the high chloride salt solution may be added separately or as a mixed solution of the iodide salt and the high chloride salt. The iodide salt is added in the form of a soluble salt, such as an alkali or alkaline earth iodide salt. Alternatively, US Patent No. 5,389,
The iodide can also be introduced by cleaving the iodide ion from the organic molecule described in JP-A-508-508. Further, fine silver iodide grains can be used as another iodide ion source.

The addition of the iodide salt solution may be carried out intensively during the grain formation, or may be carried out over a certain period of time. The position at which iodide ions are introduced into a high chloride emulsion is limited in order to obtain an emulsion having high sensitivity and low fogging. As the iodide ion is introduced into the emulsion grains, the increase in sensitivity is smaller. Therefore, the addition of the iodide salt solution is preferably performed outside 50% of the particle volume, more preferably from outside 70%, most preferably outside 80%. Also, the addition of the iodide salt solution is preferably terminated within 98% of the particle volume, most preferably within 96%. When the addition of the iodide salt solution is finished slightly inside the grain surface, an emulsion with higher sensitivity and lower fogging can be obtained.

The electron sustained release time can be determined by a reciprocity curve or a double flash photoconductive method. In the present invention, the electron sustained release time is determined from the reciprocity curve. The reciprocity curve is from the Photographic Society of Japan “Revised Basics of Photographic Engineering-Silver Halide Photography”
P. 297 can be drawn. In the case of a normal silver halide emulsion, particularly a silver chloride emulsion, the highest sensitivity is obtained in the vicinity of medium illuminance, and desensitization occurs on the low illuminance side and high illuminance side, and a downwardly convex curve is drawn. On the other hand, the reciprocity curve of the emulsion in which the high-illuminance reciprocity failure was improved by doping the electron sustained-release dopant has a flat region where desensitization does not occur in a region on the high illuminance side from a certain exposure illuminance, Different from reciprocity curve without doping. The exposure illuminance at which flattening starts, that is, the exposure time at the exposure illuminance at which a difference occurs from the characteristic curve without doping, is defined as the electron sustained release time. Since the effect of electron sustained release (re-emission of photoelectrons) is effective only after the end of exposure, the time when the electron sustained release effect appears photographically is defined as the time when re-emission of photoelectrons starts, that is, the time of electron sustained release. I can do it.

The distribution of the iodide ion concentration in the depth direction in the grain is determined by etching / TOF-SIMS (Timeo-SIMS).
f Flight-Secondary Ion Ma
ssSpectometry) method, for example, Ph
i It can be measured by using TRIF type TOF-SIMS manufactured by Evans. The TOF-SIMS method is specifically described in “Surface Analysis Technology Selection Secondary Ion Mass Spectrometry” edited by The Surface Science Society of Japan, Maruzen Co., Ltd. (1999). When the emulsion grains are analyzed by the etching / TOF-SIMS method, even if the addition of the iodide salt solution is terminated inside the grains, it can be analyzed that iodide ions are exuding toward the grain surface. When the emulsion of the present invention contains silver iodide, analysis by etching / TOF-SIMS shows that the iodide ion has a maximum concentration on the grain surface and the iodide ion concentration is attenuated inward. Is preferred.

In the case where the emulsion of the present invention contains a silver bromide localized phase, it is preferable to form a silver bromide localized phase having a silver bromide content of at least 10 mol% or more by epitaxial growth on the grain surface. The silver bromide content of the silver bromide localized phase is 10 to 10.
A range of 60 mol% is preferred, and a range of 20 to 50 mol% is most preferred. The silver bromide localized phase is preferably composed of 0.1 to 5 mol% of the total silver constituting the silver halide grains in the present invention, and 0.3 to 4 mol%.
More preferably, it is composed of silver. In the localized phase of silver bromide, iridium (III) chloride,
Iridium (III), second iridium (IV) chloride,
Group VIII metal complex ions such as sodium hexachloroiridate (III), potassium hexachloroiridate (IV), hexaammineiridium (IV) salts, trioxalatoiridium (III) salts, and trioxalatoiridium (IV) salts It is preferable to include them. The addition amount of these compounds varies widely depending on the purpose, but is preferably from 10 ^-9 to 10 ^-2 mol per mol of silver halide.

The average grain size of the silver halide grains contained in the silver halide emulsion used in the present invention (the grain size is defined by the diameter of a circle equivalent to the projected area of the grain, and the number average thereof is calculated) is 0.1. 1 μm to 2 μm is preferred. The particle size distribution is preferably a so-called monodisperse coefficient of variation (a standard deviation of the particle size distribution divided by the average particle size) of 20% or less, preferably 15% or less, more preferably 10% or less. . At this time, for the purpose of obtaining a wide latitude, it is also preferable to use the above monodispersed emulsion by blending it in the same layer, or to perform multi-layer coating.

The silver halide emulsion used in the present invention contains various compounds or their precursors for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, or stabilizing photographic performance. Can be added. Specific examples of these compounds are disclosed in the above-mentioned JP-A-62-2.
Those described on page 39 to page 72 of JP-A-15272 are preferably used. Further, a 5-arylamino-1,2,3,4-thiatriazole compound (the aryl residue has at least one electron-withdrawing group) described in EP0447647 is also preferably used.

In the present invention, the hydroxamic acid derivatives described in JP-A-11-109576 and JP-A-11-32709 are disclosed in JP-A-11-109576 in order to enhance the storage stability of the silver halide emulsion.
Cyclic ketones having a double bond in which both ends are substituted with an amino group or a hydroxyl group adjacent to the carbonyl group described in No. 4 (especially those represented by the general formula (S1), paragraphs 0036 to 0071) Can be incorporated in the specification of the present application.) And sulfo-substituted catechol and hydroquinones described in JP-A-11-143011 (for example,
4,5-dihydroxy-1,3-benzenedisulfonic acid, 2,5-dihydroxy-1,4-benzenedisulfonic acid, 3,4-dihydroxybenzenesulfonic acid, 2,
3-dihydroxybenzenesulfonic acid, 2,5-dihydroxybenzenesulfonic acid, 3,4,5-trihydroxybenzenesulfonic acid and salts thereof), and the general formulas (I) to (III) of JP-A-11-102045. The water-soluble reducing agent represented by is also preferably used in the present invention.

Spectral sensitization is performed for the purpose of imparting spectral sensitivity to a desired light wavelength range to the emulsion of each layer in the light-sensitive material of the present invention.

In the light-sensitive material of the present invention, the spectral sensitizing dye used for spectral sensitization in the blue, green, and red regions is, for example, F.I. M. Heterocyclic by Harmer
c compounds-cyanine dyes
and related compounds (Joh
n Wiley & Sons [New York, L
ondon], published in 1964). As specific examples of compounds and spectral sensitization methods, those described in the above-mentioned JP-A-62-215272, from page 22, upper right column to page 38, are preferably used. Particularly, as a red-sensitive spectral sensitizing dye for silver halide emulsion grains having a high silver chloride content, JP-A-3-123
The spectral sensitizing dye described in JP-A-340 is very preferable from the viewpoints of stability, strength of adsorption, temperature dependency of exposure and the like.

The addition amount of these spectral sensitizing dyes may vary over a wide range depending on the case, and may be 0.5 to 1 mol of silver halide.
The range is preferably from × 10 ^-6 mol to 1.0 × 10 ^-2 mol.
More preferably, 1.0 × 10 ⁻⁶ mol to 5.0 × 10 ^−3.
Range of moles.

The silver halide emulsion used in the present invention is usually subjected to chemical sensitization. Regarding the chemical sensitization method, sulfur sensitization represented by addition of an unstable sulfur compound, noble metal sensitization represented by gold sensitization, reduction sensitization, or the like can be used alone or in combination. As the compounds used for chemical sensitization, those described in JP-A-62-215272, from page 18, lower right column to page 22, upper right column, are preferably used. Among them, it is particularly preferable that the metal is subjected to gold sensitization. This is because, by performing gold sensitization, fluctuations in photographic performance when scanning exposure is performed by laser light or the like can be further reduced.

In order to sensitize the silver halide emulsion used in the present invention to gold, various inorganic gold compounds, gold (I) complexes having an inorganic ligand, and gold (I) compounds having an organic ligand can be used. It is preferable to use As inorganic gold compounds,
Examples of the gold (I) complex having a chloroauric acid or a salt thereof and an inorganic ligand include, for example, a gold dithiocyanate compound such as potassium gold (I) dithiocyanate and a gold dithiosulfate such as trisodium gold (I) dithiosulfate. It is preferable to use a compound such as a compound.

Examples of the gold (I) compound having an organic ligand include bisgold (I) mesoionic heterocycles described in JP-A-4-267249, for example, gold (I) bis (1,4 , 5-trimethyl-1,2,4-triazolium-3-thiolate), organic mercaptogold (I) complexes described in JP-A-11-218870, for example, potassium bis (1- [3- (2-sulfonatobenzamide) ) Phenyl] -5-mercaptotetrazole potassium salt) oleate (I) pentahydrate, a gold (I) compound coordinated with a nitrogen compound anion described in JP-A-4-268550, for example, bis (1-methylhydan) It is preferable to use (inert) gold (I) sodium salt tetrahydrate. Also,
Gold (I) thiolate compounds described in U.S. Pat. No. 3,503,749, gold compounds described in JP-A-8-69074, JP-A-8-69075, and JP-A-9-269554, U.S. Pat. No.5620841, 591
No. 2112, No. 5620841, No. 5939245
And No. 5,912,111 can also be preferably used.

The preferable addition amount of these compounds may vary widely depending on the case, but is preferably 5 × 10 ^{−7 to} 5 × 10 ⁻³ mol, and more preferably 5 × 10 ⁻⁶ to 1 mol of silver halide.
5 × 10 ^-4 mol.

It is also preferable to use colloidal gold sulfide, and its production method is described in Research Disclosure, 3715.
4), Solid State Ionics (Solid)
State Ionics) Vol. 79, 60-66
Page, 1995, Compt. Rend. Hebt.
Seans Acad. Sci. Sect. B second
63, p. 1328, published in 1966 and the like. Various sizes of colloidal gold sulfide can be used, and it is preferable to use one having a particle size of 50 nm or less. The amount of addition may vary widely depending on the case, but is from 5 × 10 ^{-7 to} 5 × 1 as gold atoms per mole of silver halide.
0 ^-3 mol, more preferably 5 × 10 ^-6 ~5 ×
10 ^-4 mol.

In the present invention, gold sensitization may be combined with other sensitization methods such as sulfur sensitization, selenium sensitization, tellurium sensitization, reduction sensitization, and noble metal sensitization using a compound other than a gold compound. Good.

The silver halide photographic light-sensitive material of the present invention includes
Conventionally known photographic materials and additives can be used. For example, a transmissive support or a reflective support can be used as a photographic support. Examples of the transparent support include transparent films such as cellulose nitrate film and polyethylene terephthalate, and polyesters of 2,6-naphthalenedicarboxylic acid (NDCA) and ethylene glycol (EG) and polyesters of NDCA, terephthalic acid and EG. And the like provided with an information recording layer such as a magnetic layer are preferably used. As the reflective support, a reflective support laminated with a plurality of polyethylene layers or polyester layers, and containing a white pigment such as titanium oxide in at least one of such water-resistant resin layers (laminated layers) is preferable.

As a more preferred reflection support in the present invention, a support having a polyolefin layer having micropores on a paper substrate on which a silver halide emulsion layer is provided. The polyolefin layer may consist of multiple layers, in which case the polyolefin layer adjacent to the gelatin layer, preferably on the side of the silver halide emulsion layer, has no microvoids (eg polypropylene, polyethylene) and is close to the paper substrate More preferably, it is made of a polyolefin (for example, polypropylene or polyethylene) having micropores on the side. The density of these multilayers or polyolefin layers located between the paper substrate and the photographic component layer is between 0.40 and 0.40.
1.0 g / ml, preferably 0.50 to 0.1 g / ml.
70 g / ml is more preferred. The thickness of the multilayer or one polyolefin layer located between the paper substrate and the photographic component layer is preferably from 10 to 100 μm,
~ 70 µm is more preferred. Also, the ratio of the thickness of the polyolefin layer and the paper substrate is preferably 0.05 to 0.2,
0.1-0.5 is more preferable.

It is also preferable to provide a polyolefin layer on the opposite side (back surface) of the paper base from the photographic component layer, from the viewpoint of increasing the rigidity of the reflective support. In this case, the polyolefin layer on the back surface has a matte surface. Polyethylene or polypropylene is preferred, and polypropylene is more preferred. The polyolefin layer on the back side preferably has a thickness of 5 to 50 μm, more preferably 10 to 30 μm, and further preferably has a density of 0.7 to 1.1 g / ml. In the reflection support of the present invention, a preferred embodiment relating to a polyolefin layer provided on a paper substrate is described in JP-A-10-3.
No. 33277, No. 10-333278, No. 11-52
No. 513, No. 11-65024, EP0880065
And the examples described in EP 0 880 066.

It is preferable that the water-resistant resin layer contains a fluorescent whitening agent. The fluorescent whitening agent may be dispersed in the hydrophilic colloid layer of the photosensitive material. As the fluorescent whitening agent, preferably, a benzoxazole-based, coumarin-based, or pyrazoline-based fluorescent whitening agent is used, and more preferably, a benzoxazolylnaphthalene-based or benzooxazolylstilbene-based fluorescent whitening agent is used. The amount used is not particularly limited, but is preferably 1 to 100 mg / m ² . The mixing ratio when mixed with the water-resistant resin is preferably 0.0005 to 3% by mass, more preferably 0.001 to 0.5% by mass, based on the resin.

The reflective support may be a transmissive support or the above-described reflective support provided with a hydrophilic colloid layer containing a white pigment. Further, the reflective support may be a support having a mirror-reflective or second-class diffuse-reflective metal surface.

As a support used in the light-sensitive material according to the present invention, a white polyester-based support or a layer containing a white pigment was provided on a support having a silver halide emulsion layer for a display. A support may be used. In order to further improve the sharpness, it is preferable to coat an antihalation layer on the side of the support on which the silver halide emulsion layer is coated or on the back surface. In particular, the transmission density of the support is set to 0.35 so that the display can be viewed with reflected light or transmitted light.
It is preferable to set the range to 0.8.

In the light-sensitive material according to the present invention, a hydrophilic colloid layer is added to the hydrophilic colloid layer for the purpose of improving the sharpness of an image.
P0, 337, 490A2, pages 27 to 76, a dye capable of being decolorized by processing (among others, an oxonol dye) is added so that the optical reflection density at 680 nm of the photosensitive material becomes 0.70 or more. Or to make the water-resistant resin layer of the support contain 12% by mass or more (more preferably 14% by mass or more) of titanium oxide surface-treated with a divalent or tetravalent alcohol (for example, trimethylolethane) or the like. Is preferred.

The light-sensitive material according to the present invention may contain a hydrophilic colloid layer in order to prevent irradiation or halation or to improve safelight safety.
It is preferable to add a dye (for example, an oxonol dye and a cyanine dye) which can be decolorized by the treatment described on pages 27 to 76 of the specification of No. 7490A2. Furthermore, EP0
The dyes described in 819977 are also preferably added to the invention.

Some of these water-soluble dyes deteriorate color separation and safelight safety when used in an increased amount. As dyes that can be used without deteriorating color separation,
Water-soluble dyes described in JP-A-5-127324, JP-A-5-127325 and JP-A-5-216185 are preferred.

In the present invention, instead of the water-soluble dye,
Alternatively, a colored layer that can be decolorized by a treatment in combination with a water-soluble dye is used. The colored layer that can be decolorized by the processing used may be in direct contact with the emulsion layer, or may be arranged so as to be in contact with an intermediate layer containing a processing color mixture inhibitor such as gelatin or hydroquinone. This colored layer is preferably provided below (on the side of the support) the emulsion layer that develops the same primary color as the colored color. It is possible to install all the colored layers corresponding to each primary color individually, or to arbitrarily select and install only a part of them. Further, it is also possible to provide a colored layer which is colored corresponding to a plurality of primary color gamuts. The optical reflection density of the colored layer is within the wavelength range used for exposure (400 n in normal printer exposure).
It is preferable that the optical density value at the wavelength having the highest optical density in the visible light region of m to 700 nm, or the wavelength of the scanning exposure light source used in the case of scanning exposure) is 0.2 or more and 3.0 or less. More preferably, it is 0.5 or more and 2.5 or less, particularly preferably 0.8 or more and 2.0 or less.

For forming the colored layer, a conventionally known method can be applied. For example, Japanese Patent Application Laid-Open No. 2-282244-3
The dyes described on page 8 from the upper right column of the page and JP-A-3-79
No. 31, page 3, upper right column to page 11, lower left column, a method in which a solid fine particle dispersion is contained in a hydrophilic colloid layer, a method in which an anionic dye is mordanted to a cationic polymer, and a dye is halogenated. Examples thereof include a method of adsorbing fine particles such as silver and fixing it in a layer, and a method of using colloidal silver as described in JP-A-1-239544. As a method of dispersing the fine powder of the dye in a solid state, for example, a method of containing a fine powder dye which is substantially water-insoluble at least at pH 6 or less but is substantially water-soluble at least at pH 8 or more is disclosed in 2-30824
No. 4, pages 4-13. Also, for example,
A method of mordanting an anionic dye into a cationic polymer is described in JP-A-2-84637, pp. 18-26. For the preparation of colloidal silver as a light absorber, see U.S. Pat. Nos. 2,688,601 and 3,45.
No. 9,563. Among these methods, a method of incorporating a fine powder dye and a method of using colloidal silver are preferred.

The silver halide photographic light-sensitive material of the present invention is used for a color negative film, a color positive film, a color reversal film, a color reversal photographic paper, a color photographic paper, and the like, and among them, a color photographic paper is preferable.
Color photographic paper has a yellow coloring silver halide emulsion layer,
It is preferable to have at least one layer each of a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer. A silver halide emulsion layer, a magenta color-forming silver halide emulsion layer, and a cyan color-forming silver halide emulsion layer.

However, a different layer configuration may be adopted. The silver halide emulsion layer containing the yellow coupler may be located at any position on the support. However, when the yellow coupler containing layer contains silver halide tabular grains, the silver halide emulsion layer containing the magenta coupler may be used. It is preferable that the coating is provided at a position farther from the support than at least one of the silver emulsion layer and the cyan coupler-containing silver halide emulsion layer. Further, from the viewpoint of accelerating color development, accelerating desilvering, and reducing residual color by the sensitizing dye, the yellow-coupler-containing silver halide emulsion layer is located farthest from the support than the other silver halide emulsion layers. Preferably, it is coated. Further, from the viewpoint of reducing Blix fading, the cyan coupler-containing silver halide emulsion layer is preferably a layer at the center of the other silver halide emulsion layers, and from the viewpoint of reducing photo-fading, the cyan coupler-containing silver halide emulsion layer is preferably The lowermost layer is preferred. Further, each of the color forming layers of yellow, magenta and cyan may be composed of two or three layers. For example, as described in JP-A-4-75055, JP-A-9-114035, JP-A-10-246940, and U.S. Pat. No. 5,576,159, a coupler layer containing no silver halide emulsion is used to form a silver halide emulsion. It is also preferable to provide a color-forming layer provided adjacent to the emulsion layer.

The silver halide emulsion and other materials (additives, etc.) and photographic constituent layers (layer arrangements, etc.) used in the present invention, and the processing methods and processing additions applied for processing this light-sensitive material As the agent, JP-A-62-2
No. 15272, JP-A-2-33144, EP0,35
5,660A2, especially EP0,
Those described in No. 355,660A2 are preferably used. Further, Japanese Patent Application Laid-Open Nos.
No. 359249, No. 4-313375, No. 4-270
No. 344, No. 5-66527, No. 4-34548,
4-145433, 2-854, 1-158
No. 431, No. 2-90145, No. 3-194439
And silver halide color photographic light-sensitive materials described in JP-A No. 2-93641, EP 0520457A2 and the like, and a processing method therefor are also preferable.

In particular, in the present invention, the above-mentioned reflective support, silver halide emulsion, different metal ion species doped in silver halide grains, storage stabilizer of silver halide emulsion or antifoggant , Chemical sensitization method (sensitizer),
Spectral sensitization (spectral sensitizer), cyan, magenta, yellow couplers and their emulsifying and dispersing methods, color image preservability improvers (anti-stain and anti-fading agents), dyes (colored layers), gelatin, photosensitive materials With respect to the layer constitution and the coating pH of the photosensitive material, those described in the patents of Tables 1 and 2 can be particularly preferably applied.

[0082]

[Table 1]

[0083]

[Table 2]

The cyan, magenta and yellow couplers used in the present invention are described in
No. 2-215272, page 91, upper right column, line 4 to page 121, upper left column, line 6, JP-A-2-33144, page 3, upper right column, line 14 to page 18, upper left column, last line and page 30, upper right Lines 6 to 35, lower right column, line 11 and EP 0355,660A2, page 4, lines 15 to 27, page 5, line 30 to page 28, last line, page 45, lines 29 to 31 Eye, page 47, lines 23-6
The couplers described on page 3, line 50 are also useful.

Also, the present invention relates to the compounds of the general formulas (II) and (III) of WO-98 / 33760,
A compound represented by the formula (D) of No. 825 may be added, which is preferable.

A more specific description is given below. As a cyan coupler usable in the present invention, a pyrrolotriazole coupler is preferably used.
The couplers represented by the general formula (I) or (II) of No. 4 and the couplers represented by the general formula (I) of JP-A-6-347960 and the couplers described in these patents are particularly preferred. Phenol and naphthol cyan couplers are also preferable.
Preferred is a cyan coupler represented by the general formula (ADF) described in JP-A-333297.

Other cyan couplers include those described in EP
Nos. 4,488,248 and EP0491197A1, pyrroloazole type cyan couplers described in U.S. Pat. No. 5,888,716, 2,5-diacylaminophenol couplers described in U.S. Pat. No. 5,888,716, U.S. Pat.
No. 83, No. 4,916,051, pyrazoloazole-type cyan couplers having an electron-withdrawing group and a hydrogen bonding group at the 6-position, particularly JP-A Nos. 8-171185 and 8-171.
Pyrazoloazole-type cyan couplers having a carbamoyl group at the 6-position described in JP-A Nos. 311360 and 8-339060 are also preferable.

Further, it is described in JP-A-2-33144.
In addition to the diphenylimidazole cyan coupler of
3-hydroxyl described in P03333185 A2
Pyridine cyan coupler (listed as specific examples
Leaving group to 4-equivalent coupler (42)
And two equivalents, coupler (6)
(9) is particularly preferred) and JP-A-64-32260.
Cyclic active methylene cyan couplers described in
However, coupler examples 3, 8, and 34 listed as specific examples
Are particularly preferred) and EP 0 456 226 A1.
Pyrrolopyrazole type cyan coupler described in EP048
Pyrroloimidazole-type cyanka described in No. 4909A1
Pullers can also be used.

As the magenta coupler used in the present invention, a 5-pyrazolone-based magenta coupler or a pyrazoloazole-based magenta coupler as described in the publicly known documents in the above table can be used.
A pyrazolotriazole coupler in which a secondary or tertiary alkyl group is directly linked to the 2, 3 or 6-position of the pyrazolotriazole ring as described in JP-A-61-65245 in terms of color development and the like. Pyrazoloazole couplers containing a sulfonamide group in the molecule as described in JP-65246, pyrazoloazole couplers having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254 and EP It is preferable to use a pyrazoloazole coupler having an alkoxy group or an aryloxy group at the 6-position described in Nos. 226,849A and 294,785A. In particular, magenta couplers represented by the general formula (M-) described in JP-A-8-122984
Pyrazoloazole couplers represented by I) are preferred,
Paragraph numbers 0009 to 0026 of that patent apply directly to this application and are incorporated as part of the specification of this application. In addition, EP 854384, EP 846640
Pyrazoloazole couplers having a sterically hindered group at both the 3- and 6-positions described in (1) are also preferably used.

As the yellow coupler, in addition to the compounds described in the above table, an acylacetamide type yellow coupler having a 3- to 5-membered cyclic structure in an acyl group described in EP0447969A1, EP04825
No. 5,118,5, a malondianilide-type yellow coupler having a cyclic structure described in US Pat.
An acylacetamide type yellow coupler having a dioxane structure described in JP-A-99-9999 is preferably used. Among them, it is particularly preferable to use an acylacetamide-type yellow coupler in which the acyl group is a 1-alkylcyclopropane-1-carbonyl group and a malondianilide-type yellow coupler in which one of the anilides forms an indoline ring. These couplers can be used alone or in combination.

The couplers used in the present invention can be prepared by loading a loadable latex polymer (for example, US Pat. No. 4,2,100) in the presence (or absence) of the high boiling organic solvent described in the above table.
No. 03,716) or dissolved together with a water-insoluble and organic solvent-soluble polymer and emulsified and dispersed in a hydrophilic colloid aqueous solution. Water-insoluble and organic solvent-soluble polymers which can be preferably used are described in U.S. Pat. No. 4,857,449, columns 7 to 15 and WO 88/00723, pages 12 to 30. The homopolymer or copolymer described above may be used. More preferably, use of a methacrylate-based or acrylamide-based polymer, particularly, an acrylamide-based polymer is preferred from the viewpoint of color image stability and the like.

In the present invention, known color mixing inhibitors can be used, and among them, those described in the following patents are preferable. For example, high-molecular-weight redox compounds described in JP-A-5-333501, WO98 / 33
No. 760, U.S. Pat. No. 4,923,787, etc .; phenidone and hydrazine compounds;
No. 37, JP-A-10-282615 and German Patent No. 19629142A1 can be used. In particular, the pH of the developer is increased,
In the case of speeding up development, German Patent No. 1961878
No. 6A1, EP 839623 A1, EP 8429
It is also preferable to use the redox compounds described in, for example, No. 75A1, German Patent 19806846A1 and French Patent No. 2760460A1.

In the present invention, it is preferable to use a compound having a triazine skeleton having a high molar extinction coefficient as an ultraviolet absorber. For example, the compounds described in the following patents can be used. JP-A-46-3335, 55
-152776, JP-A-5-197074, and 5-
No. 232630, No. 5-307232, No. 6-211
No. 813, No. 8-53427, No. 8-234364
Nos. 8-239368, 9-31067, 1
Nos. 0-115598, 10-147577, 10
182621, German Patent No. 19739797A,
EP 711804A and Tokuhyo Hei 8-501291
And the like.

As a binder or protective colloid that can be used in the light-sensitive material according to the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin. As a preferred gelatin, heavy metals contained as impurities such as iron, copper, zinc, and manganese are preferably 5 ppm.
Or less, more preferably 3 ppm or less. The amount of calcium contained in the photosensitive material is preferably 20 m
g / m ² or less, more preferably 10 mg / m ² or less, and most preferably 5 mg / m ² or less.

In the present invention, in order to prevent various fungi and bacteria which propagate in the hydrophilic colloid layer and deteriorate the image, a bactericidal / antifungal agent as described in JP-A-63-271247 is used. It is preferably added.

Further, the coating pH of the photosensitive material is 4.0 to 4.0.
7.0 is preferred, and more preferably 4.0 to 6.5.

In the present invention, a surfactant can be added to the light-sensitive material from the viewpoints of improving the coating stability of the light-sensitive material, preventing generation of static electricity, and adjusting the charge amount. Examples of the surfactant include an anionic surfactant, a cationic surfactant, a betaine surfactant, and a nonionic surfactant, and examples thereof include those described in JP-A-5-333492. As the surfactant used in the present invention, a fluorine atom-containing surfactant is preferable. In particular, a fluorine atom-containing surfactant can be preferably used.

The amount of these surfactants added to the photosensitive material
Is not particularly limited, but generally 1 × 10
^-Five~ 1g / m^Two , Preferably 1 × 10^-Four~ 1 × 10^-1g
/ M ^Two , More preferably 1 × 10^-3~ 1 × 10^-2g / m
^Two It is. These fluorine atom-containing surfactants can be used alone
Used in combination with other conventionally known surfactants.
Although not mentioned, it is preferable to use together with other conventionally known surfactants.
It is for.

The light-sensitive material of the present invention is suitable for a scanning exposure method using a cathode ray (CRT), in addition to being used for a printing system using a normal negative printer. A cathode ray tube exposure apparatus is simpler, more compact, and lower in cost than an apparatus using a laser. Further, adjustment of the optical axis and color is also easy.

For the cathode ray tube used for image exposure, various luminous bodies which emit light in a spectral region are used as necessary. For example, any one of a red light emitter, a green light emitter, and a blue light emitter, or a mixture of two or more thereof is used.
The spectral region is not limited to the above red, green, and blue, and a phosphor that emits light in a yellow, orange, purple, or infrared region is also used. In particular, a cathode ray tube which emits white light by mixing these light emitters is often used.

When the photosensitive material has a plurality of photosensitive layers having different spectral sensitivity distributions and the cathode tube also has a phosphor that emits light in a plurality of spectral regions, a plurality of colors are exposed at a time, that is, the cathode ray is exposed. A plurality of color image signals may be input to the tube to emit light from the tube surface. A method of sequentially inputting image signals for each color, sequentially emitting light of each color, and exposing through a film that cuts a color other than that color (plane sequential exposure)
In general, plane-sequential exposure is preferable for improving image quality because a cathode ray tube with high resolution can be used.

The photosensitive material of the present invention is a second harmonic emission light source (SHG) in which a gas laser, a light emitting diode, a semiconductor laser, a semiconductor laser or a solid laser using a semiconductor laser as an excitation light source is combined with a nonlinear optical crystal.
A digital scanning exposure method using monochromatic high-density light is preferably used. In order to make the system compact and inexpensive, it is preferable to use a semiconductor laser, a semiconductor laser or a second harmonic generation light source (SHG) in which a solid-state laser is combined with a nonlinear optical crystal. Particularly, in order to design an apparatus that is compact, inexpensive, and has a long life and high stability, it is preferable to use a semiconductor laser, and it is preferable to use a semiconductor laser as at least one of the exposure light sources.

When such a scanning exposure light source is used,
The spectral sensitivity maximum wavelength of the light-sensitive material of the present invention can be arbitrarily set according to the wavelength of the scanning exposure light source to be used.
In a solid-state laser using a semiconductor laser as an excitation light source or an SHG light source obtained by combining a semiconductor laser and a nonlinear optical crystal, the laser oscillation wavelength can be halved, so that blue light and green light can be obtained. Therefore, the spectral sensitivity maximum of the photosensitive material can be provided in the usual three wavelength ranges of blue, green and red. If the exposure time in such scanning exposure is defined as the exposure time for the pixel size when the pixel density is 400 dpi, the preferred exposure time is 10 ^-4 seconds or less, more preferably 10 ^-6 seconds or less.

Preferred scanning exposure systems applicable to the present invention are described in detail in the patents listed in the above table. Further, for processing the light-sensitive material of the present invention, JP-A-2-207250, page 26, lower right column, line 1 to page 34, upper right column, line 9 and JP-A-4-97355, page 5 upper left column The processing materials and processing methods described in the 17th line to the 20th line on the lower right column on page 18 can be preferably applied. As the preservative used in the developer, compounds described in the patents listed in the above table are preferably used.

The present invention is preferably applied to light-sensitive materials having rapid processing suitability. The color development time refers to the time from when the photosensitive material enters the color developing solution to when it enters the bleach-fix solution in the next processing step. For example, when processing is performed by an automatic developing machine or the like, the time during which the photosensitive material is immersed in the color developing solution (so-called in-solution time) and the time when the photosensitive material leaves the color developing solution and is bleach-fixed in the next processing step The sum of the time during which it is transported in the air toward the bath (the so-called air time) is referred to as the color development time. Similarly, the bleach-fixing time refers to the time from when the photosensitive material enters the bleach-fixing solution to when it enters the next washing or stabilizing bath. The term “washing or stabilizing time” refers to the time during which the photosensitive material is in the washing or stabilizing solution and is in the solution for the drying step (so-called in-solution time).

In the case where rapid processing is performed in the present invention,
The color development time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, and still more preferably 30 seconds or less and 6 seconds or more. Similarly, the bleach-fixing time is preferably 60 seconds or less, more preferably 50 seconds or less and 6 seconds or more, and still more preferably 30 seconds or less and 6 seconds or more. The washing or stabilizing time is preferably 150 seconds or less, more preferably 130 seconds or less.
It is less than second and more than 6 seconds.

As a method of developing the photosensitive material of the present invention after exposure, a conventional method of developing with a developer containing an alkali agent and a developing agent, an alkaline solution containing a developing agent incorporated in the photosensitive material and containing no developing agent In addition to a wet method such as a method of developing with an activator solution such as a method described above, a thermal developing method without using a processing solution can be used. In particular, the activator method is a preferable method from the viewpoint of environmental protection because the developing agent is not contained in the processing solution, so that the processing solution can be easily managed and handled, and the load at the time of processing the waste solution is small. In the activator method, examples of the developing agent or its precursor incorporated in the photosensitive material include, for example, JP-A-8-234.
No. 388, No. 9-152686, No. 9-152693
And hydrazine-type compounds described in JP-A Nos. 9-218814 and 9-160193.

A developing method in which the amount of silver applied to the light-sensitive material is reduced and image amplification processing (intensification processing) using hydrogen peroxide is preferably used. In particular, it is preferable to use this method for the activator method. Specifically, Japanese Patent Application Laid-Open
An image forming method using an activator liquid containing hydrogen peroxide described in JP-A-297354 and JP-A-9-152699 is preferably used. In the activator method, after processing with an activator solution, usually a desilvering process is performed, but in an image amplification processing method using a low silver content photosensitive material,
The desilvering process can be omitted, and a simple method such as washing with water or stabilizing process can be performed. Further, in a method in which image information is read from a photosensitive material by a scanner or the like, a processing mode that does not require desilvering processing can be adopted even when a photosensitive material having a high silver content such as a photosensitive material for photographing is used.

As the activator solution, desilvering solution (bleaching / fixing solution), washing and stabilizing solution used in the present invention, known processing materials and processing methods can be used. Preferably, Research Disclosure Item 365
44 (September 1994), pages 536 to 541, and JP-A-8-234388 can be used.

When exposing the light-sensitive material of the present invention to a printer, it is preferable to use a band stop filter described in US Pat. No. 4,880,726. As a result, light color mixing is removed, and color reproducibility is significantly improved. In the present invention, EP0778970A1 and EP0778970A1
As described in 89480A1, before the image information is added, a yellow microdot pattern may be pre-exposed in advance to control copying.

[0111]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. Example 1 "Emulsion 1-1; Preparation of Cubic Silver Chloride Sample (1)" (Comparative Example) 5.6% sodium chloride in 5% aqueous solution of lime-processed gelatin
g of 1N sulfuric acid and N, N′-dimethylimidazolidin-2-thione (1% aqueous solution) in 1.1%.
mL was added. An aqueous solution (241.2 mL) containing 0.21 mol of silver nitrate and an aqueous solution (241.2 mL) containing 0.21 mol of sodium chloride are stirred in this aqueous solution while stirring.
The mixture was added at 24 ° C. for 24 minutes. Subsequently, while maintaining the temperature at 61 ° C., an aqueous solution containing 1.91 mol of silver nitrate (720 m
L) and an aqueous solution containing 1.91 mol of sodium chloride (7
(20 mL) over 40 minutes to obtain cubic particles having an average particle size of 0.62 μm (variation coefficient: 10%). Thereafter, the precipitate was washed by settling at 40 ° C. and desalted.
Further, 168.0 g of lime-processed gelatin was added, and p
H and pAg were adjusted to 7.3 and 5.6, respectively. This emulsion contains a gold sensitizer (gold (I) tetrafluoroborate bis (1,
4,5-trimethyl-1,2,4-triazolium-3
-Thiolate)) was added at 1.5 × 10 ⁻⁵ mol per mol of silver, and a sulfur sensitizer (sodium thiosulfate) was added at 6 × 10 ⁻⁷ mol per mol of silver. A and B) were optimally chemically sensitized and spectrally sensitized at 60 ° C. by adding 2.3 × 10 ⁻⁴ mol and 1.5 × 10 ⁻⁴ mol per mol of silver. -Methylureidophenyl) -5-mercaptotetrazole in silver 1
Emulsion 1 was obtained by adding 4.4 × 10 ^-4 mole per mole.
-1 was obtained.

[0112]

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[0113] "Emulsion 1-2; [IrCl _6] ^3- Preparation of doped silver cubic samples chloride" (Comparative Example) 92 to 97% hexachloroiridate the emulsion of the emulsion 1-1 from grains central portion in grain volume the emulsion 1-2 in the same manner as emulsion 1-1 except that the addition of 2 × 10 ^-8 mol relative to the amount of silver was added to the emulsion was prepared in the layer.

[Emulsion 1-3; [IrCl ₅ (H ₂ O)]
^Preparation of ^2- Doped Silver Chloride Cube Sample "(Comparative Example) Emulsion 1-1 was added with pentachloroaquoiridium in a 92-97% layer in an amount of 8 × 10
Emulsion 1-3 was prepared in the same manner as Emulsion 1-1 except that ^-7 mol or 6 × 10 ^-7 mol was added, respectively.

[Emulsion 1-4, 1-5; [IrBr ₅ (H
Preparation of Cubic Silver Chloride Sample Doped with ₂ O)] ^2- and [IrBr ₅ (OCN)] ^3- (Invention) Pentabromoaquoiridium or pentabromoisocyanatoiridium was added to the emulsion 1-1. Emulsions 1-4 and 1-5 were prepared in the same manner as Emulsion 1-1 except that 8 × 10 ⁻⁸ mol was added to the silver amount added to the emulsion in a layer of 92 to 97% from the center of the grain in terms of grain volume. Was prepared.

[Emulsion 1-6; Preparation of Cubic Silver Chloride Sample Doped with [IrBr ₄ F ₂ ] ^3- ”(in the present invention) The emulsion 1-6 was prepared in the same manner as in the emulsion 1-1 except that 1 × 10 ⁻⁷ mol was added to the 92-97% layer based on the amount of silver added to the emulsion.

"Emulsion 1-7, 1-8; [IrBr ₄ Cl
Preparation of Cubic Silver Chloride Sample Doped with (H ₂ O)] ²⁻ , [IrBr ₃ Cl ₂ (H ₂ O)] ² (invention) Emulsion 1 except that 1 × 10 ⁻⁷ mol or 2 × 10 ⁻⁷ mol was added to the silver amount of tribromodichloroaquoiridium added to the emulsion in a layer of 92 to 97% from the central part of the particle in terms of particle volume. Emulsion 1 as in -1
-7 and 1-8 were prepared.

"Emulsion 1-9; Preparation of Cubic Silver Chloride Sample Doped with [IrBr ₅ (N (CN) ₂ )] ^2- " (Invention) Pentabromo (dicyanamide) iridium was added to emulsion 1-1. Emulsion 1-9 was prepared in the same manner as Emulsion 1-1 except that 1 × 10 ⁻⁷ mol of silver was added to the emulsion in a layer of 92 to 97% from the central part of the grain by grain volume. .

[Emulsion 1-10, 1-11, [IrBr_Five(2,5-
Dichloro-1,3,4-thiadiazole)] ^2-, [IrBr_Five(2-black
Ro-5-fluoro-1,3,4-thiadiazole)]^2-Dope
Preparation of Cubic Silver Chloride Sample ”(Invention) Pentabromo (2,5-dichloro-1,
3,4-thiadiazole) iridium or pentabromo (2
-Chloro-5-fluoro-1,3,4-thiadiazole) iridi
From the center of the particle to the 92-97% layer by particle volume
1 × 10 with respect to the amount of silver added to the agent^-7, 3 × 1
0^-7Emulsion as in Emulsion 1-1 except that mol was added.
1-10 and 1-11 were prepared.

"Emulsion 1-12; Preparation of Cubic Silver Chloride Sample Doped with [IrBr ₅ (2,5-Difluoro-1,3,4-thiadiazole)] ^2- " (Embodiment) Emulsion of Emulsion 1-1 Pentabromo (2,5-difluoro-
Same as Emulsion 1-1 except that 1,3,4-thiadiazole) iridium was added in an amount of 1 × 10 ^-7 mol based on the silver amount added to the emulsion in a layer of 92 to 97% from the center of the grain in terms of grain volume. To prepare Emulsion 1-12.

[Emulsions 1-13, 14, 15; [IrBr ₅ (H ₂ N
C (= S) NH ₂ )] ^2- , [IrBr ₅ (H ₂ NC (= NH) SCH ₃ )] ^2- , [IrBr ₅ (S = P
(NH2) ₂ (OH))] ^Preparation of ^2- Doped Cubic Silver Samples "
The emulsion of the (present invention) Emulsion _{1-1, [IrBr 5 (H 2} NC (= S) NH 2)] 2-, [IrBr 5
(H ₂ NC (= NH) SCH ₃ )] ²⁻ , [IrBr ₅ (S = P (NH ₂ ) ₂ (OH))] ²⁻ in a 92-97% layer from the grain center to the emulsion by grain volume 1 × 10 ⁻⁷ , 3 × 10 ⁻⁷ , 5 ×
Emulsions 1-13, 1-14 and 1-15 were prepared in the same manner as Emulsion 1-1 except that 10 ^-7 mol was added.

After a corona discharge treatment was applied to the surface of a support obtained by coating these emulsions on both sides of a paper with a polyethylene resin, a gelatin subbing layer containing sodium dodecylbenzenesulfonate was provided. To the seventh layer were sequentially coated to prepare samples (101) to (115) of silver halide color photographic light-sensitive materials having the following layer constitution. The coating solution for each photographic constituent layer was prepared as follows.

Preparation of Coating Solution for First Layer 57 g of yellow coupler (ExY), color image stabilizer (Cp
d-1) 7 g, color image stabilizer (Cpd-2) 4 g, color image stabilizer (Cpd-3) 7 g, color image stabilizer (Cpd-8) 2
g of solvent (Solv-1) 21 g and ethyl acetate 80 m
1 g of a 23.5% by weight aqueous gelatin solution containing 4 g of sodium dodecylbenzenesulfonate.
In 0 g, the mixture was emulsified and dispersed by a high-speed stirring emulsifier (dissolver), and water was added to prepare 900 g of emulsified dispersion A. On the other hand, the emulsified dispersion A and the emulsion 1-1 were mixed and dissolved to prepare a coating solution for the first layer so as to have the following composition. The emulsion coating amount indicates a coating amount in terms of silver amount.

The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt (H-1), (H-2), (H-3) was used. The total amount of Ab-1, Ab-2, Ab-3, and Ab-4 was 15.0 mg / m ² , 60.
0 mg / m ² , 5.0 mg / m ² and 10.0 mg / m
² was added.

[0125]

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[0126]

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The silver and chlorobromide emulsions of the green and red-sensitive emulsion layers include:
The following spectral sensitizing dyes were used respectively. Green-sensitive emulsion layer

[0128]

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(Sensitizing dye D was added per mole of silver halide,
3.0 × 10 for large emulsions ^-FourMol, small size
3.6 × 10 for emulsion^-FourMol and sensitizing dye E
Per mole of silver halide and for large emulsions
4.0 × 10^-Five7.0 × for mole, small size emulsions
10^-FiveMol of sensitizing dye F per mol of silver halide.
2.0 × 10^-FourMol, small sa
2.8 × 10^-FourMole was added. ) Red-sensitive emulsion layer

[0130]

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(The sensitizing dyes G and H were used in an amount of 8.0 × 1 for the large-size emulsion per mole of silver halide.)
0 ^-5 mol, it was added 10.7 × 10 ^-5 mol to the small size emulsion. Further, the following compound I was added to the red-sensitive emulsion layer in an amount of 3.0 × 10 ⁻³ mol per mol of silver halide. )

[0132]

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Also, 1- (3-methylureidophenyl) -5-mercaptotetrazole was added to the green-sensitive emulsion layer and the red-sensitive emulsion layer in an amount of 3.3 × 10 ^-4 mol, 4.0 × 10 ^-3 mol and 5.
9 × 10 ^-4 mol was added. Further, each of the second layer, the fourth layer, the sixth layer and the seventh layer also has 0.2 mg / m ² ,
0.2 mg / m ² , 0.6 mg / m ² , 0.1 mg / m
² was added.

Further, 4-hydroxy-6-methyl-1,3,3a, 7 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
Tetrazindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide.

The red-sensitive emulsion layer was coated with 0.05 g / copolymer latex of methacrylic acid and butyl acrylate (mass ratio 1: 1, average molecular weight 200000 to 400,000).
m ² was added.

Further, disodium catechol-3,5-disulfonate was added to the second, fourth and sixth layers, respectively.
mg / m ² , 6 mg / m ² and 18 mg / m ² .

For the purpose of preventing irradiation, the following dyes were added (in parentheses, the coating amount is shown).

[0138]

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(Layer Structure) The structure of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion is
It represents the silver equivalent coating amount. Support Polyethylene resin laminated paper [A white pigment (TiO ₂ ; content: 16% by mass, ZnO: content: 4% by mass) and a fluorescent whitening agent (4,4′-bis (5 -Methylbenzooxosazolyl) stilbene, containing 0.03% by mass and a bluish dye (ultra blue)] First layer (blue-sensitive emulsion layer) Emulsion 1-1 0.24 Gelatin 1.25 Yellow coupler (ExY ) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stabilizer (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0 .02 Solvent (Solv-1) 0.21

Second layer (color mixture prevention layer) Gelatin 0.99 Color mixture prevention agent (Cpd-4) 0.09 Color image stabilizer (Cpd-5) 0.018 Color image stabilizer (Cpd-6) 0.13 Color image stabilizer (Cpd-7) 0.01 Solvent (Solv-1) 0.06 Solvent (Solv-2) 0.22

Third Layer (Green-Sensitive Emulsion Layer) Silver chlorobromide emulsion Em-1 (gold-sulfur sensitized cube, large-sized emulsion having an average grain size of 0.45 mm and small-sized emulsion having an average grain size of 0.35 mm) (Molar ratio of silver) The variation coefficient of the grain size distribution is 0.10 and 0.08, respectively.Emulsion of each size contains 0.15 mol% of silver iodide near the grain surface and 0.14 Gelatin 1.36 Magenta coupler (ExM) 0.15 Ultraviolet absorber (UV-A) 0.14 Color image stabilizer (Cpd- 2) 0.02 color image stabilizer (Cpd-4) 0.002 color image stabilizer (Cpd-6) 0.09 color image stabilizer (Cpd-8) 0.02 color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0.01 Color image stabilizer (Cpd-11) 0.0001 solvent (Solv-3) 0.11 solvent (Solv-4) 0.22 solvent (Solv-5) 0.20

Fourth layer (color mixture prevention layer) Gelatin 0.71 Color mixture prevention layer (Cpd-4) 0.06 Color image stabilizer (Cpd-5) 0.013 Color image stabilizer (Cpd-6) 0.10 Color image stabilizer (Cpd-7) 0.007 Solvent (Solv-1) 0.04 Solvent (Solv-2) 0.16

Fifth Layer (Red-Sensitive Emulsion Layer) Silver chlorobromide emulsion Em-2 (gold-sulfur sensitized cube, large-sized emulsion having an average grain size of 0.40 mm and small-sized emulsion having an average grain size of 0.30 mm) (Molar ratio of silver) The coefficient of variation of the grain size distribution was 0.09 and 0.11, respectively.Each size emulsion and each size emulsion contained 0.1 mol% of silver iodide near the grain surface. 0.12 gelatin 1.11 cyan coupler (ExC-2) 0.13 cyan coupler (ExC-3) 0.03 color image stabilizer (Cpd-1) 0.05 Color image stabilizer (Cpd-6) 0.06 Color image stabilizer (Cpd-7) 0.02 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd) -10) 0.01 color image stabilizer (Cpd-14) 0.01 color image Stabilizer (Cpd-15) 0.12 Color image stabilizer (Cpd-16) 0.03 Color image stabilizer (Cpd-17) 0.09 Color image stabilizer (Cpd-18) 0.07 Solvent (Solv- 5) 0.15 Solvent (Solv-8) 0.05

Sixth layer (ultraviolet absorbing layer) Gelatin 0.46 Ultraviolet absorbing agent (UV-B) 0.45 Compound (S1-4) 0.0015 Solvent (Solv-7) 0.25 Seventh layer (protective layer) ) Gelatin 1.00 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-13) 0.01

[0145]

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[0146]

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[0147]

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[0148]

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[0149]

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[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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Similarly, the emulsion 1-1 of Sample (101) was changed to Emulsions 1-2 to 1-15, and Samples (102) to (11)
5) was produced.

The following experiment was conducted to examine the photographic characteristics of these samples.

Experiment 1: Sensitometry Each coating sample was subjected to sensitometric gradation exposure using a photometer (FWH type, manufactured by Fuji Photo Film Co., Ltd.). Exposure was performed for 10 seconds at low illuminance with an SP-1 filter attached.

Further, gradation exposure for sensitometry was performed using a high-illuminance exposure sensitometer (HIE type manufactured by Yamashita Denso Co., Ltd.). An SP-1 filter was attached, and exposure was performed at a high illuminance of 10 ^-4 seconds. After the exposure, the following color development processing A was performed.

The processing steps will be described below. [Processing A] The photosensitive material 101 was processed into a roll having a width of 127 mm, and was imagewise exposed using a minilab printer processor PP1258AR manufactured by Fuji Photo Film Co., Ltd., and then replenished twice the capacity of the color developing tank in the following processing steps. Until this was done, continuous processing (running test) was performed. This treatment using the running liquid was designated as treatment A. Processing process Temperature Time Replenishment amount * Color development 38.5 ° C 45 seconds 45mL Bleaching and fixing 38.0 ° C 45 seconds 35mL Rinse (1) 38.0 ° C 20 seconds-Rinse (2) 38.0 ° C 20 seconds-Rinse (3) ** 38.0 ° C 20 seconds-Rinse (4) ** 38.0 ° C 30 seconds 121mL * Replenishment amount per 1 m ^{2 of} photosensitive material ** Rinse phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. (3) The rinsing liquid is taken out of the rinse (3) and sent to a reverse osmosis membrane module (RC50D) by a pump. The permeated water obtained in the tank is supplied to the rinse (4), and the concentrated water is returned to the rinse (3). The pump pressure was adjusted so that the amount of permeated water to the reverse osmosis module was maintained at 50 to 300 ml / min, and the temperature was circulated for 10 hours a day. (Rinsing was carried out in a tank countercurrent system from (1) to (4).)

The composition of each processing solution is as follows. [Color developer] [Tank solution] [Replenisher] Water 800 mL 800 mL Dimethylpolysiloxane-based surfactant 0.1 g 0.1 g (Silicone KF351A / Shin-Etsu Chemical Co., Ltd.) Tri (isopropanol) amine 8.8 g 8.8 g Ethylenediaminetetraacetic acid 4.0 g 4.0 g polyethylene glycol (molecular weight 300) 10.0 g 10.0 g 4,5-dihydroxybenzene-1,3-disulfonate sodium 0.5 g 0.5 g potassium chloride 10.0 g-potassium bromide 0.040 g 0.010 g Triazinylaminostilbene-based fluorescent whitening agent (Hakkol FWA-SF / Showa Kagaku) 2.5 g 5.0 g Sodium sulfite 0.1 g 0.1 g Disodium-N, N-bis 8.5 g of (sulfonatoethyl) hydroxylamine 1 g N-ethyl-N- (β-methanesulfonamidoethyl) -3-methyl-4-amino-4-aminoaniline / 3/2 sulfuric acid monohydrate 5.0 g 15.7 g potassium carbonate 26.3 g 26.3 g Water is added and 1000 mL 1000 mL pH (adjusted at 25 ° C./potassium hydroxide and sulfuric acid) 10.15 12.50

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 700 mL 600 mL Iron (III) ammonium ethylenediaminetetraacetate 47.0 g 94.0 g 1.4 g ethylenediaminetetraacetic acid 2.8 g m-Carboxybenzene fulphinic acid 8 0.3 g 16.5 g nitric acid (67%) 16.5 g 33.0 g imidazole 14.6 g 29.2 g ammonium thiosulfate (750 g / l) 107.0 mL 214.0 mL ammonium sulfite 16.0 g 32.0 g ammonium bisulfite 23.1 g 46.2 g Water is added to the mixture. 1000 mL 1000 mL pH (adjusted at 25 ° C./acetic acid and ammonia) 6.0 6.0

[Rinse solution] [Tank solution] [Replenishment solution] Chlorinated sodium isocyanurate 0.02 g 0.02 g Deionized water (conductivity of 5 μS / cm or less) 1000 mL 1000 mL pH 6.5 6.5

The samples (101) to (1) subjected to the above treatment
For 15), the yellow color density was measured. Fog is determined by the lowest color density of the sample, and sensitivity is defined by the reciprocal of the exposure required to obtain a color density of fog +1.0,
The sensitivity was expressed as a relative value when the sensitivity of the developed sample (101) was defined as 100. Table 3 shows the relative sensitivity of each sample.

[0164]

[Table 3]

From Table 3, it can be seen that the emulsion using the dopant of the present invention has less desensitization upon exposure to light for 10 seconds than the emulsion using the known dopant, and is excellent in high illuminance reciprocity characteristics.

Example 2 "Emulsion 2-1; Preparation of Cubic Silver Chloride Sample (2)" (Comparative Example) In the preparation method of emulsion 1-1 described in Example 1, N,
Grain formation was carried out in exactly the same manner as in the preparation of Emulsion 1-1, except that N′-dimethylimidazolidin-2-thione (1% aqueous solution) was not added and the temperature of the reaction solution was 55 ° C. , Average particle size 0.38 mm (coefficient of variation is 8
%) Of a silver chloride cubic emulsion. Further, a gold sensitizer (gold (I) tetrafluoroborate bis (1,4,5-trimethyl-1,2,4-triazolium-3-thiolate)) was added to the emulsion at 2.4 × 10 ^-5 mol / mol. Ag, sulfur sensitizer (sodium thiosulfate) 1 × 10 ⁻⁷ mol / mol Ag, green-sensitive spectral sensitizing dyes (D, E and F) 3.6 × 10 ⁻⁴ mol / mol Ag, 7.0 × 10 ⁻⁵ mol / mol Ag and 2.8 × 1
^0-4 mol / mol Ag was added, and the mixture was optimally subjected to chemical sensitization and spectral sensitization at 60 ° C, and further 1- (5-methylureidophenyl) -5-mercaptotetrazole 4.4 × 10 ^-4.
Emulsion 2-1 was obtained by adding mol / mol Ag.

"Emulsion 2-2: Preparation of Cubic Silver Chloride Sample Doped with [IrCl ₆ ] ^3- " (Comparative Example) Emulsion 2-1 was prepared by adding hexachloroiridium 92-9
Emulsion 2-2 was prepared in the same manner as Emulsion 2-1 except that 4 × 10 ⁻⁸ mol was added to the amount of silver added to the emulsion in the 7% layer.

[Emulsion 2-3, 2-4; [IrCl_Five (H
_Two O)]^2-, [IrCl_Five (Thiazole)]^2-Dope
Preparation of Cubic Silver Chloride Sample ”(Comparative Example) Pentachloroaquoiridium or
Or pentachloro (thiazole) iridium in 92-9
The amount of silver added to the emulsion in the 7% layer was 2 × 10 ^-6Morma
Or 6 × 10^-7Emulsion except that each mole was added
Emulsions 2-3 and 2-4 were prepared in the same manner as 2-1.

[Emulsion 2-5, 2-6; [IrBr ₅ (H
Preparation of Cubic Silver Chloride Sample Doped with ₂ O)] ^2- and [IrBr ₅ (OCN)] ^3- (Invention) Pentabromoaquoiridium or pentabromoisocyanatoiridium was added to emulsion 2-1. Emulsions 2-5 and 2-6 were prepared in the same manner as Emulsion 2-1 except that 1 × 10 ^-7 mol was added to the silver added to the emulsion in a layer of 92 to 97% of the grain volume from the center of the grain. Was prepared.

"Emulsion 2-7; [IrBr ₃ Cl ₂ (H ₂
O)] ^{2-Preparation} of Doped Cubic Silver samples chloride "(the emulsion of the present invention) Emulsion 2-1 was added to the emulsion from 92 to 97% layer of particles central portion tribromometoxy dichloro aquo iridium grain volume Emulsion 2-7 was prepared in the same manner as Emulsion 2-1 except that 1 × 10 ⁻⁶ mol was added to the silver amount.

[0171]; the "Emulsion _{2-9 [IrBr 5 (N (CN} ) 2)] 2- Preparation of doped silver cubic samples chloride" (present invention) The emulsions 2-1, Pentaburomo (dicyanamide) iridium Emulsion 2-9 was prepared in the same manner as Emulsion 2-1 except that 3 × 10 ⁻⁷ mol was added to the layer of 92-97% of the grain volume from the central part of the grain with respect to the amount of silver added to the emulsion. .

[Emulsion 2-10, 2-11; [IrBr_Five(2,5-
Dichloro-1,3,4-thiadiazole)] ^2-, [IrBr_Five(2-black
Ro-5-fluoro-1,3,4-thiadiazole)]^2-Dope
Preparation of Cubic Silver Chloride Sample ”(Invention) Pentabromo (2,5-dichloro-1,
3,4-thiadiazole) iridium or pentabromo (2
-Chloro-5-fluoro-1,3,4-thiadiazole) iridi
From the center of the particle to the 92-97% layer by particle volume
3 × 10 with respect to the amount of silver added to the agent^-7, 6 × 1
0^-7Emulsion as in Emulsion 2-1 except that mol was added.
2-10 and 2-11 were prepared.

“Emulsion 2-12; Preparation of Cubic Silver Chloride Sample Doped with [IrBr ₅ (2,5-Difluoro-1,3,4-thiadiazole)] ^2- ” (Embodiment) Emulsion of Emulsion 2-1 Pentabromo (2,5-difluoro-
Same as Emulsion 2-1 except that 1,3,4-thiadiazole) iridium was added in an amount of 3 × 10 ^-7 mol based on the amount of silver added to the emulsion in a layer of 92 to 97% from the central part of the grain by grain volume. To prepare emulsion 2-12.

[Emulsion 2-13, 14, 15; [IrBr ₅ (H ₂ N
C (= S) NH ₂ )] ^2- , [IrBr ₅ (H ₂ NC (= NH) SCH ₃ )] ^2- , [IrBr ₅ (S = P
(NH ₂ ) ₂ (OH))] ^Preparation of ^2- Doped Cubic Silver Cube Samples ”
The emulsion of the (present invention) Emulsion _{2-1, [IrBr 5 (H 2} NC (= S) NH 2)] 2-, [IrBr 5
(H ₂ NC (= NH) SCH ₃ )] ²⁻ , [IrBr ₅ (S = P (NH ₂ ) ₂ (OH))] ²⁻ in a 92-97% layer from the center of the grain by grain volume to the emulsion 3 × 10 ⁻⁷ , 6 × 10 ⁻⁷ , 8 ×
Emulsions 2-13, 2-14 and 2-15 were prepared in the same manner as Emulsion 2-1 except that 10 ^-7 mol was added.

A sample (20) having exactly the same layer structure as in Example 1 except that the emulsion of the first layer was replaced with emulsions 2-1 to 2-15.
1) to (215) were produced. Example 1 for this sample
And the following experiment 2 was performed.

Experiment 2 Stability of Latent Image after Exposure The sensitometry was measured for each sample while changing the time from 1/10 second exposure to processing A, and the results were as follows. The sensitivity and the sensitivity at 30 minutes after the treatment were determined.

The results of these two experiments are shown in Table 4.

[0178]

[Table 4]

The emulsion of the present invention does not suffer from high illuminance failure between 10 seconds exposure and 10-4 seconds exposure, and gives the same sensitivity stably even when the time from exposure to processing is different (to improve the latent image stability). Excellent).

Example 3 Samples (301) to (315) were obtained by changing the layer structure of each sample of Example 2 as follows, and preparing thin samples. Experiment 1 of Example 1 and Experiment 2 of Example 2
As a result, similarly to the result of Example 2, the effect of the present invention was recognized even in the ultra-rapid processing of a thinned sample, and good results were obtained. The layer structure is shown in Sample (301), and Samples (302) to (315) are emulsion 2 of Sample (301).
1 was changed to emulsions 2-2 to 2-15, respectively.

Preparation of Sample 301 First layer (blue-sensitive emulsion layer) Emulsion 1-1 0.24 Gelatin 1.25 Yellow coupler (ExY) 0.57 Color image stabilizer (Cpd-1) 0.07 Color image stability Agent (Cpd-2) 0.04 Color image stabilizer (Cpd-3) 0.07 Color image stabilizer (Cpd-8) 0.02 Solvent (Solv-1) 0.21

Second layer (color mixture preventing layer) Gelatin 0.60 Color mixture inhibitor (Cpd-19) 0.09 Color image stabilizer (Cpd-5) 0.007 Color image stabilizer (Cpd-7) 0.007 UV absorber (UV-C) 0.05 Solvent (Solv-5) 0.11

Third layer (green-sensitive emulsion layer) Emulsion 2-1 0.14 Gelatin 0.73 Magenta coupler (ExM) 0.15 Ultraviolet absorber (UV-A) 0.05 Color image stabilizer (Cpd-2) ) 0.02 Color image stabilizer (Cpd-7) 0.008 Color image stabilizer (Cpd-8) 0.07 Color image stabilizer (Cpd-9) 0.03 Color image stabilizer (Cpd-10) 0 0.000 Color image stabilizer (Cpd-11) 0.0001 Solvent (Solv-3) 0.06 Solvent (Solv-4) 0.11 Solvent (Solv-5) 0.06

Fourth layer (color mixture prevention layer) Gelatin 0.48 Color mixture prevention layer (Cpd-4) 0.07 Color image stabilizer (Cpd-5) 0.006 Color image stabilizer (Cpd-7) 0.006 UV absorber (UV-C) 0.04 Solvent (Solv-5) 0.09

Fifth layer (red-sensitive emulsion layer) Emulsion 2-1 0.12 Gelatin 0.59 Cyan coupler (ExC-2) 0.13 Cyan coupler (ExC-3) 0.03 Color image stabilizer (Cpd- 7) 0.01 Color image stabilizer (Cpd-9) 0.04 Color image stabilizer (Cpd-15) 0.19 Color image stabilizer (Cpd-18) 0.04 Ultraviolet absorber (UV-7) 0 .02 Solvent (Solv-5) 0.09

Sixth layer (ultraviolet absorbing layer) Gelatin 0.32 Ultraviolet absorbing agent (UV-C) 0.42 Solvent (Solv-7) 0.08 Seventh layer (protective layer) Gelatin 0.70 Acrylic of polyvinyl alcohol Modified copolymer (degree of modification 17%) 0.04 Liquid paraffin 0.01 Surfactant (Cpd-13) 0.01 Polydimethylsiloxane 0.01 Silicon dioxide 0.003

Each of the manufactured samples was exposed in the same manner as in Experiment 1 of Example 1, and the color development was performed in the following development processing B
, Ultra-rapid processing was performed.

[Processing B] The above photosensitive material was processed into a roll having a width of 127 mm, and a minilab printer processor PP350 manufactured by Fuji Photo Film Co., Ltd. was modified so that the processing time and processing temperature could be changed. A photosensitive material sample is exposed imagewise from a negative film having an average density, and is subjected to continuous processing (running test) until the volume of the color developing replenisher used in the following processing steps becomes 0.5 times the volume of the color developing tank. Was.

Processing Step Temperature Time Replenishment amount * Color development 45.0 ° C. 15 seconds 45 mL Bleaching and fixing 40.0 ° C. 15 seconds 35 mL Rinse 1 40.0 ° C. 8 seconds-Rinse 2 40.0 ° C. 8 seconds-Rinse 3 ** 40.0 ° C for 8 seconds-Rinse 4 ** 38.0 ° C for 8 seconds 121 mL Drying 80 ° C for 15 seconds (Note) * Replenishment amount per 1 m ^{2 of} photosensitive material ** Use phosphorus screening system RC50D manufactured by Fuji Photo Film Co., Ltd. Attached to the rinse (3), the rinse liquid is taken out of the rinse (3) and sent to the reverse osmosis module (RC50D) by a pump. The permeated water sent in the tank is supplied to the rinse (4), and the concentrated liquid is returned to the rinse (3). Permeate volume to reverse osmosis module is 50-300mL
/ Min was maintained, and the temperature was circulated for 10 hours a day. Rinsing was performed in a 4-tank countercurrent system from (1) to (4).

The composition of each processing solution is as follows. [Color developing solution] [Tank solution] [Replenisher] Water 800 mL 600 mL Fluorescent brightener (FL-1) 5.0 g 8.5 g Triisopropanolamine 8.8 g 8.8 g Sodium p-toluenesulfonate 20.0 g 20 0.0 g ethylenediaminetetraacetic acid 4.0 g 4.0 g sodium sulfite 0.10 g 0.50 g potassium chloride 10.0 g-sodium 4,4,5-dihydroxybenzene-1,3-disulfonate 0.50 g 0.50 g disodium-N N-bis (sulfonatoethyl) hydroxylamine 8.5 g 4.5 g 4-amino-3-methyl-N-ethyl-N- (β-methanesulfonamidoethyl) aniline 3/2 sulfate monohydrate 10 0.0g 22.0g Potassium carbonate 26.3g 26.3g Water was added to make the total amount 1000m L 1000 mL pH (25 ° C, adjusted with sulfuric acid and KOH) 10.35 12.6

[Bleach-fixing solution] [Tank solution] [Replenisher] Water 800 mL 800 mL Ammonium thiosulfate (750 g / mL) 107 mL 14 mL Succinic acid 29.5 g 59.0 g Ethylene (III) ammonium ethylenediaminetetraacetate 47.0 g 94.0 g Ethylenediamine Tetraacetic acid 1.4 g 2.8 g Nitric acid (67%) 17.5 g 35.0 g Imidazole 14.6 g 29.2 g Ammonium sulfite 16.0 g 32.0 g Potassium metabisulfite 23.1 g 46.2 g Water was added and the total amount was 1000 mL. 1000mL pH (25 ° C, adjusted with nitric acid and ammonia water) 6.00 6.00

[Rinse solution] [Tank solution] [Replenisher] 0.02 g 0.02 g of chlorinated sodium isocyanurate Deionized water (conductivity 5 μs / cm or less) 1000 mL 1000 mL pH (25 ° C.) 6.5 6. 5 FL-1

[0193]

Embedded image

Example 4 Using the samples (301) to (315), an image was formed by laser scanning exposure. As a laser light source,
Semiconductor laser GaAlAs (oscillation wavelength 808.5n
m) as an excitation light source for a YAG solid-state laser (oscillation wavelength
946 nm) of LiNbO ₃ having an inverted domain structure.
473 nm extracted by wavelength conversion by SHG crystal
And a semiconductor laser GaAlAs (oscillation wavelength 808.
7 nm) as an excitation light source, and a YVO ₄ solid-state laser (oscillation wavelength 1064 nm) using a Li having an inversion domain structure.
Wavelength converted by NbO ₃ SHG crystal and extracted 5
32 nm and AlGaInP (oscillation wavelength about 680 n
m: Matsushita Densan type No. LN9R20). The laser light of each of the three colors was moved in a direction perpendicular to the scanning direction by a polygon mirror, so that the sample could be sequentially scanned and exposed. Fluctuations in light intensity due to the temperature of the semiconductor laser are suppressed by using a Peltier element to keep the temperature constant. The effective beam diameter is 8
0 μm, scanning pitch 42.3 μm (600 dpi)
And the average exposure time per pixel is 1.7 × 10
^-7 seconds.

After the exposure, the sample was subjected to a color development process B. As in the case of the high illuminance exposure in Example 2, the sample (304) of the present invention exhibited high sensitivity, and the image using laser scanning exposure was used. It was found to be suitable for forming.

(Synthesis Method of Complex) Example 5: Synthesis of Cs ₃ [IrBr ₅ (N (NC) ₂ )] 560 mg (0.64 mmol) of Cs ₂ [IrBr ₅ (H ₂ O)] and NaN (CN) ₂ 170mg
(1.91 mmol) was dissolved in 5.0 mL of water. Place the reaction solution in the dark,
After stirring at room temperature for 3 days, ethanol was added. The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried.
360 mg of crude crystals of the desired product were obtained. After dissolving the crude crystals in water, the purified product Cs ₃ [IrBr ₅ (N (NC) ₂ )] is added by adding ethanol.
328 mg (0.31 mmol) were obtained (49% yield). Elemental analysis value C ₂ N ₃ Br ₅ IrCs ₃ = 1056.49 Calculated value C 2.27, N 3.98, Br 37.82 (%) Observed value C 2.11, N 3.86, Br 38.01 (%)

[0197] Example _{6: K 2 [IrBr 5 (} 2,5- dichloro -
Synthesis of 1,3,4-thiadiazole)] 440 mg (0.64 mmol) of crude K ₂ [IrBr ₅ (H ₂ O)] and 300 mg (1.94 mmol) of 2,5-dichloro-1,3,4-thiadiazole in water 9
and 1 mL of dimethylacetamide. After the reaction solution was stirred at room temperature for 3 days in the dark, ethanol was added. The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. 253 mg of crude crystals of the desired product were obtained. After dissolving the crude crystals in water, ethanol is added to the purified K ₂ [IrBr
₅ (2,5-dichloro-1,3,4-thiadiazole)]
222 mg (0.27 mmol) were obtained (yield 42%). Elemental analysis value C ₂ Br ₅ Cl ₂ IrK ₂ N ₂ S = 824.94 Calculated value C 2.91, N 3.40, Br 48.43, Cl 8.60, S 3.89 (%) Observed value C 2.78, N 3.22, Br 48.67, Cl 8.35, S 3.58 (%)

Example 7: Synthesis of K ₂ [IrBr ₅ (2-chloro-5-fluoro-1,3,4-thiadiazole)] Crude K ₂ [IrBr ₅ (H ₂ O)] 440 mg (0.64 mmol) 2-chloro-5
-Fluoro-1,3,4-thiadiazole 267 mg (1.92 mm
ol) was dissolved in 9 mL of water and 1 mL of dimethylacetamide. After the reaction solution was stirred at room temperature for 3 days in the dark, ethanol was added. The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. 280 mg of crude crystals of the desired product were obtained. After dissolving the crude crystals in water, ethanol is added to the purified K
The ₂ [I _{rBr 5} (2- chloro-5-fluoro-1,3,4-thiadiazole)] to give 202mg (0.25mmol) (39% yield). Elemental analysis _{C 2 Br 5 ClFIrK 2 N 2} S = 808.49 Calculated C 2.97 as, N 3.46, Br 49.42, Cl 4.39, S 3.97 (%) Found C 3.09, N 3.72, Br 49.14 , Cl 4.62, S 4.10 (%)

Example 8: Synthesis of K ₂ [IrBr ₅ (2,5-difluoro-1,3,4-thiadiazole)] 440 mg (0.64 mmol) of crude K ₂ [IrBr ₅ (H ₂ O)] 240 mg (1.97 mmol) of 5-difluoro-1,3,4-thiadiazole was added to water 9
and 1 mL of dimethylacetamide. After the reaction solution was stirred at room temperature for 5 days in the dark, ethanol was added. The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. 281 mg of crude crystals of the desired product were obtained. After dissolving the crude crystals in water, ethanol is added to the purified K ₂ [IrBr ₅
(2,5-difluoro-1,3,4-thiadiazole)]
177 mg (0.22 mmol) was obtained. (35% yield). Elemental analysis value: C ₂ Br ₅ F ₂ IrK ₂ N ₂ S = 792.03 Calculated value: C 3.03, N 3.54, Br 50.44, S 4.05 (%) Actual value: C 3.31, N 3.71, Br 50.19, S 4.22 (%)

[0200] Example _{9: K 2 [IrBr 5 (} NH 2 C (= S) NH 2)] of the synthetic crude _{K 2 [IrBr5 (H 2 O} )] 440mg (0.64mmol) and thiourea 146 mg (1.
91 mmol) was dissolved in 4.5 mL of water. After stirring the reaction solution at 80 ° C. for 1 hour, ethanol was added. The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. K ₂ [IrBr ₅ (N
_{H 2 C (= S) NH} 2)] was obtained 220mg (0.29mmol) (46% yield). Elemental analysis value CH ₄ Br ₅ IrK ₂ N ₂ S = 746.06 Calculated values H 0.54, C 1.61, N 3.75, Br 53.55, S 4.30 (%) Observed values H 0.62, C 1.73, N 3.90, Br 53.31, S 4.55 (%)

Example 10: Cs ₂ [IrBr ₅ (NH ₂ C (= NH) SCH ₃ )]
560 mg (0.64 mmol) of Cs ₂ [IrBr ₅ (H ₂ O)] and 270 mg (0.97 mmol) of S-methylthiourea sulfate were dissolved in 4.5 mL of water. After stirring the reaction solution at 80 ° C. for 1 hour, ethanol was added.
The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried. 281 mg of crude crystals of the desired product were obtained. After dissolving the crude crystals in water, ethanol is added for crystallization, and purified K ₂ [IrBr ₅ (NH ₂ C
(= NH) SCH ₃ )] (214 mg, 0.40 mmol) (61% yield). Elemental analysis value C ₂ H ₆ Br ₅ IrK ₂ N ₂ S = 760.08 Calculated value H 0.80, C 3.16, N 3.69, Br 33.0, S 4.22 (%) Observed value H 0.88, C 3.31, N 3.85, Br 32.7, S 4.43 (%)

Example 11: Synthesis of Cs ₂ [IrBr ₅ (S = P (NH ₂ ) ₂ (OH)] Cs ₂ [IrBr ₅ (H ₂ O)] 376 mg (0.43 mmol) and S = P (NH ₃ ) ₃ 150mg
(1.35 mmol) was dissolved in 3.0 mL of water. Place the reaction solution in the dark,
After stirring at room temperature for 3 days, ethanol was added. The precipitated solid was collected by filtration, washed with water and EtOH, and air-dried.
213 mg (0.22 mmol) of Cs ₂ [IrBr ₅ (S = P (NH ₂ ) ₂ (OH)] was obtained (51% yield) Elemental analysis value Calculated value as Br ₅ Cs ₂ H ₅ IrN ₂ OPS = 969.64 H 0.52, N 2.89, Br 41.20, S 3.31 (%) Actual measured values H 0.61, N 3.03, Br 40.97, S 3.42 (%)

[0203]

According to the present invention, by using a dopant having a sustained release time adapted to the exposure illuminance required by the emulsion, reciprocity failure can be achieved without deteriorating the latent image preservability over a wide range of exposure illuminance. No emulsion could be obtained.

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Tadanobu Sato 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H023 BA02 4G048 AA01 AA06 AB02 AC08 AE06

Claims (9)

[Claims] 1. A silver halide emulsion comprising an iridium complex having at least one bromide ion represented by the following general formula as a ligand. In the general formula I [IrBr _n L _m ] ^l , L represents an inorganic ligand other than Br, and may be monodentate or polydentate with iridium as the central metal. n represents an integer of 1 to 5, and m represents an integer of 1 to 5. l represents an integer from +3 to -8. 2. In the iridium complex, n is 3, 4
2. The silver halide emulsion according to claim 1, wherein 5, m is 1, 2 or 3, and l is an integer from +1 to -3. 3. The silver halide emulsion according to claim 1, wherein the iridium complex is represented by the following general formula II. Formula _{II [IrBr x L '(6} -x)] ^y in formula, L' represents a fluoride ion, a chloride ion. x
Represents an integer from 1 to 5, and y represents -2 or -3. 4. The silver halide emulsion according to claim 1, wherein the iridium complex is represented by the following general formula III. General formula III [IrBr _a Cl _(ba) L ″ _c ] ^{d In the} formula, L ″ represents an arbitrary inorganic ligand, and can be monodentate or polydentate with iridium as a central metal. Is also good.
a is an integer from 1 to 4; b is 4 or 5;
b and c represent 1 or 2. d represents an integer from +1 to -3. 5. The silver halide emulsion according to claim 1, wherein said iridium is trivalent. 6. The time required for electrons trapped at the center of iridium by light irradiation to be released from iridium is 10 ^−4.
The silver halide emulsion according to any one of claims 1 to 5, wherein the time is from 10 seconds to 10 seconds. 7. A silver halide emulsion containing an iridium complex having at least one bromide ion represented by the following general formula IV as a ligand. In the general formula ^{_{IV [IrBr 6-p L 1}} p] r formula, L ¹ is pyrrole, thiophene, pyrazoles, isoxazoles include, isothiazoles, imidazoles, oxazoles, furazan compound, or a nitrogen atom, an oxygen Contains at least three atoms selected from atoms and sulfur atoms, has five or less carbon atoms, and may contain other atoms, and may further contain (number of carbon atoms) / (number of nitrogen atoms + number of oxygen atoms + sulfur atom Number) is less than 0.5. The central metal, iridium, may be monodentate or polydentate. p represents an integer of 1 to 3. r is 0
Represents an integer from to -3. 8. A metal complex represented by the following general formula V. Formula V N _k [IrBr _{6-p ′} L ² _{p ′} ] (wherein N represents a counter cation. _K represents the number of counter cations required for neutralizing the charge of the complex salt. L ² represents a nitrogen atom, oxygen It contains three or more atoms selected from atoms or sulfur atoms, has five or less carbon atoms, may contain other atoms, and may further contain (number of carbon atoms) / (number of nitrogen atoms + number of oxygen atoms + sulfur atom Number) is less than 0.5, and p ′ represents an integer of 1 or 2.) 9. The method for producing a metal complex according to claim 1, wherein the metal complex represented by the general formula A is used as a raw material. General formula A N ¹ _{k ′} [IrBr _6-q (H ₂ O) _q ] (wherein N ¹ represents a counter cation. K ′ represents the number of counter cations necessary for neutralizing the charge of the complex salt. 1
Or an integer of 2. )