JP2003270753A - Silver halide photographic sensitive material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having enhanced sensitivity. <P>SOLUTION: The silver halide photographic sensitive material contains at least two compounds represented by formula (I) in which the structure of D<SB>1</SB>, D<SB>2</SB>or La is different from each other. In the formula, D<SB>1</SB>and D<SB>2</SB>are each a dye chromophore; La is a linking group; q and r are each an integer of 1-100; M is a counter ion equilibrated with an electric charge; and m is a number required to neutralize electric charges in each molecule. <P>COPYRIGHT: (C)2003,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] FIELD OF THE INVENTION This invention relates to spectrally sensitized halos.
Silver halide photographic emulsion and photographic light-sensitive material using the same
To do. [0002] Conventionally, silver halide photographic light-sensitive materials
Great efforts have been made to increase sensitivity. halogen
In silver halide photographic emulsion, adsorbed on the surface of silver halide grains
The absorbed sensitizing dye absorbs the light incident on the photosensitive material and
Sensitive by transferring the energy to silver halide grains
Sex is obtained. Therefore, for spectral sensitization of silver halide
Light per unit surface area of silver halide grains
Transmitted to silver halide by increasing the absorption rate
Light energy can be increased, and spectral sensitivity
High sensitivity is expected to be achieved. Silver halide grains
In order to improve the light absorption rate of the surface, the unit particle surface area
What is necessary is just to increase the adsorption amount of the spectral sensitizing dye. Shi
However, the amount of sensitizing dye adsorbed on the surface of silver halide grains
Limited and more than single layer saturated adsorption (ie single layer adsorption)
It is difficult to adsorb other dye chromophores. Therefore,
Incident light of individual silver halide grains in the spectral sensitization region
The quantum absorptivity is still low. It has been proposed as a method for solving these problems.
The following is described. PB Gilman Juni
P. B. Gilman, Jr. et al.
Rafic Science and Engine Nearing
(Photographic Science and
  (Engineering) Vol. 20, No. 3, p. 97
(1976) Adsorption of cationic dye in the first layer
In the second layer, an anionic dye is absorbed by electrostatic force.
It states that it was put on. GG Bird (GB)
Bird) et al. In US Pat. No. 3,622,316.
Multiple layers of dyes on silver halide
Forster-type excitation energy transfer contribution
It has been sensitized by. Sugimoto et al. Disclosed JP-A-63-138,341.
, And 64-84, 244
Spectral sensitization by energy transfer from R
・ R. Steiger et al.
Fick Science and Engine Nearing
(Photographic Science and
  (Engineering) Vol. 27, No. 2, p. 59
(1983), gelatin-substituted cyanine dyes
State that they tried spectral sensitization by energy transfer.
Yes. Ikekawa et al., In Japanese Patent Laid-Open No. 61-251842
Energy transfer from cyclodextrin substituted dyes
Spectral sensitization was performed. Also, Richard Parton
Et al., European Patent 0985964A1, European Patent 0985
965A1, European Patent 0985966A1, European Patent 0
985965A1 with cationic dyes and anio
Multi-layer adsorption by combination of two or more dyes, two layers
Sensitization by energy transfer from eye pigment to one eye pigment
States that they have tried. However, these methods actually do halo
The degree of multilayer adsorption of sensitizing dyes on the surface of silver halide grains is insignificant.
It was sufficient and the effect of improving sensitivity was extremely small. Yamashita et al. In Japanese Patent Application Laid-Open No. 10-239789.
Multilayer absorption by cationic and anionic dyes containing aromatic groups
We realized wearing and made high sensitivity. Two separate, not conjugated, covalent bonds
So-called linked dyes with linked chromophores are halogenated.
A dye portion that is not adsorbed on silver halide and a dye portion that is adsorbed
Can be accessed by covalent bonds, so efficiency
Thoroughly enhances sensitivity by transmitting light absorption energy to silver halide
Promising to improve the stability of the second layer dye
It is a simple method. Concerning connecting dyes, for example, US Pat.
393,351, 2,425,772, 2,5
18,732, 2,521,944, 2,59
2,196, European Patent 565,083, etc.
It is. However, these are aimed at improving the light absorption rate
It wasn't. It is intended to actively improve the light absorption rate
G.B.Bird, A.
El Boror et al. US Patent
Nos. 3,622,317 and 3,976,493
A linked sensitizing dye having a plurality of cyanine chromophores
Adsorbing the child to increase the light absorption rate,
Increased sensitivity. Ukai, Okazaki, and Sugimoto
In 4-91134, at least two sulfo groups
And / or substantially non-adsorptive
Of the anine, merocyanine, and hemicyanine dyes
At least one spectral enhancement that can be adsorbed on silver halide
Proposed to bind to dyes. Also, L. C. Bishwakarma (L.
C. Vishwakarma) is disclosed in JP-A-6-57235.
No. 2 linked by dehydration condensation reaction of two dyes
The method of synthesizing the dye was shown. Further, JP-A-6-27
In 578, monomethine cyanine and pentamethine
Oxonol linking dye showed red sensitivity
In this case, however, the weight of oxonol emission and cyanine absorption
Unusual, Forster-type excitation energy between dyes
-No spectral sensitization by migration,
Sensitivity is not expected due to the light condensing action. In addition, MR Roberts (M.R.
Roberts) et al., US Pat. No. 4,950,587.
Proposed spectral sensitization to become cyanine dye polymer
did. Further, R.L. Parton (RL)
Parton et al. In European Patent No. 887,770A1.
The merocyanine dye contains a heteroatom in the cyanine dye
We reported high sensitization with compounds linked by linking groups.
The effect of improving light absorption was not sufficient. In these methods, they are adsorbed on silver halide.
Efficient light absorption from the undyed dye part to the adsorbed dye part
Inability to transmit energy and sufficient sensitivity
The current situation is not done. We are dedicated to research
As a result, two types of dyes with different structures were absorbed in the silver halide.
We found that it can be enhanced by wearing. [0013] The present invention has a different structure.
By adsorbing two types of dyes to silver halide
Halogens containing sensitized silver halide photographic emulsions
It is to provide a silver halide photographic light-sensitive material. [0014] Means for Solving the Problems (1) The following general formula (I)
In the compound represented by D₁, D₂Or L_aThe structure of
Characterized by comprising at least two different compounds
Silver halide photographic material. Formula (I) [0015] [Chemical 2] Where D₁And D₂Represents a dye chromophore. La
Represents a linking group. q and r are each an integer from 1 to 100
Represents. M represents a charge balanced counter ion, m represents the charge of the molecule
Represents the number required to neutralize. (2) To the compound represented by the general formula (I) described in (1)
Including at least two compounds having different La structures
The silver halide photographic light-sensitive material as described in (1)
material. (3) To the compound represented by the general formula (I) described in (1)
Containing at least two compounds having different lengths of La
The silver halide photographic light-sensitive material as described in (1)
material. (4) The compound represented by the general formula (I) described in (1)
However, there are few compounds where the difference in the length of La differs by 3 mm or more.
Halogen as described in (1), characterized in that both are included
Silver halide photographic material. (5) The compound represented by the general formula (I) described in (1)
D₂Including at least two compounds having different structures
(1), (2), (3) or (4)
The silver halide photosensitive material as described. (6) The compound represented by the general formula (I) described in (1)
D₂Containing at least two different compounds
Characteristic (1), (2), (3), (4) or
(5) The silver halide photographic light-sensitive material described in (5). (7) The compound described in (1) on the surface of the silver halide grain
The dye chromophore is adsorbed in multiple layers
(1), (2), (3), (4), (5), or
(6) The silver halide photographic light-sensitive material according to any one of (6). (8) Spectral absorption maximum wavelength is less than 500nm and light absorption intensity is 5
Light absorption is strong at 0 or more, or spectral absorption maximum wavelength is 500nm or more
Characterized by containing silver halide grains having a degree of 70 or more
(1), (2), (3), (4), (5),
(6) or the silver halide according to any one of (7)
Photosensitive material. (9) (1), (2), (3),
(4), (5), (6), (7), or (8)
Silver halide grains in the silver halide photographic light-sensitive material of
The maximum value of the spectral absorptance due to the dye chromophore in the first layer of the child is A1.
max The maximum spectral absorptance due to the dye chromophore in the second and subsequent layers
The value is A2max, the dye chromophore of the first layer of silver halide grains
The maximum spectral sensitivity due to S1max, coloring of the second and subsequent layers
When the maximum value of the spectral sensitivity by the group is S2max, A1max
And A2max or S1max and S2max are 400 to 500n
m, or 500 to 600 nm, or 600 to 70
Be in the range of 0 nm or 700 to 1000 nm
Features (1), (2), (3), (4), (5),
(6), (7), or halo according to any of (8)
Silver halide photographic material. (10) (1), (2), (3), (4), (5),
(6) Halogen according to (7), (8) or (9)
For silver halide photographic materials, the maximum value of spectral absorptance is
x, Amax or Smax when the maximum value of spectral sensitivity is expressed as Smax
The longest wavelength showing 50% spectral absorption of 460 nm
510 nm, or 560 nm to 610 nm, or 640
(1), characterized by being in the range of nm to 730 nm
(2), (3), (4), (5), (6), (7),
(8) The silver halide copy as described in either (9)
True photosensitive material. (11) (1), (2), (3), (4), (5),
(6), (7), (8), (9) or (10)
Of silver halide grains in silver halide photographic materials
The excitation energy of the dye chromophore after the second layer
Energy transfer to more than 10% efficiency
(1), (2), (3), (4),
(5), (6), (7), (8), (9) or (1
0) The silver halide photographic light-sensitive material according to any one of 0). (12) The compound represented by the general formula (I) described in (2)
In D₁Is a compound that forms a J-aggregate
(1), (2), (3), (4),
(5), (6), (7), (8), (9), (10)
Or the silver halide photographic light-sensitive material according to any one of (11)
material. (13) It is represented by the general formula (I) described in (2).
D having a different structure₁Mixed
Including a compound that forms a J-aggregate
(12). (14) (1), (2), (3), (4), (5),
(6), (7), (8), (9), (10), (1
Silver halide copy according to 1), (12) or (13)
In a true photosensitive material, a silver halide photograph in the photosensitive material
The emulsion has a tabular grain surface area with an aspect ratio of 2 or greater.
50% or more of the surface area of all silver halide grains in the agent
(1), (2),
(3), (4), (5), (6), (7), (8),
(9), (10), (11), (12) or (13)
The silver halide photographic light-sensitive material according to any one of the above. (15) (1), (2), (3), (4), (5),
(6), (7), (8), (9), (10), (1
1), (12), (13) or (14)
In a silver halide photographic light-sensitive material, a halo in the light-sensitive material
Silver photographic emulsion is characterized by selenium sensitization
(1), (2), (3), (4), (5),
(6), (7), (8), (9), (10), (1
1), any one of (12), (13) or (14)
The silver halide photographic light-sensitive material described. (16) (1), (2), (3), (4), (5),
(6), (7), (8), (9), (10), (1
1), (12), (13), (14) or (15)
Silver halide grains of the silver halide photographic light-sensitive material described
Has a silver halide adsorbing compound other than a sensitizing dye
(1), (2), (3), (4),
(5), (6), (7), (8), (9), (10),
(11), (12), (13), (14) or (1
5) The silver halide photographic light-sensitive material described in any one of 5). (17) (1), (2), (3), (4), (5),
(6), (7), (8), (9), (10), (1
Silver halide copy according to 1), (12) or (13)
In a true photosensitive material, a silver halide photograph in the photosensitive material
The emulsion has a tabular grain surface area with an aspect ratio of 2 or greater.
50% or more of the surface area of all silver halide grains in the agent
(1), (2),
(3), (4), (5), (6), (7), (8),
(9), (10), (11), (12) or (13)
The silver halide color photographic light-sensitive material according to any one of the above. [0019] DETAILED DESCRIPTION OF THE INVENTION The present invention will be described in detail below.
The The present invention adsorbs two or more dyes having different structures.
High sensitivity silver halide photographic materials.
The In the present invention, two or more dye chromophores
(Hereinafter referred to as a linking dye).
Next, a compound containing two or more dye chromophores used in the present invention.
Explain things. The compound is preferred as a sensitizing dye
Can be used. Preferred as these chromophores
Or D described later₁, D₂The same thing is mentioned.
Also, even though these dye chromophores are the same,
However, it is preferably different. The
The number of dye chromophores contained in the compound should be two or more
Any number can be used, but preferably 2 to 10,000.
2 to 1000, more preferably 2 to 10
0, more preferably 2 to 10, more preferably 2 to
5, more preferably 2, 3 and most preferably 2.
The In the compound, two or more dye chromophores are shared
Linked by a bond or a coordinate bond,
This is the case where they are connected with a bond. In addition, the compound
In this case, the covalent bond or the coordinate bond is formed in advance.
In the process of making a silver halide photosensitive material (for example, halo
In a silver halide emulsion). The latter method
For example, for example, the method described in JP-A-2000-81678
Can be used. Preferably the bond is preformed
This is the case. Preferred linking dyes are those represented by the general formula
It is a compound represented by (I). First, the group used in the present invention will be described.
This will be described in detail. In the present invention, a specific portion is referred to as a “group”.
The part is not itself replaced
Even with one or more (up to the maximum possible) substituents
Means that may have been. For example, "alkyl
“Group” means a substituted or unsubstituted alkyl group. Ma
In addition, the substituents that can be used in the compounds of the present invention are substituted
Any substituent may be used regardless of the presence or absence of. When such a substituent is W, it is represented by W.
Any substituent may be used, and particularly limited.
For example, a halogen atom, an alkyl group [(
Loalkyl group, bicycloalkyl group, tricycloalkyl
Alkenyl group (cycloalkenyl)
Groups, including bicycloalkenyl groups), alkynyl groups, and
To include. ], Aryl group, heterocyclic group (heterocycle
Group), cyano group, hydroxyl group, nito
B group, carboxyl group, alkoxy group, aryloxy
Group, silyloxy group, heterocyclic oxy group, acyloxy
Group, carbamoyloxy group, alkoxycarbonyloxy
Si group, aryloxycarbonyloxy group, amino group
(Including anilino group), ammonio group, acylamino
Group, aminocarbonylamino group, alkoxycarbonyl
Amino group, aryloxycarbonylamino group, sulf
Amoylamino, alkyl and arylsulfonyl groups
Mino group, mercapto group, alkylthio group, arylthio
Group, heterocyclic thio group, sulfamoyl group, sulfo group,
Alkyl and arylsulfinyl groups, alkyl and ant
Arylsulfonyl group, acyl group, aryloxycarboni
Group, alkoxycarbonyl group, carbamoyl group, ant
And azo, imide, phosphino,
Sufinyl group, phosphinyloxy group, phosphinyl group
Mino group, phosphono group, silyl group, hydrazino group, urei
Group, boronic acid group (-B (OH)₂), Phosphato groups (-OPO (O
H)₂), Sulfato groups (-OSO_ThreeH) Other known substitutions
The group is given as an example. More specifically, W is a halogen atom (for example,
Fluorine atom, chlorine atom, bromine atom, iodine atom),
Alkyl group [[linear, branched, cyclic substituted or unsubstituted
Represents an alkyl group. They are alkyl groups (preferably
Is an alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl
, N-propyl, isopropyl, t-butyl, n-o
Cutyl, eicosyl, 2-chloroethyl, 2-cyanoe
Til, 2-ethylhexyl), cycloalkyl group (preferably
Or a substituted or unsubstituted cyclohexane having 3 to 30 carbon atoms.
Alkyl groups such as cyclohexyl, cyclopentyl
, 4-n-dodecylcyclohexyl), bicycloal
A kill group (preferably a substitution of 5 to 30 carbon atoms or
Unsubstituted bicycloalkyl group, ie, having 5 to 3 carbon atoms
One hydrogen atom removed from 0 bicycloalkane
Is a valent group. For example, bicyclo [1,2,2] hepta
N-2-yl, bicyclo [2,2,2] octane-3-
Yl) and tricyclo structures with more ring structures
Is. Alkyl groups in the substituents described below
(For example, an alkyl group of an alkylthio group)
Represents the intended alkyl group, but also alkenyl group, alkyl
Nyl group is also included. ], Alkenyl group [straight chain, minute
Represents a cyclic substituted or unsubstituted alkenyl group.
They are alkenyl groups (preferably having 2 to 30 carbon atoms).
Substituted or unsubstituted alkenyl groups such as vinyl,
Allyl, prenyl, geranyl, oleyl), cycloal
A kenyl group (preferably a substitution of 3 to 30 carbon atoms or
Is an unsubstituted cycloalkenyl group, that is, from 3 carbon atoms
Monovalent with 30 hydrogen atoms removed from cycloalkene
It is the basis of. For example, 2-cyclopenten-1-yl,
2-cyclohexen-1-yl), bicycloalkenyl
Group (substituted or unsubstituted bicycloalkenyl group, preferably
Or a substituted or unsubstituted bismuth having 5 to 30 carbon atoms.
Chloalkenyl group, that is, bicyclo with one double bond
It is a monovalent group with one hydrogen atom of the alkene removed.
For example, bicyclo [2,2,1] hept-2-ene-1
-Yl, bicyclo [2,2,2] oct-2-ene-4
-Yl). ], An alkynyl group (preferably
Preferably, the substituted or unsubstituted alkyl having 2 to 30 carbon atoms
Quinyl groups, such as ethynyl, propargyl, trimethyl
Rusilylethynyl group)], aryl group (preferably carbon
A substituted or unsubstituted aryl group of formula 6 to 30, for example
Phenyl, p-tolyl, naphthyl, m-chloropheny
, O-hexadecanoylaminophenyl), heterocyclic group
(Preferably 5 or 6 membered substituted or unsubstituted, good
One hydrogen source from an aromatic or non-aromatic heterocyclic compound
A monovalent group with the child removed, more preferably carbon
A 5- or 6-membered aromatic heterocyclic group of 3 to 30
The For example, 2-furyl, 2-thienyl, 2-pyrimidi
Nyl, 2-benzothiazolyl, 1-methyl-2-
Pyridinio, 1-methyl-2-quinolinio
An on-ring heterocyclic group may be used. ), Cyano group, hydroxy
Group, nitro group, carboxyl group, alkoxy group (preferred
Or a substituted or unsubstituted alkyl having 1 to 30 carbon atoms.
Coxy groups such as methoxy, ethoxy, isopropoxy
Si, t-butoxy, n-octyloxy, 2-methoxy
Ethoxy), an aryloxy group (preferably having 6 carbon atoms)
To 30 substituted or unsubstituted aryloxy groups, eg
For example, phenoxy, 2-methylphenoxy, 4-t-butyl
Tylphenoxy, 3-nitrophenoxy, 2-tetrade
Canoylaminophenoxy), silyloxy group (preferred
Or a silyloxy group having 3 to 20 carbon atoms such as
Limethylsilyloxy, t-butyldimethylsilyloxy
Ii) a heterocyclic oxy group (preferably having 2 to 3 carbon atoms)
0 substituted or unsubstituted heterocyclic oxy group, 1-phen
Nyltetrazol-5-oxy, 2-tetrahydropyra
Nyloxy), acyloxy groups (preferably formylio)
Xyl group, substituted or unsubstituted alkyl having 2 to 30 carbon atoms
Kill carbonyloxy group, substitution of 6 to 30 carbon atoms
Or an unsubstituted arylcarbonyloxy group such as
Lumiloxy, acetyloxy, pivaloyloxy,
Thearoyloxy, benzoyloxy, p-methoxyph
Enylcarbonyloxy), carbamoyloxy group (preferably
Preferably, a substituted or unsubstituted carbon having 1 to 30 carbon atoms.
Rubamoyloxy group, for example, N, N-dimethylcarba
Moyloxy, N, N-diethylcarbamoyloxy,
Morpholinocarbonyloxy, N, N-di-n-octy
Ruaminocarbonyloxy, Nn-octylcarbamo
Yloxy), alkoxycarbonyloxy group (preferred
Or substituted or unsubstituted alkoxy having 2 to 30 carbon atoms.
Sicarbonyloxy groups such as methoxycarbonyloxy
Si, ethoxycarbonyloxy, t-butoxycarboni
Ruoxy, n-octylcarbonyloxy), aryl
Oxycarbonyloxy group (preferably having 7 to 7 carbon atoms)
30 substituted or unsubstituted aryloxycarbonyls
An oxy group such as phenoxycarbonyloxy, p-
Methoxyphenoxycarbonyloxy, pn-hexa
Decyloxyphenoxycarbonyloxy), amino group
(Preferably an amino group, a C 1-30 substituent.
Or an unsubstituted alkylamino group having 6 to 30 carbon atoms.
Substituted or unsubstituted anilino groups such as amino, methyl
Ruamino, dimethylamino, anilino, N-methyl-ani
Lino, diphenylamino), ammonio groups (preferably
Ammonio group, substituted or unsubstituted having 1 to 30 carbon atoms
Ammonio substituted with alkyl, aryl or heterocycle
Groups such as trimethylammonio, triethylammo
Nio, diphenylmethylammonio), acylamino group
(Preferably a formylamino group having 1 to 30 carbon atoms
Substituted or unsubstituted alkylcarbonylamino group, charcoal
Substituted or unsubstituted arylcarbo having a prime number of 6 to 30
Nylamino groups such as formylamino, acetylamido
, Pivaloylamino, lauroylamino, benzoyl
Amino, 3,4,5-tri-n-octyloxypheny
Rucarbonylamino), aminocarbonylamino group (preferably
Preferably, it is a substituted or unsubstituted atom having 1 to 30 carbon atoms.
Minocarbonylamino, such as carbamoylamino,
N, N-dimethylaminocarbonylamino, N, N-di
Ethylaminocarbonylamino, morpholinocarbonyl
Amino), an alkoxycarbonylamino group (preferably
C2-C30 substituted or unsubstituted alkoxycal
A bonylamino group, for example, methoxycarbonylamino,
Ethoxycarbonylamino, t-butoxycarbonyla
Mino, n-octadecyloxycarbonylamino, N-
Methyl-methoxycarbonylamino), aryloxy
A carbonylamino group (preferably having 7 to 30 carbon atoms)
Substituted or unsubstituted aryloxycarbonylamino
Groups such as phenoxycarbonylamino, p-chloro
Enoxycarbonylamino, mn-octyloxyphene
Noxycarbonylamino), sulfamoylamino group
(Preferably substituted or unsubstituted having 0 to 30 carbon atoms
A sulfamoylamino group such as sulfamoyla
Mino, N, N-dimethylaminosulfonylamino, N-
n-octylaminosulfonylamino), alkyl and
Arylsulfonylamino group (preferably from 1 carbon atom)
30 substituted or unsubstituted alkylsulfonylamines
No, substituted or unsubstituted aryl having 6 to 30 carbon atoms
Sulfonylamino, such as methylsulfonylamino,
Butylsulfonylamino, phenylsulfonylamino,
2,3,5-trichlorophenylsulfonylamino, p
-Methylphenylsulfonylamino), mercapto group,
Alkylthio groups (preferably substituted with 1 to 30 carbon atoms)
Or an unsubstituted alkylthio group such as methylthio,
Ethylthio, n-hexadecylthio), arylthio group
(Preferably substituted or unsubstituted having 6 to 30 carbon atoms
Arylthio, such as phenylthio, p-chlorophene
Nylthio, m-methoxyphenylthio), heterocyclic thio
Group (preferably substituted or unsubstituted having 2 to 30 carbon atoms)
A heterocyclic thio group such as 2-benzothiazolylthio,
1-phenyltetrazol-5-ylthio), sulfa
Moyl group (preferably substituted with 0 to 30 carbon atoms or
Unsubstituted sulfamoyl groups such as N-ethylsulf
Amoyl, N- (3-dodecyloxypropyl) sulfur
Amoyl, N, N-dimethylsulfamoyl, N-ace
Tilsulfamoyl, N-benzoylsulfamoyl,
N- (N′-phenylcarbamoyl) sulfamoy
), Sulfo group, alkyl and arylsulfinyl group
(Preferably substituted or unsubstituted having 1 to 30 carbon atoms
Alkylsulfinyl group, substituted or unsubstituted 6 to 30
Substituted arylsulfinyl groups such as methylsulfinyl
Nyl, ethylsulfinyl, phenylsulfinyl, p
-Methylphenylsulfinyl), alkyl and aryl
A rusulfonyl group (preferably a substitution of 1 to 30 carbon atoms)
Or an unsubstituted alkylsulfonyl group, from 6 to 30
Substituted or unsubstituted arylsulfonyl groups such as meth
Rusulfonyl, ethylsulfonyl, phenylsulfoni
, P-methylphenylsulfonyl), acyl group (preferred
Or a formyl group, substituted or non-substituted with 2 to 30 carbon atoms
Substituted alkylcarbonyl groups, and those with 7 to 30 carbon atoms
Or an unsubstituted arylcarbonyl group having 4 to 3 carbon atoms
Bonded to a carbonyl group with zero substituted or unsubstituted carbon atoms
Combined heterocyclic carbonyl groups such as acetyl,
Pivaloyl, 2-chloroacetyl, stearoyl, ben
Zoyl, pn-octyloxyphenylcarbonyl,
2-pyridylcarbonyl, 2-furylcarbonyl), a
A reeloxycarbonyl group (preferably having 7 to 7 carbon atoms)
30 substituted or unsubstituted aryloxycarbonyls
Groups such as phenoxycarbonyl, o-chloropheno
Xyloxycarbonyl, m-nitrophenoxycarbonyl, p
-T-butylphenoxycarbonyl), alkoxycal
A bonyl group (preferably a C 2-30 substituent or
Is an unsubstituted alkoxycarbonyl group such as methoxy
Rubonyl, ethoxycarbonyl, t-butoxycarbonyl
, N-octadecyloxycarbonyl), carbamoy
(Preferably substituted or non-substituted with 1 to 30 carbon atoms)
Substituted carbamoyl, eg carbamoyl, N-methyl
Rucarbamoyl, N, N-dimethylcarbamoyl, N,
N-di-n-octylcarbamoyl, N- (methylsulf
Phonyl) carbamoyl), aryl and heterocyclic azo groups
(Preferably substituted or unsubstituted having 6 to 30 carbon atoms
Arylazo group, substituted or unsubstituted 3 to 30 carbon atoms
Substituted heterocyclic azo groups such as phenylazo, p-chloro
Rophenylazo, 5-ethylthio-1,3,4-thiadi
Azol-2-ylazo), an imide group (preferably N
-Succinimide, N-phthalimide), phosphino group
(Preferably substituted or unsubstituted having 2 to 30 carbon atoms
Phosphino groups such as dimethylphosphino, diphe
Nylphosphino, methylphenoxyphosphino), phos
A finyl group (preferably substituted with 2 to 30 carbon atoms)
Or an unsubstituted phosphinyl group such as phosphinyl,
Dioctyloxyphosphinyl, diethoxyphosphini
Or phosphinyloxy group (preferably having 2 carbon atoms)
30 substituted or unsubstituted phosphinyloxy groups,
For example, diphenoxyphosphinyloxy, dioctyl
Oxyphosphinyloxy), phosphinylamino group
(Preferably substituted or unsubstituted having 2 to 30 carbon atoms
Phosphinylamino group such as dimethoxyphosphite
Nylamino, dimethylaminophosphinylamino), pho
Phospho group, silyl group (preferably having 3 to 30 carbon atoms)
Substituted or unsubstituted silyl groups such as trimethyl
Ril, t-butyldimethylsilyl, phenyldimethylsilane
Ryl), a hydrazino group (preferably having 0 to 30 carbon atoms)
Substituted or unsubstituted hydrazino groups such as trimethyl
Ruhydrazino), ureido group (preferably having 0 carbon atoms)
30 substituted or unsubstituted ureido groups such as N, N
-Dimethylureido). In addition, the two Ws are combined to form a ring (aromatic,
Is a non-aromatic hydrocarbon ring or heterocyclic ring. These are more
Can be combined to form a polycyclic fused ring.
For example, benzene ring, naphthalene ring, anthracene ring,
Enanthrene ring, fluorene ring, triphenylene ring, na
Phthacene ring, biphenyl ring, pyrrole ring, furan ring, thi
Offen ring, imidazole ring, oxazole ring, thiazo
Ring, pyridine ring, pyrazine ring, pyrimidine ring,
Dazine ring, indolizine ring, indole ring, benzofura
Ring, benzothiophene ring, isobenzofuran ring, quino
Lysine ring, quinoline ring, phthalazine ring, naphthyridine
Ring, quinoxaline ring, quinoxazoline ring, isoquinoline
Ring, carbazole ring, phenanthridine ring, acridine
Ring, phenanthroline ring, thianthrene ring, chromene
Ring, xanthene ring, phenoxathiin ring, phenothiazi
Ring and phenazine ring. Forming)
You can also. Among the above substituents W, it has a hydrogen atom.
Are removed and further substituted with the above groups
Also good. Examples of such substituents include -CONHS
O₂-Group (sulfonylcarbamoyl group, carbonylsulfuryl group)
Famoyl group), -CONHCO- group (carbonyl cal)
Bamoyl group), -SO₂NHSO₂-Group (sulfonyls
Rufamoyl group). More specifically, a
Alkylcarbonylaminosulfonyl group (for example, acetyl
Ruaminosulfonyl), arylcarbonylaminosulfur
Phonyl group (for example, benzoylaminosulfonyl group),
An alkylsulfonylaminocarbonyl group (eg, methyl)
Rusulfonylaminocarbonyl), arylsulfonyl
An aminocarbonyl group (for example, p-methylphenylsulfur
Phonylaminocarbonyl). Next, a dye chromophore, D₁, D₂And La
Describe. Dye chromophore, D₁, And D₂Represented by
Any dye chromophore may be used. For example,
Cyanine dye, styryl dye, hemicyanine dye, melo
Cyanine dye, trinuclear merocyanine dye, tetranuclear merocyanine
Dye, rhodacyanine dye, complex cyanine color
Elementary, complex merocyanine dye, allopolar color
Element, oxonol dye, hemioxonol dye, squa
Lithium dye, Croconium dye, Azamethine dye, Bear
Phosphorous dye, arylidene dye, anthraquinone dye, toner
Riphenylmethane dye, azo dye, azomethine dye,
Pyro compound, metallocene dye, fluorenone dye, full
Gido dye, perylene dye, phenazine dye, phenothia
Gin dye, quinone dye, indigo dye, diphenyl meta
Dye, polyene dye, acridine dye, acridinone
Dye, diphenylamine dye, quinacridone dye, quino
Phthalon dye, phenoxazine dye, phthaloperylene color
Element, porphyrin dye, chlorophyll dye, phthalocyanine
Examples thereof include a nin dye and a metal complex dye. Preferably, cyanine dye, styryl color
Element, hemicyanine dye, merocyanine dye, trinuclear merosi
Anine dye, tetranuclear merocyanine dye, rhodacyanine color
Element, complex cyanine dye, complex melo
Cyanine dyes, allopolar dyes, oxonol dyes,
Hemioxonol dye, squalium dye, croconium
Examples include methine dye chromophores such as mu dye and azamethine dye
It is done. More preferably a cyanine dye or merocyanine
Dye, trinuclear merocyanine dye, tetranuclear merocyanine dye,
Oxonol dyes and rhodacyanine dyes.
Cyanine dyes, merocyanine dyes, oxonol
Particularly preferred are cyanine dyes and merocyanes.
Most preferably one is a cyanine dye.
One is the merocyanine dye. For details of these dyes, see F.E.
F.M.Harmer, `` Heterocyclic
Compound Soybean Soybean and Relaided
Heterocyclic Compounds-Cyanine Dyes a
nd Related Compounds) ", John Willie &
・ John Wiley & Sons-New York, Ron
Don, 1964, D.M. Sturmer (D.M.Stu
rmer) "Heterocyclic Compound Suspeci"
Topics in Heterocyclic Chemis
Tree (Heterocyclic Compounds-Special topics in he
terocyclic chemistry) ", Chapter 18, Section 14, Section 4
82-515, John Willie and Sons
(John Wiley & Sons)-New York, London, 1
Published in 977, “Rods Chemistry of Carbon”
・ Compods (Rodd's Chemistry of Carbon Compound)
s) "2nd. Ed. vol. IV, part B, 1977, Chapter 15, Chapter 3
69-422, Elsevier Science Public
Company Inc. (Elsevier Science Publishing
 Company Inc.), published in New York, etc.
Yes. Preferred general formulas of dyes include U.S. Pat.
994,051 pages 32 to 36, and
US Pat. No. 5,747,236, pages 30-34
The general formula is mentioned. Also preferred cyanine dyes, melo
General formula of cyanine dye and rhodacyanine dye
(XI), (XI of columns 21-22 of No. 5,340,694)
I), (XIII) (except for n12, n15,
The number of n17 and n18 is not limited and is an integer of 0 or more (preferably 4
The following)). In the present invention, it has a plurality of dye chromophores
As compounds, multiple dye chromophores are linked by covalent bonds
Any compound is acceptable as long as it is
Or a compound represented by the general formula (I). D of general formula (I) of the present invention<sub>1</sub>And D<sub>2</sub>Are the same
However, it is preferably a different case. D<sub>1</sub>And D<sub>2</sub>
Are different, the multilayer adsorption is as shown below.
Is preferable. In the present invention, it is represented by the general formula (I)
If the linking dye is adsorbed on the silver halide grains, D<sub>1</sub>
Adsorbs on silver halide and D<sub>2</sub>Absorbs directly into silver halide
A chromophore that is not worn is preferred. That is, D<sub>2</sub>Of silver into silver halide grains
Wear power is D<sub>1</sub>The weaker is preferable. In addition, halogen
The order of adsorption power to silver halide grains is D<sub>1</sub>> La> D<sub>2</sub>Become
The case is most preferable. As noted above, D<sub>1</sub>To silver halide grains
It is preferable that the sensitizing dye part has an adsorptive property of
Whether it is adsorbed by physical adsorption or chemical adsorption
I do not care. D<sub>2</sub>Is weakly adsorbed on silver halide grains
In addition, a luminescent dye is preferable. Luminescent dye seeds
For example, the skeleton structure of dyes used for dye lasers
Those having are preferred. These are, for example, Maeda Mitsuo,
Laser Research, Vol. 8, 694, 803, 958
(1980) and Volume 9, page 85 (1981), and
By F. Sehaefer, "Dye Lasers", Springer (197
(3 years). In addition, D<sub>1</sub>Silver halide photographic light-sensitive material
The absorption maximum wavelength in the inside is D<sub>2</sub>Longer than the absorption maximum wavelength of
A wavelength is preferred. In addition, D<sub>2</sub>The light emission of D<sub>1</sub>of
It is preferable to overlap with absorption. D<sub>1</sub>J-aggregate
It is preferable to form it. Furthermore, it is represented by the general formula (I)
Linking dyes have absorption and spectral sensitivity in the desired wavelength range
To do that, D<sub>2</sub>It is also preferable that J aggregates are formed
Good. D<sub>1</sub>And D<sub>2</sub>Is the reduction potential and oxidation potential of
D<sub>1</sub>The reduction potential of D is<sub>2</sub>Of reduction potential
It is preferable to be noble than the value obtained by subtracting 0.2V from the value.
That's right. La is a linking group (preferably a divalent linking group).
Represents. These linking groups also include single bonds.
To do. These linking groups are preferably single bonds or charcoal.
Less than elementary, nitrogen, sulfur and oxygen atoms
Both consist of atoms or atomic groups containing one species. Preferably
A alkylene group (eg methylene, ethylene, trimethyle)
, Tetramethylene, pentamethylene), arylene group
(Eg phenylene, naphthylene), alkenylene groups
(Eg, ethenylene, propenylene), alkynylene
Groups (eg ethynylene, propynylene), amide groups,
Ester group, sulfoamide group, sulfonate group,
Ureido group, sulfonyl group, sulfinyl group, thioate
Tell group, ether group, carbonyl group, -N (V<sub>a</sub>)-(V<sub>a</sub>
Represents a hydrogen atom or a monovalent substituent. With a monovalent substituent
For example, W described later can be given. ), A heterocyclic divalent group (for example,
6-chloro-1,3,5-triazine-2,4-di
Yl group, pyrimidine-2,4-diyl group, quinoxaline
One or more of -2,3-diyl groups)
Configured from 0 to 100 carbon atoms, preferably carbon
A linking group having a number of 1 to 20 is represented. The above linking group is further represented by the aforementioned W.
You may have a substituent. In addition, these linking groups are ring
Contains aromatic or non-aromatic hydrocarbon rings or heterocyclic rings)
You may do it. More preferably, the catalyst has 1 to 10 carbon atoms.
A alkylene group (eg methylene, ethylene, trimethyle)
, Tetramethylene, pentamethylene), 6 or more carbon atoms
Up to 10 arylene groups (eg phenylene, naphthylene)
), Alkenylene groups having 2 to 10 carbon atoms (for example,
Eg) ethenylene, propenylene), 2 or more carbon atoms
Up to 10 alkynylene groups (eg, ethynylene, propylene
Ropinylene), ether group, amide group, ester group,
One or more sulfoamide groups or sulfonic acid ester groups
A divalent valence of 1 to 10 carbon atoms composed of the above combination
The linking group of These are replaced by the aforementioned W
Also good. In the present invention, the length of La is D<sub>1</sub>And D<sub>2</sub>
The atoms connecting atoms, the bond distance between the atoms
It shall be expressed as the sum of At this time, D<sub>1</sub>And D<sub>2</sub>Bondage
It also includes the distance between the bond atom of the child and La. Configure La here
For the calculation of the sum of the bond distances between atoms
A atom to use<sub>n</sub>Represented by n is an integer from 1 to m. A <sub>1</sub>
Is D<sub>1</sub>A atom bonded to A<sub>m</sub>Is D<sub>2</sub>Bound to
Atom. 2 ≦ n ≦ m-1 A<sub>n</sub>Is all A<sub>n-1</sub>And A<sub>n +1</sub>In
Are connected. A<sub>n</sub>How many atoms are not used in the calculation?
May be combined. A<sub>n</sub>May be part of the ring. here,
A<sub>n</sub>When two or more kinds of choices are considered, atom-atom
When the sum of bond distances between them is calculated, the value is minimized
You have to choose like this. As the value of bond distance,
The Chemical Society of Japan, published by Maruzen in 1991, “Revised 3rd edition Chemical Handbook
Use the values listed in Table 15.12.
For example, C-C bond, C-N bond, and C-0 bond are each 1.541
Use Å, 1.48Å and 1.43Å. In the present invention, La represented by the general formula (I)
Preferably contain at least two compounds with different structures
More preferably, there are few compounds with different La lengths.
It is to contain at least two kinds. Contains two or more general formulas (I)
The shortest length of La among the represented compounds is expressed as r<sub>a</sub>,most
The length of long La is r<sub>b</sub>Represented by 1.5Å <r<sub>b</sub>-R<sub>a</sub><100cm
More preferably, 3Å <r<sub>b</sub>-R<sub>a</sub><50
Å, more preferably 5 Å <r<sub>b</sub>-R<sub>a</sub><50cm, especially good
Preferably, 7Å <r<sub>b</sub>-R<sub>a</sub><20 cm. At this time, 2Å <r<sub>a</sub><50cm
More preferably, 4Å <r<sub>a</sub><30cm
Particularly preferably, 6Å <r<sub>a</sub><20 mm. Also, 3Å <r<sub>b</sub><100cm
More preferably, 10Å <r<sub>a</sub><60cm
Particularly preferably, 15Å <r<sub>a</sub><30 mm. Containing two or more general formulas (I)
D of a linking dye having the shortest La among the compounds represented<sub>1</sub>When
D<sub>2</sub>D<sub>1a</sub>And D<sub>2a</sub>Of linking dyes with the longest La
D<sub>1</sub>And D<sub>2</sub>D<sub>1b</sub>And D<sub>2b</sub>Represented by D<sub>2a</sub>Halogenation of
The maximum absorption wavelength in silver photographic materials is D<sub>2b</sub>Absorption pole
It is preferable that the wavelength is longer than the large wavelength. D<sub>1a</sub>
Absorption maximum wavelength in silver halide photographic materials
D<sub>2a</sub>It is preferable that the wavelength is longer than the absorption maximum wavelength of
Yes. La is a through-bond phase.
Even if energy transfer or electron transfer is performed by interaction
Good linking group. Tunnel for through-bond interaction
Interaction, super-exchange interaction, etc.
However, in particular, through-bond mutual interaction based on super-exchange interaction
The action is preferable. Through-bond interaction and super-exchange interaction
The effect is Shammai Speiser
Author, Chemical Review (Chem. Rev.) Vol. 96, Vol. 1960
-Interaction defined in 1963, 1996. This
Energy transfer or electron transfer by interactions like
As a connecting group, Shamai Spacer (Shammai
Speiser), Chemical Review (Chem. Rev.) 96th
Volume 1, 1967-1969, 1996 is preferred. Q and r are integers from 1 to 100.
The Preferably it is an integer from 1 to 5, more preferably
Is an integer of 1 to 2, particularly preferably 1.
a plurality of La included when q and r are 2 or more, and
D<sub>2</sub>Are different linking groups and dye chromophores,
Also good. La is D<sub>1</sub>And D<sub>2</sub>Even if it binds at any part of
Although it is good, it is preferably not a methine chain moiety. In general formula (I), the dye chromophores are each other.
It can be connected in any connection style.
It represents something. The dye of the general formula (I) has a total electric power of −1 or less.
Preferably with a load, more preferably -1 charge
This is the case. More preferably, in the general formula (I):
D<sub>1</sub>And D<sub>2</sub>Are independently represented by the following general formulas (II) and (II
When it is a methine dye represented by I), (IV), or (V)
is there. Formula (II) [0054] [Chemical 3] In the formula (II), L<sub>11</sub>, L<sub>12</sub>, L<sub>13</sub>, L<sub>14</sub>, L
<sub>15</sub>, L<sub>16</sub>, And L<sub>17</sub>Each represents a methine group. p<sub>11</sub>,
And p<sub>12</sub>Represents 0 or 1. n<sub>11</sub>Is 0, 1, 2, 3
Or 4. Z<sub>11</sub>And Z<sub>12</sub>Forms a nitrogen-containing heterocycle
Represents an atomic group necessary for the purpose. However, these rings are condensed
You may do it. M<sub>11</sub>Represents a charge balanced counter ion and m <sub>11</sub>
Represents a number of 0 or more necessary to neutralize the charge of the molecule.
R<sub>11</sub>And R<sub>12</sub>Are hydrogen atom, alkyl group, and aryl, respectively.
Represents a ruthenium group or a heterocyclic group. General formula (III) [0056] [Formula 4] In the formula (III), L<sub>18</sub>, L<sub>19</sub>, L<sub>20</sub>, And L<sub>twenty one</sub>
Each represents a methine group. p<sub>13</sub>Represents 0 or 1. q
<sub>11</sub>Represents 0 or 1. n<sub>12</sub>Represents 0, 1, 2, 3 or 4
The Z<sub>13</sub>Is the group of atoms required to form a nitrogen-containing heterocycle
Represents. Z<sub>14</sub>And Z<sub>14</sub>'(N-R<sub>14</sub>Q<sub>11</sub>Together with
Necessary to form a heterocyclic or acyclic acidic end group.
Represents an important atomic group. However, Z<sub>13</sub>And Z<sub>14</sub>And Z<sub>14</sub>To
The ring may be condensed. M<sub>12</sub>Represents a charge-balanced counterion
M<sub>12</sub>Is a number greater than or equal to zero required to neutralize the charge of the molecule
Represents. R<sub>13</sub>And R<sub>14</sub>Are hydrogen atom and alkyl respectively
Represents a group, an aryl group, or a heterocyclic group. Formula (IV) [0058] [Chemical formula 5] In the formula (IV), L<sub>twenty two</sub>, L<sub>twenty three</sub>, L<sub>twenty four</sub>, L<sub>twenty five</sub>, L
<sub>26</sub>, L<sub>27</sub>, L<sub>28</sub>, L<sub>29</sub>And L<sub>30</sub>Each represents a methine group
The p<sub>14</sub>And p<sub>15</sub>Represents 0 or 1, respectively. q<sub>12</sub>Is 0
Or 1 is represented. n<sub>13</sub>And n<sub>14</sub>Is 0, 1, 2, 3 or 4
Represent. Z<sub>15</sub>And Z<sub>17</sub>Each form a nitrogen-containing heterocycle
Represents an atomic group necessary for the purpose. Z<sub>16</sub>And Z<sub>16</sub>'(N-R
<sub>16</sub>Q<sub>12</sub>Necessary to form a heterocycle together with
Represents an atomic group. However, Z<sub>15</sub>, Z<sub>16</sub>And Z<sub>16</sub>'And Z<sub>17</sub>
The ring may be condensed. M<sub>13</sub>Charge balance counter ion
M<sub>13</sub>Is greater than zero required to neutralize the charge of the molecule
Represents a number. R<sub>15</sub>, R<sub>16</sub>And R<sub>17</sub>Are hydrogen atoms,
Represents an alkyl group, an aryl group, or a heterocyclic group; General formula (V) [0060] [Chemical 6] In the formula (V), L<sub>31</sub>, L<sub>32</sub>, And L<sub>33</sub>Is that
Represents a methine group. q<sub>13</sub>And q<sub>14</sub>Is 0 or 1 respectively
Represent. n<sub>15</sub>Represents 0, 1, 2, 3 or 4. Z<sub>18</sub>When
Z<sub>18</sub>'(N-R<sub>18</sub>Q<sub>13</sub>Together with and Z<sub>19</sub>
And Z<sub>19</sub>'(N-R<sub>19</sub>Q<sub>14</sub>Together with the heterocycle,
Or a group of atoms necessary to form an acyclic acidic end group
Represents. However, Z<sub>18</sub>And Z<sub>18</sub>'And Z<sub>19</sub>And Z<sub>19</sub>Ring to ‘
May be condensed. M <sub>14</sub>Represents a charge-balanced counterion
M<sub>14</sub>Is a number greater than or equal to zero required to neutralize the charge of the molecule
Represents. R<sub>18</sub>And R<sub>19</sub>Are hydrogen atom and alkyl respectively
Represents a group, an aryl group, or a heterocyclic group. D in the general formula (I)<sub>1</sub>Preferably, as above
In the case of methine dyes represented by general formulas (II), (III), and (IV)
And more preferably a methyl represented by the general formula (II)
This is the case for dyes. D in general formula (I)<sub>2</sub>As preferred
Is a methyl group represented by the above general formula (II), (III), or (V).
More preferably, the general formula (II),
This is the case of the methine dye represented by (III) and is particularly preferred.
Or a methine dye represented by the general formula (II). In the following, the general formulas (I), (II), (III), (I
V) and methine compounds represented by (V) are described in detail.
Bell. General formulas (II), (III), (IV) and (V)
Medium, Z<sub>11</sub>, Z<sub>12</sub>, Z<sub>13</sub>, Z<sub>15</sub>And Z<sub>17</sub>Is nitrogen-containing complex
To form a ring, preferably a 5- or 6-membered nitrogen-containing heterocycle
Represents an atomic group necessary for. However, when these rings are condensed
May be. As the ring, an aromatic ring or a non-aromatic ring
Misalignment is acceptable. An aromatic ring is preferable, for example, ben
Hydrocarbon aromatic rings such as zen and naphthalene rings,
Heteroaromatic rings such as gin ring and thiophene ring
The Nitrogen-containing heterocycles include thiazoline nuclei and thia
Zole nucleus, benzothiazole nucleus, oxazoline nucleus, oxy
Sazole nucleus, benzoxazole nucleus, selenazoline nucleus,
Selenazole nucleus, benzoselenazole nucleus, tellrazoline
Nucleus, tellurazole nucleus, benzotelrazole nucleus, 3,3-
Dialkyl indolenine nuclei (eg 3,3-dimethyli
Ndrenine), imidazoline nucleus, imidazole nucleus, ben
Zoimidazole nucleus, 2-pyridine nucleus, 4-pyridine nucleus,
2-quinoline nucleus, 4-quinoline nucleus, 1-isoquinoline
Nucleus, 3-isoquinoline nucleus, imidazo [4,5-b] quino
A kizarin nucleus, an oxadiazole nucleus, a thiadiazole nucleus,
Examples include tetrazole nucleus and pyrimidine nucleus.
Preferably, benzothiazole nucleus, benzoxazo
Nuclei, 3,3-dialkylindolenine nuclei (eg
3,3-dimethylindolenine), benzimidazole
Nucleus, 2-pyridine nucleus, 4-pyridine nucleus, 2-quinoline
Nucleus, 4-quinoline nucleus, 1-isoquinoline nucleus, 3-isoquinoline
Norrin nucleus, more preferably benzothiazole
Nucleus, benzoxazole nucleus, 3,3-dialkyl India
Renin nucleus (eg 3,3-dimethylindolenine),
Nzoimidazole nucleus, particularly preferably benzox
Sazole nucleus, benzothiazole nucleus, benzimidazole
A nucleus, most preferably a benzoxazole nucleus, and
Is the benzothiazole nucleus. These include the substituent represented by the aforementioned W,
And the ring may be substituted or condensed. preferable
The thing is alkyl group, aryl group, alkoxy group, halo
Gen atom, aromatic ring condensation, sulfo group, carboxyl group, hydrogen
It is a droxyl group. Z<sub>11</sub>, Z<sub>12</sub>, Z<sub>13</sub>, Z<sub>15</sub>And Z<sub>17</sub>By
Specific examples of the heterocyclic ring formed by the
340,694 No. 23-24 Z<sub>11</sub>, Z<sub>12</sub>, Z<sub>13</sub>,
Z<sub>14</sub>And Z<sub>16</sub>Similar to those listed as examples
Things. Represented by the general formula (II), (III) or (IV)
The methine dye to be produced is D in the general formula (I)<sub>1</sub>Departure represented by
Z for color group<sub>11</sub>, Z<sub>12</sub>, Z<sub>13</sub>, Z<sub>15</sub>And Z<sub>17</sub>Up
More preferably, the substituent W is a halogen atom,
Aromatic group, aromatic ring condensation. Represented by the general formula (II), (III) or (IV)
The methine dye to be produced is D in the general formula (I)<sub>2</sub>Departure represented by
Z for color group<sub>11</sub>, Z<sub>12</sub>, Z<sub>13</sub>, Z<sub>15</sub>And Z<sub>17</sub>Up
The substituent W is more preferably an acid group. Here, the acid group will be described. With acid groups
Is a group having a dissociable proton. Specifically, an example
For example, sulfo group, carboxyl group, sulfato group, -CO
NHSO<sub>2</sub>-Group (sulfonylcarbamoyl group, carboni
Rusulfamoyl group), -CONHCO- group (carboni
Rucarbamoyl group), -SO<sub>2</sub>NHSO<sub>2</sub>-Group (sulfo
Nylsulfamoyl group), sulfonamide group, sulfa
Moyl group, phosphato group, phosphono group, boronic acid group,
These pka and surrounding pH such as enolic hydroxyl groups
Depending on the case, a group capable of dissociating protons may be used. example
Protons capable of dissociating 90% or more between pH 5-11
A dissociable acidic group is preferred. More preferably, a sulfo group or a carboxyl group is used.
Group, -CONHSO<sub>2</sub>-Group, -CONHCO- group, -S
O<sub>2</sub>NHSO<sub>2</sub>-Group, particularly preferably a sulfo group,
A carboxyl group, most preferably a sulfo group.
The Z<sub>14</sub>And Z<sub>14</sub>'And (N-R<sub>14</sub>Q<sub>11</sub>, Z<sub>18</sub>When
Z<sub>18</sub>'And (N-R<sub>18</sub>Q<sub>13</sub>And Z <sub>19</sub>And Z<sub>19</sub>'And (N-
R<sub>19</sub>Q<sub>14</sub>Together are heterocycles or acyclic rings
Represents a group of atoms necessary to form an acidic end group of the formula.
What is a heterocycle (preferably a 5- or 6-membered heterocycle)?
The acid nucleus is preferred. Next, the acidic nucleus
The acyclic acidic terminal group will be described. Acidic nucleus and
Acyclic acidic end groups can be any common merocyanine color
It can also take the form of an acidic nucleus of the element and an acyclic acidic end group.
Yes. Z in the preferred form<sub>14</sub>, Z<sub>18</sub>, Z<sub>19</sub>Is thiocar
Bonyl, carbonyl, ester, acyl, cal
A vamoyl group, a cyano group, and a sulfonyl group;
Preferably, it is a thiocarbonyl group or a carbonyl group.
Z<sub>14</sub>', Z<sub>18</sub>', Z<sub>19</sub>′ Is acidic nucleus and acyclic acidic terminal
Represents the remaining atomic groups necessary to form a group. Acyclic
When forming an acidic end group of
Nyl, carbonyl, ester, acyl, carba
A moyl group, a cyano group, a sulfonyl group, and the like. Q<sub>11</sub>, Q<sub>13</sub>And q<sub>14</sub>Is 0 or 1
Is preferably 1. The acidic nucleus and acyclic acidic end group mentioned here
For example, “The Theory” edited by James (James)
Of the Photographic Process "(The
  Theory of the Photograph
ic Process) 4th edition, Macmillan Publisher, 1
977, pages 197-200. here
Is an acyclic acidic end group
Of the terminal groups of, meaning that they do not form a ring
To do. Acid nuclei and acyclic acidic end groups are specifically
U.S. Pat. Nos. 3,567,719, 3,575,86
9, No. 3, 804, 634, No. 3, 837, 862
No. 4, 002, 480, No. 4, 925, 777
No. 1, JP-A-3-167546, US Pat. No. 5,995
4,051, U.S. Pat. No. 5,747,236, etc.
There are listed. Acid nuclei are carbon, nitrogen and / or chalcone.
Gen (typically oxygen, sulfur, selenium, and tellurium)
A heterocycle consisting of a child (preferably a 5- or 6-membered nitrogen-containing compound)
Carbon) is preferred, more preferably charcoal
Elemental, nitrogen, and / or chalcogen (typically oxygen, sulfur
Yellow, selenium, and tellurium) 5- or 6-membered atoms
This is when a nitrogen-containing heterocycle is formed. Specifically, for example
For example, the following nuclei are mentioned. 2-pyrazolin-5-one, pyrazolidine
-3, 5-dione, imidazoline 5-on, hydanto
In, 2 or 4-thiohydantoin, 2-iminooki
Sazolidin-4-one, 2-oxazoline-5-one,
2-thiooxazolidine-2,5-dione, 2-thioo
Xazoline-2, 4-dione, isoxazoline-5-
ON, 2-thiazoline-4-one, thiazolidine-4-
ON, thiazolidine-2, 4-dione, rhodanine, thio
Azolidine-2,4-dithione, isorhodanine, in
Dan-1,3-dione, Thiophene-3-one, Chioff
Yen 3-On-1, 1-dioxide, Indoline-2
-On, indoline-3-on, 2-oxoindazoli
Nium, 3-oxoindazolinium, 5,7-diochi
So 6, 7-dihydrothiazolo [3,2-a] pyrimidine, shi
Chlohexane-1, 3-dione, 3, 4-dihydroiso
Quinoline-4-one, 1,3-dioxane-4,6-di
ON, barbituric acid, 2-thiobarbituric acid, black
Man-2, 4-dione, Indazolin-2-one, Piri
[1,2-a] pyrimidine-1,3-dione, pyrazo
B [1,5-b] quinazolone, pyrazolo [1,5-a]
Benzimidazole, pyrazolopyridone, 1, 2, 3,
4-tetrahydroquinoline-2, 4-dione, 3-oki
So 2, 3-dihydrobenzo [d] thiophene-1, 1
-Dioxide, 3-dicyanomethine-2, 3-dihydride
Lobenzo [d] thiophene-1, 1-dioxide
Nuclear. Furthermore, the carbo forming these nuclei.
Nyl group or thiocarbonyl group
A nucleus having an exomethylene structure substituted at the len position, and
And ketomethylene and shim which are raw materials for acyclic acidic end groups
Of active methylene compounds having a structure such as anomethylene
Has an exomethylene structure substituted at the active methylene position.
Nuclear. These acidic nuclei and acyclic acidic end groups
In the above, the substituent or ring represented by the substituent W described above is substituted.
Or may be condensed. Z<sub>14</sub>And Z<sub>14</sub>'And (N-R<sub>14</sub>Q<sub>11</sub>, Z<sub>18</sub>When
Z<sub>18</sub>'And (N-R<sub>18</sub>Q<sub>13</sub>And Z <sub>19</sub>And Z<sub>19</sub>'And (N-
R<sub>19</sub>Q<sub>14</sub>Preferably, hydantoin, 2 or
4-thiohydantoin, 2-oxazoline-5-one,
2-thiooxazoline-2,4-dione, thiazolidine
-2, 4-dione, rhodanine, thiazolidine-2, 4
-Dithione, barbituric acid, 2-thiobarbituric acid
And more preferably hydantoin, 2 or 4
-Thiohydantoin, 2-oxazoline-5-one, b
-Danine, barbituric acid, 2-thiobarbituric acid
is there. Methyl represented by the general formula (III) or (V)
The dye is D in the general formula (I)<sub>1</sub>Represents the chromophore represented by
In particular, 2 or 4-thiohydantoy is particularly preferred.
, 2-oxazoline-5-one, rhodanine. Methyl represented by the general formula (III) or (V)
The dye is D in the general formula (I)<sub>2</sub>Represents the chromophore represented by
In the case, barbituric acid is particularly preferred. Z<sub>16</sub>And Z<sub>16</sub>'And (N-R<sub>16</sub>Q<sub>12</sub>By
As the heterocyclic ring formed, the above-mentioned Z<sub>14</sub>And Z<sub>14</sub>'And (N
-R<sub>14</sub>Q<sub>11</sub>, Z<sub>18</sub>And Z<sub>18</sub>'And (N-R<sub>18</sub>Q<sub>13</sub>,as well as
Z<sub>19</sub>And Z<sub>19</sub>'And (N-R<sub>19</sub>Q<sub>14</sub>In the description of the heterocycle of
The same thing is mentioned. Preferably the aforementioned Z<sub>14</sub>
And Z<sub>14</sub>'And (N-R<sub>14</sub>Q<sub>11</sub>, Z<sub>18</sub>And Z<sub>18</sub>'And (N-R
<sub>18</sub>Q<sub>13</sub>And Z<sub>19</sub>And Z<sub>19</sub>'And (N-R<sub>19</sub>Q<sub>14</sub>Complex of
From the acidic nucleus described in the explanation of the ring, an oxo group or a thioxo group
Is excluded. More preferably, the aforementioned Z<sub>14</sub>And Z<sub>14</sub>'When
(N-R<sub>14</sub>Q<sub>11</sub>, Z<sub>18</sub>And Z<sub>18</sub>'And (N-R<sub>18</sub>Q<sub>13</sub>,
And Z<sub>19</sub>And Z<sub>19</sub>'And (N-R<sub>19</sub>Q<sub>14</sub>As a concrete example
A product obtained by removing the oxo group or thioxo group from the acidic nucleus
And More preferably hydantoin, 2 or
4-thiohydantoin, 2-oxazoline-5-one,
2-thiooxazoline-2,4-dione, thiazolidine
-2, 4-dione, rhodanine, thiazolidine-2, 4
Dithion, barbituric acid, 2-thiobarbituric acid
From which the oxo group or thioxo group is removed.
Preferably, hydantoin, 2 or 4-thiohydan
Toin, 2-oxazoline-5-one, rhodanine,
Rubituric acid, 2-thiobarbituric acid to oxo group,
Or a thioxo group, most preferably 2
Or 4-thiohydantoin, 2-oxazoline-5-
ON, remove oxo group or thioxo group from rhodanine
It is a thing. Q<sub>12</sub>Is 0 or 1, but preferably 1
is there. R<sub>11</sub>, R<sub>12</sub>, R<sub>13</sub>, R<sub>14</sub>, R<sub>15</sub>, R<sub>16</sub>, R
<sub>17</sub>, R<sub>18</sub>And R<sub>19</sub>Are a hydrogen atom, an alkyl group,
An aryl group and a heterocyclic group, preferably alkyl
A group, an aryl group, and a heterocyclic group. R<sub>11</sub>, R<sub>12</sub>, R
<sub>13</sub>, R<sub>14</sub>, R<sub>15</sub>, R<sub>16</sub>, R<sub>17</sub>, R<sub>18</sub>And R<sub>19</sub>As table
As an alkyl group, aryl group, and heterocyclic group
Specifically, for example, carbon atoms 1 to 18, preferably
1 to 7, especially preferably 1 to 4 unsubstituted alkyl groups
(E.g. methyl, ethyl, propyl, isopropyl,
Butyl, isobutyl, hexyl, octyl, dodecyl,
Octadecyl), 1 to 18 carbon atoms, preferably 1
7, particularly preferably 1 to 4 substituted alkyl groups {eg
Examples of the substituent include an alkyl group substituted with the aforementioned W.
It is. In particular, alkyl groups having the acid groups described above are preferred.
Yes. Preferably an aralkyl group (eg benzyl, 2-phenyl)
Enylethyl), unsaturated hydrocarbon groups (eg allyl groups,
The vinyl group, i.e.
Nyl group and alkynyl group are also included. ), Hide
Roxyalkyl groups (eg 2-hydroxyethyl, 3
-Hydroxypropyl), carboxyalkyl groups (eg
2-carboxyethyl, 3-carboxypropyl,
4-carboxybutyl, carboxymethyl), alkoxy
Cialkyl groups (eg 2-methoxyethyl, 2- (2
-Methoxyethoxy) ethyl), aryloxyalkyl
Groups such as 2-phenoxyethyl, 2- (1-naphthoxy
Ii) ethyl), alkoxycarbonylalkyl groups (eg
For example, ethoxycarbonylmethyl, 2-benzyloxycar
Bonylethyl), aryloxycarbonylalkyl group
(Eg 3-phenoxycarbonylpropyl), acyl
Oxyalkyl groups (eg 2-acetyloxyethyl)
), An acylalkyl group (for example, 2-acetylethyl)
), A carbamoylalkyl group (eg 2-morpholino)
Carbonylethyl), sulfamoylalkyl groups (eg
N, N-dimethylsulfamoylmethyl), sulfoa
Alkyl group (for example, 2-sulfoethyl, 3-sulfopro
Pill, 3-sulfobutyl, 4-sulfobutyl, 2- [3
-Sulfopropoxy] ethyl, 2-hydroxy-3-s
Rufopropyl, 3-sulfopropoxyethoxyethyl
), Sulfoalkenyl groups, sulfatoalkyl groups (eg
For example, 2-sulfatoethyl group, 3-sulfatopropi
, 4-sulfatobutyl), a heterocyclic-substituted alkyl group
(Eg 2- (pyrrolidin-2-one-1-yl) ethyl
, Tetrahydrofurfuryl), alkylsulfonylca
Rubamoylalkyl group (eg methanesulfonylcarba
Moylmethyl group), acylcarbamoylalkyl group (eg
Acetylcarbamoylmethyl group), acylsulfa
Moylalkyl groups (eg acetylsulfamoylmethyl)
Group), alkylsulfonylsulfamoylalkyl
Groups (eg methanesulfonylsulfamoylmethyl)
Group)}, 6 to 20 carbon atoms, preferably 6 to 1 carbon atoms
0, more preferably 6 to 8 carbon atoms substituted or unsubstituted
A substituted aryl group (substituent includes W described above.
And phenyl group, 1-naphthyl group, p-methoxypheny
Group, p-methylphenyl group, p-chlorophenyl group, etc.
And so on. ), Carbon number 1 to 20, preferably charcoal
A prime number of 3 to 10, more preferably 4 to 8 carbon atoms.
Substituted or unsubstituted heterocyclic group (substituent includes the aforementioned W
The Specifically, 2-furyl group, 2-thienyl group, 2-pi
Lysyl group, 3-pyrazolyl, 3-isoxazolyl, 3
-Isothiazolyl, 2-imidazolyl, 2-oxazoly
2, 2-thiazolyl, 2-pyridazyl, 2-pyrimidi
, 3-pyrazyl, 2- (1,3,5-triazolyl), 3-
(1,2,4-triazolyl), 5-tetrazolyl, 5-methyl
A leu-2-thienyl group, 4-methoxy-2-pyridyl group, etc.
And so on. ). General formula (II), (III), (IV), or
The methine dye represented by (V) is D in the general formula (I)<sub>1</sub>In the table
R represents the chromophore to be<sub>11</sub>, R<sub>12</sub>, R<sub>13</sub>, R<sub>14</sub>, R
<sub>15</sub>, R <sub>16</sub>, R<sub>17</sub>, R<sub>18</sub>And R<sub>19</sub>As a substituent represented by
Preferably an unsubstituted alkyl group or a substituted alkyl group.
The substituted alkyl group preferably has the above acid group
It is an alkyl group. As an acid group, preferably a sulfo group,
Carboxyl group, -CONHSO<sub>2</sub> -Group, -CONHC
O-group, -SO<sub>2</sub> NHSO<sub>2</sub> -Group, particularly preferred
Is a sulfo group or a carboxyl group, most preferably
It is a sulfo group. General formula (II), (III), (IV), or
The methine dye represented by (V) is D in the general formula (I)<sub>2</sub>In the table
R represents the chromophore to be<sub>11</sub>, R<sub>12</sub>, R<sub>13</sub>, R<sub>14</sub>, R
<sub>15</sub>, R <sub>16</sub>, R<sub>17</sub>, R<sub>18</sub>, And R<sub>19</sub>As a substituent represented by
Preferably an unsubstituted alkyl group or a substituted alkyl group.
More preferably, it is an alkyl group having an acid group as described above.
The As an acid group, preferably a sulfo group or a carboxyl group
Group, -CONHSO<sub>2</sub>-Group, -CONHCO- group, -S
O<sub>2</sub>NHSO<sub>2</sub>-Group, particularly preferably a sulfo group,
A carboxyl group, most preferably a sulfo group.
The L<sub>11</sub>, L<sub>12</sub>, L<sub>13</sub>, L<sub>14</sub>, L<sub>15</sub>, L<sub>16</sub>, L
<sub>17</sub>, L<sub>18</sub>, L<sub>19</sub>, L<sub>20</sub>, L<sub>twenty one</sub>, L<sub>twenty two</sub>, L<sub>twenty three</sub>, L<sub>twenty four</sub>,
L<sub>twenty five</sub>, L<sub>26</sub>, L<sub>27</sub>, L<sub>28</sub>, L<sub>29</sub>, L<sub>30</sub>, L<sub>31</sub>, L<sub>32</sub>, And
And L<sub>33</sub>Each independently represents a methine group. L<sub>1</sub>~ L<sub>33</sub>so
The methine group represented may have a substituent.
Is the aforementioned W. For example, substituted or unsubstituted
Having 1 to 15 carbon atoms, preferably 1 to 10 carbon atoms,
Preferably, the alkyl group has 1 to 5 carbon atoms (for example,
Til, ethyl, 2-carboxyethyl), substituted or absent
Carbon number of substitution 6 to 20, preferably 6 to 1
5, more preferably an aryl group having 6 to 10 carbon atoms (eg
Phenyl, o-carboxyphenyl), substituted or
Unsubstituted C 3-20, preferably 4 C 1
5, more preferably a heterocyclic group having 6 to 10 carbon atoms (eg
N, N-dimethylbarbituric acid group), halogen source
Child (for example, chlorine, bromine, iodine, fluorine), 1 carbon
15, preferably 1 to 10 carbon atoms, more preferably
Alkoxy groups having 1 to 5 carbon atoms (eg methoxy, eth
Xi), 0 to 15 carbon atoms, preferably 2 to 1 carbon atoms
0, more preferably an amino group having 4 to 10 carbon atoms (eg
Methylamino, N, N-dimethylamino, N-methyl
-N-phenylamino, N-methylpiperazino), carbon
Number 1 to 15, preferably 1 to 10 carbons, more preferred
Or an alkylthio group having 1 to 5 carbon atoms (for example, methyl
Thio, ethylthio), 6 to 20 carbon atoms, preferably charcoal
Prime number 6 to 12, more preferably 6 to 10 carbon atoms
A reelthio group (eg phenylthio, p-methylpheny
Lucio) and the like. Also forms a ring with other methine groups
Or Z<sub>11</sub>~ Z<sub>19</sub>, R<sub>11</sub>~ R<sub>19</sub>With
Rings can also be formed. L<sub>11</sub>, L<sub>12</sub>, L<sub>16</sub>, L<sub>17</sub>, L<sub>18</sub>, L<sub>19</sub>, L
<sub>twenty two</sub>, L<sub>twenty three</sub>, L<sub>29</sub>, And L<sub>30</sub>Preferably, an unsubstituted
It is a chin group. N<sub>11</sub>, N<sub>12</sub>, N<sub>13</sub>, N<sub>14</sub>And n<sub>15</sub>Is it
Each independently represents 0, 1, 2, 3 or 4. Preferably
0, 1, 2, 3 and more preferably 0, 1, 2
Particularly preferred are 0 and 1. n<sub>11</sub>, N<sub>12</sub>, N<sub>13</sub>,
n<sub>14</sub>And n<sub>15</sub>When is 2 or more, the methine group is repeated
Need not be identical. P<sub>11</sub>, P<sub>12</sub>, P<sub>13</sub>, P<sub>14</sub>And p<sub>15</sub>Is it
Each independently represents 0 or 1. Preferably it is 0. M<sub>1</sub>, M<sub>11</sub>, M<sub>12</sub>, M<sub>13</sub>And M<sub>14</sub>Is a pigment
When necessary to neutralize the ionic charge of
Included in formulas to indicate the presence of on or anions
ing. Typical cations are hydrogen ions
(H<sup>+</sup>), Alkali metal ions (eg sodium
, Potassium ion, lithium ion), alkaline earth
Inorganic positive ions such as metal ions (eg calcium ions)
On, ammonium ion (eg ammonium ion
, Tetraalkylammonium ions, triethylammonium
Ammonium ion, pyridinium ion, ethyl pyridi
Ni-ion, 1,8-diazabicyclo [5.4.0]-
Organic ions such as 7-undecenium ion)
It is. Anions are inorganic or organic anions.
Any of these may be used, and halogen anions (eg, fluorine
Elementary ion, chlorine ion, iodine ion), substituted aryl
Sulfonate ions (eg p-toluenesulfonate ion)
P-chlorobenzenesulfonate ion), aryl
Disulfonate ion (eg 1,3-benzenesulfone)
Acid ion, 1,5-naphthalenedisulfonic acid ion,
2,6-naphthalenedisulfonic acid ion), alkyl sulfur
Acid ion (eg methyl sulfate ion), sulfate ion,
Ocynate ion, perchlorate ion, tetrafluorophor
Oxalate, picrate, acetate, triflu
Examples include olomethanesulfonate ion. In addition,
Use other dyes that have an opposite charge to the on-state polymer or dye
May be. CO<sub>2</sub> <sup>-</sup>, SO<sub>Three</sub> <sup>-</sup>As a counter ion
CO with hydrogen ions<sub>2</sub>H, SO<sub>Three</sub>Indicate H
Both are possible. M<sub>1</sub>, M<sub>11</sub>, M<sub>12</sub>, M<sub>13</sub>And m<sub>14</sub>Is the charge
Represents a number greater than or equal to zero required to balance, preferably
It is a number from 0 to 4, more preferably a number from 0 to 1.
That is, it is 0 when a salt is formed in the molecule. In the present invention, at least linking dyes having different structures are used.
Any number of linking dyes
Preferably 10 or less, more preferably
5 or less. Particularly preferred is 3 to 2. In addition, what is the mixing ratio of the linking dyes?
But preferably contains the least amount of linking dye
Value P expressed as a percentage<sub>min</sub>Is 5 / z <P<sub>min</sub>≦ 10
When 0 / z. Where z represents the number of linked dyes.
The More preferably, 20 / z <P<sub>min</sub>≤100 / z
It is. More preferably, 40 / z <P<sub>min</sub>≦ 100 / z,
Is the time. Particularly preferably, 70 / z <P<sub>min</sub>≦ 100 /
z. Next, a detailed description will be given in the description of the embodiment of the invention.
Only specific examples of dyes used in particularly preferred technology
It is shown below. Of course, the present invention is not limited to these.
Not. First, D of the present invention<sub>1</sub>Specific examples of − are shown. This
Here, = N- represents a nitrogen atom linked to La. [0098] [Chemical 7] Next, -D of the present invention<sub>2</sub>A specific example is shown. This
Here, N in N-La represents a nitrogen atom linked to La.
The [0100] [Chemical 8] [0101] [Chemical 9] [0102] Embedded image Next, specific examples of La of the present invention will be shown. [0104] Embedded image [0105] Embedded image [0106] Embedded image [0107] Embedded image Next, the dye represented by the general formula (I) of the present invention.
A specific example is shown. [0109] Embedded image [0110] Embedded image [0111] Embedded image [0112] Embedded image [0113] Embedded image [0114] Embedded imageThe coloring matter of the present invention is FMM
(F.M.Harmer) "Heterocyclic Compounds-
Cyanid Soybean and Relevant Compounds
(Heterocyclic Compounds-Cyanine Dyes and Related C
ompounds), John Willie & Sons (Joh
n Wiley & Sons)-New York, London, 196
4th year, D.M. Sturmer
Terror Cyclic Compounds-Special Topic
Cus in Heterocyclic Chemistry (Heter
ocyclic Compounds-Special topics in recycled c
hemistry) ", Chapter 18, Section 14, 482-51
Page 5, John Wiley and Sons
& Sons)-New York, London, 1977,
"The Rods Chemistry of Carbon Compound
(Rodd's Chemistry of Carbon Compounds) '' 2nd.Ed.v
ol. IV, part B, 1977, Chapter 15, 369-42
2 pages, Elsevier Science Public Company
-Ink (Elsevier Science Publishing Company In
c.) Company, New York, and the above-mentioned patents and documents
(Quoted for explanation of example)
Can be synthesized on the basis. In the present invention, only the sensitizing dye of the present invention is used.
Without using other sensitizing dyes other than the present invention, or in combination
Also good. The dye used is preferably a cyanine color
Element, merocyanine dye, rhodacyanine dye, trinuclear merosi
Anine dye, tetranuclear merocyanine dye, allopolar color
Element, hemicyanine dye, styryl dye, etc.
The More preferably cyanine dye, merocyanine color
And rhodacyanine dyes, particularly preferably cyanine
It is a pigment. For more information on these dyes, see F.E.
F.M.Harmer, `` Heterocyclic
Compound Soybean Soybean and Relaided
Heterocyclic Compounds-Cyanine Dyes a
nd Related Compounds) ", John Willie &
・ John Wiley & Sons-New York, Ron
Don, 1964, D.M. Sturmer (D.M.Stu
rmer) "Heterocyclic Compound Suspeci"
Topics in Heterocyclic Chemis
Tree (Heterocyclic Compounds-Special topics in he
terocyclic chemistry) ", Chapter 18, Section 14, Section 4
82-515, John Willie and Sons
(John Wiley & Sons)-New York, London, 1
Published in 977, “Rods Chemistry of Carbon”
・ Compods (Rodd's Chemistry of Carbon Compound)
s) "2nd. Ed. vol. IV, part B, 1977, Chapter 15, Chapter 3
69-422, Elsevier Science Public
Company Inc. (Elsevier Science Publishing
 Company Inc.), published in New York, etc.
Yes. Preferred dyes include US Pat. No. 5,994,
No. 051, pages 32-44, and US Pat. No. 5,74.
No. 7,236, general formulas described on pages 30 to 39, and specific examples
And sensitizing dyes shown in FIG. Also preferred shear
General of nin, merocyanine and rhodacyanine dyes
Formula is US Pat. No. 5,340,694 column 21-22
Of (XI), (XII), (XIII)
(However, the number of n12, n15, n17, and n18 is not limited and is 0 or more.
An integer of (preferably 4 or less). ). These sensitizing dyes may be used alone,
Two or more types may be used.
Often used for supersensitization. A typical example is rice
National Patents 2,688,545 and 2,977,229
No. 3,397,060 No. 3,522,052
No. 3,527,641, No. 3,617,293
No., No. 3,628,964, No. 3,666,480
No. 3,672,898 No. 3,679,428
No. 3,303,377 No. 3,769,301
No. 3,814,609 No. 3,837,862
No. 4,026,707, British Patent 1,344,2
81, 1,507,803, Shoko 43-493
36, 53-12375, Japanese Patent Laid-Open No. 52-1106
18 and 52-109925 etc.
The Spectral sensitizing effect itself with sensitizing dye
Dyes that do not have visible light or substances that do not substantially absorb visible light
The emulsion may contain a substance that is high in quality and exhibits supersensitization.
Yes. Strong intensity useful in spectral sensitization in the present invention
Color sensitizers (eg, pyrimidylamino compounds, triazis
Nylamino compounds, azolium compounds, aminostyryl
Compound, aromatic organic acid formaldehyde condensate, azai
Compounds, cadmium salts), and supersensitizers and sensitizers
For example, US Pat. No. 3,511,66
No. 4, No. 3,615,613, No. 3,615,632
No.3,615,641, No.4,596,767
No. 4,945,038, No. 4,965,182
No. 4,965,182 No. 2,933,390
Nos. 3,635,721, 3,743,510
No., No. 3,617,295, No. 3,635,721
The above patents are also used for their usage.
Is preferred. The sensitizing dye of the present invention (and other sensitizing colors)
The same applies to elementary and supersensitizers).
It is recognized that the timing of addition to the silver emulsion has been useful so far.
Can be used during any process of emulsion preparation
Yes. For example, U.S. Pat. Nos. 2,735,766 and 3,6
28,960, 4,183,756, 4,22
5,666, JP-A-58-184142, 60-
Halogenation as disclosed in No. 196749 etc.
Silver particle formation process and / or time before desalting, desalting process
The period from middle and / or after desalting to before the start of chemical ripening,
As disclosed in Japanese Patent Application Laid-Open No. 58-11939
In addition, just before chemical aging or during the process, after chemical aging
Any time before the emulsion until the cloth is applied
It may be added at a later stage. U.S. Pat. No. 4,22
No. 5,666, Japanese Patent Laid-Open No. 58-7629, etc.
The same compound alone or of different structures
In combination with the compound, for example, during the grain formation process and chemical ripening
Separated during or after completion of chemical aging or chemical aging
Before or during the process and after completion
It may be added, and the compound to be added in portions and the compound
The kinds of combinations may be changed and added. The sensitizing dye of the present invention (and other sensitizing colors)
The same is true for elementary and supersensitizers)
Depending on the shape and size of silver halide grains, either
The amount added may be 1 x 1 per mole of silver halide
0^-6~ 8x10^-3Can be used in moles. For example,
When the silver halide grain size is 0.2 to 1.3 μm
Is 2 x 10 per mole of silver halide.^-6~ 3.5x
10^-3Molar addition amount is preferred, 7.5 × 10^-6~ 1.
5 × 10^-3A molar addition amount is more preferable. However, as mentioned above
As described above, in the case of multilayer adsorption of the sensitizing dye of the present invention,
It is preferable to add an amount necessary for layer adsorption. The sensitizing dye of the present invention (and other sensitizing colors)
The same applies to elementary and supersensitizers).
can do. These are also suitable solvents, eg
For example, methyl alcohol, ethyl alcohol, methyl cello
Solve, acetone, water, pyridine or a mixture of these
It is dissolved in a solvent and added to the emulsion in the form of a solution.
You can also. At this time, addition of base, acid, surfactant, etc.
Additives can coexist. Also, use ultrasonic waves for dissolution
It can also be used. In addition, the addition method of this compound and
As described in U.S. Pat. No. 3,469,987.
When the compound is dissolved in a volatile organic solvent, the solution is
Disperse in hydrophilic colloid and add this dispersion into emulsion
As described in Japanese Patent Publication No. 46-24185
Dispersed in a water-soluble solvent, and this dispersion is added to the emulsion.
Method described in US Pat. No. 3,822,135
The compound is dissolved in the surfactant and the solution is added to the emulsion.
As described in JP-A-51-74624
When using red shift compounds, dissolve
A method for adding a liquid into an emulsion, Japanese Patent Application Laid-Open No. 50-80826
The compound is dissolved in an acid substantially free of water as described in
And a method of adding the solution to the emulsion is used.
The In addition, U.S. Pat. No. 2,91
2,343, 3,342,605, 2,99
Those described in 6,287, 3,429,835, etc.
The method is also used. In the present invention, sensitizing dyes having different structures are used.
When two or more types are used, the next period to be added is different at the same time.
The period may be acceptable. Preferably, it is a case where it adds simultaneously. In the present invention, multilayer adsorption means halogen.
More dye chromophores are laminated on the surface of the silver halide grains.
Means that. In the present invention, multilayer adsorption is performed.
Is preferred. In the present invention, the light absorption intensity is the unit particle.
It is the light absorption area intensity by the sensitizing dye per surface area,
The amount of light incident on the unit surface area of a particle is I₀ Sensitization at the surface
Optical density Log when the amount of light absorbed by the dye is I
(I₀ / (I₀ -I)) to wave number (cm^-1) Integral for
Define the value as Integration range is 5000cm^-1To 35
000cm^-1Up to. Silver halide photographic emulsion according to the present invention
In the case of particles whose spectral absorption maximum wavelength is 500 nm or more
Has a light absorption intensity of 100 or more and a spectral absorption maximum wavelength of 500.
In the case of particles smaller than nm, a light absorption intensity of 60 or more
More than 1/2 of the total silver halide grain projected area
It is preferable to include the above. The spectral absorption maximum wavelength is 50.
In the case of particles of 0 nm or more, the light absorption intensity is preferably
150 or more, more preferably 170 or more, particularly preferred
Or 200 or more, and the spectral absorption maximum wavelength is 500 n.
For particles less than m, the light absorption intensity is preferably 90.
Or more, more preferably 100 or more, particularly preferably 1
20 or more. There is no upper limit, but preferably 200
0 or less, more preferably 1000 or less, particularly preferably
Is 500 or less. Spectral absorption maximum wavelength is 500n
For particles less than m, the spectral absorption maximum wavelength is 350 n
It is preferable that it is m or more. As an example of a method for measuring light absorption intensity
Can include a method using a microspectrophotometer
The Microspectrophotometer measures the absorption spectrum of a small area
Can measure the transmission spectrum of a single particle.
Noh. Absorption spectrum of one particle by microspectroscopy
Regarding the measurement, Yamashita et al.
Refer to the 6th Annual Conference Abstracts, page 15)
You can. From this absorption spectrum, the absorption per particle
Yield strength is required, but the light passing through the particles
Because it is absorbed by two surfaces of the part, the unit area of the particle surface
The absorption intensity of each particle is the absorption per particle obtained by the above method.
It can be determined as 1/2 of the yield strength. At this time,
The interval where the absorption spectrum is integrated is defined as the light absorption intensity.
5000cm ^-1To 35000cm^-1But experimentally
Is 500 cm before and after the section with absorption by the sensitizing dye^-1About
Integration of intervals including degrees is acceptable. In addition, the light absorption intensity is the oscillator strength of the sensitizing dye.
And the value uniquely determined by the number of adsorbed molecules per unit area
The oscillator strength of the sensitizing dye, the dye adsorption amount and the particles
If a surface area is calculated | required, it can convert into light absorption intensity.
The vibrator strength of the sensitizing dye is the absorption area strength of the sensitizing dye solution.
(Optical density x cm^-1) Experimentally obtained as a value proportional to
The absorption area intensity of the dye per 1M
A (optical density x cm^-1), The adsorption amount of the sensitizing dye is B (m
ol / molAg), the particle surface area is C (m² / MolA
g), the light absorption intensity is estimated to be about 10% by the following equation.
It can be obtained in the range of degrees. 0.156 x A x B / C Even if the light absorption intensity is calculated from this equation, it is based on the above definition.
Measured light absorption intensity (Log (I₀ / (I₀ −
I))) wavenumber (cm^-1) Integrated with) and real
The same value is obtained. The multilayer adsorption will be described in more detail.
The More dye adsorbed on the particle surface
The state is that a dye bound in the vicinity of the silver halide grains
Means that there is more, color that exists in the dispersion medium
Does not contain element. In addition, the dye chromophore adsorbs on the particle surface.
Even if the substance is covalently linked to the
Very long, if the dye chromophore is present in the dispersion medium
When the effect of increasing the light absorption intensity is small and undesirable
There is. In this case, more adsorption is not considered.
Yes. The chromophore mentioned here is the physics and chemistry dictionary (No. 1).
4th edition, Iwanami Shoten, 1987), 985-986
Means the atomic group that is the main cause of the absorption band of molecules, for example
Atomic groups with unsaturated bonds such as C = C, N = N, etc.
Any atomic group is possible. Specifically, D in the general formula (I)₁, And D₂so
The dye chromophore mentioned as a specific example of the dye chromophore represented
Can be mentioned. Polymethine chromophore is preferable
The Adsorption of dye chromophores on silver halide grains
Is preferably 1.5 layers or more, more preferably 1.7 layers.
There are two or more layers, particularly preferably two or more layers. The upper limit is
Although not particularly, 10 layers or less are preferable, more preferably
5 layers or less. One of the methods for evaluating the adsorption state of the multilayer adsorbing dye
There are the following methods. Add to silver halide emulsion
Sensitizing dyes with dye chromophores linked by covalent bonds
I.e., halogenated among the individual dyes that are not linked.
It is achieved by the dye that has the smallest dye occupation area on the silver particle surface.
Saturated adsorption amount per unit surface area reached
And the unit surface of the dye chromophore with respect to the saturated coating amount.
If the amount of adsorption per product is large, it can be said that multilayer adsorption is performed.
The In addition, the number of adsorbed layers is based on the saturated coating amount as a standard.
It means the amount of adsorption. The dye occupation area is determined by the free dye concentration and the adsorbed dye.
Calculated from adsorption isotherm indicating particle quantity relationship and particle surface area
Rukoto can. The adsorption isotherm is, for example, A Hearts
(A. Herz) et al. Adsorption from Ak
Ayth Solution (Adsorption fr
om Aqueous Solution) Advance
In Chemistry Series (Advanced
s in Chemistry Series) no.
See pages 17, 173 (1968)
You can The amount of the sensitizing dye adsorbed on the emulsion grains is determined by the amount of the dye.
The adsorbed emulsion is centrifuged to obtain emulsion grains and supernatant.
Of the aqueous solution of gelatin and measuring the absorbance of the supernatant
Calculate the amount of unadsorbed dye from the amount and subtract from the amount of added dye.
To determine the amount of adsorbed dye and drying the precipitated emulsion grains
A constant mass of precipitate with sodium thiosulfate aqueous solution and
Dissolve in a 1: 1 mixture of nor and measure spectral absorption
It is possible to use two methods of obtaining the amount of adsorbed dye with
I can do it. High-speed liquid when multiple sensitizing dyes are used
About individual dyes by methods such as body chromatography
The amount of adsorption can also be obtained. Determine the amount of pigment in the supernatant
The method for obtaining the dye adsorption amount by measuring
Journal of W. West et al.
  Physical chemistry (Journal of
(Physical Chemistry) Volume 56, 1
By referring to page 054 (1952)
Yes. However, under conditions where the amount of added dye is large, unadsorbed dye
However, it may settle, and the pigment concentration in the supernatant is quantified.
The correct adsorption amount may not always be obtained by this method.
It was. On the other hand, the precipitated silver halide grains are dissolved to absorb the dye.
Emulsion grains are overwhelmingly settled if it is a method for measuring the amount of deposit.
The falling speed is so fast that the particles and the settled pigment can be separated easily.
Thus, only the amount of dye adsorbed on the particles can be accurately measured. This
Is the most reliable method for determining the amount of dye adsorbed.
Yes. Of silver halide adsorbing compounds (useful photographic compounds)
The amount adsorbed on the particles can be measured in the same way as the sensitizing dye, but visible
Because the absorption in the light region is small, it is more than the quantitative method using spectral absorption.
However, quantitation by high performance liquid chromatography is preferred
Yes. Example of measuring method of silver halide grain surface area
As an example, take a transmission electron micrograph by the replica method
The method to calculate and calculate the shape and size of individual particles
is there. In this case, the thickness of the tabular grains is that of the replica.
Calculated from the length of the shadow. Transmission electron microscope
For example, the Japanese Society of Electron Microscopy
Kanto Chapter “Electron Microscope Sample Technology Collection” Seikodo Shinkosha 19
70 years, Butterworth (Butwrworth)
s), London, 1965, BB Hirsch
(P.B.Hirsch) et al. Electron Micro
Scope of Chin Crystal (Electron
  Microscope of ThinCrysta
ls) can be referred to. As other methods, for example, A.M.
Journal of A.M. Kragin et al.
Of Photographic Science (The Jo
urnal of Photographic Sci
ence), volume 14, page 185 (1966), di
Transformer of JF Paddy
Actions of the Faraday Society
(Transactions of the Fara
day Society) Volume 60, page 1325 (1
964), S. Boyer et al.
Nal de Simiphysique e de Physicosimi Business
Journal de Chimier Ph
ysique et de Physicochimi
e biologic) 63, 1123
(1963), W. Wes
t) et al. Journal of Physical Chemistry
(Journal of Physical Chem
(istry) vol. 56, page 1054 (1952)
H. Sauvenie (year)
r) Edited by E. Klein et al.
International Colloquium (International)
al Coloquium, Liege
e), 1959, “Scientific Photogram
Raffy (Scientific Photogram
hy) "and the like. Dye occupation area
Is experimentally determined for each case by the above method
However, the molecular occupying area of the sensitizing dye usually used is approximately 80.
ŲBecause it is near, color for all dyes easily
80 square meters²Estimate the approximate number of adsorbed layers as
You can also. In multilayer adsorption, the particle surface is directly applied.
Spectral sensitization may occur due to non-adsorbing dyes
For this purpose, it must be adsorbed directly on the silver halide.
Excitation energy from undyed dye to dye directly adsorbed on particles
Transmission of energy or transmission of electrons is required. Excitation energy
The transmission of excitation energy is good for electron transmission and electron transmission.
More preferable. 10 levels of excitation energy or electron transfer
The final excitation energy
Rugged or electronic transmission efficiency is low.
Yes. An example of this is a polymer such as JP-A-2-113239.
Most of the dye chromophore, like the dye, is present in the dispersion medium,
Cases where more than 10 stages of excitation energy transfer are required
It is done. In the present invention, the number of dye chromophores per molecule is two.
3 is preferred, and 2 is more preferred. In the present invention, a dye is added to the silver halide grains.
If the chromophore is adsorbed in multiple layers, the silver halide grains
Directly adsorbed so-called first layer chromophore and second layer
What is the reduction potential and oxidation potential of the above dye chromophores?
The reduction potential of the dye chromophore in the first layer is the second layer.
0.2 v was subtracted from the reduction potential value of the above dye chromophore.
It is preferable to be noble rather than a value. The reduction potential and oxidation potential can be measured in various ways.
The method is possible, but preferably the phase discriminating second harmonic
This is an accurate value when using wave AC polarography.
Can be requested. The above phase discrimination type second high
The method of measuring potential by harmonic alternating current polarography is
-Null of Imaging Science (Journ
al of Imaging Science), 3rd
0, page 27 (1986). In addition, the dye chromophore in the second layer or more is luminescent.
A dye is preferred. As a kind of luminescent dye, dye
Those with a dye skeleton structure used for lasers are preferred.
Good. These include, for example, Maeda Mitsuo, Laser Research, No.
8, 694, 803, 958 (1980) and
9:85 (1981), and F. Sehaefer
In the book, "Dye Lasers", Springer (1973)
It is managed. Furthermore, the halogenation of the dye chromophore in the first layer
Absorption maximum wavelength in silver photographic material is 2nd layer or more
It is preferable that the wavelength is longer than the absorption maximum wavelength of the dye chromophore.
Good. In addition, the light emission of the dye chromophore in the second layer or higher
It preferably overlaps with the absorption of the dye chromophore. Also 1
The dye chromophore in the layer is preferably formed as a J-aggregate.
In addition, it has absorption and spectral sensitivity in the desired wavelength range
For this purpose, the dye chromophores in the second and higher layers also form J aggregates.
It is preferable. Excitation energy of the second layer dye chromophore
Lugie's energy transfer efficiency to the first pigment chromophore
Is preferably 30% or more, more preferably 60%,
Particularly preferably, it is 90% or more. Where the second layer dye
The excitation energy of the chromophore means that the dye chromophore in the second layer is light
Excited dye produced by absorbing energy has
It refers to energy. Excitation energy of one molecule is another
When moving to other molecules, the excited electron transfer mechanism, Fers
Forster Mode
l) Dexter energy transfer mechanism (Dextor)
The excitation energy moves via Model)
Therefore, even in the multilayer adsorption system of the present invention, this
Efficient excitation energy transfer conceivable from these mechanisms
It is preferable to satisfy the conditions for waking up. In addition,
The conditions for causing the Elster energy transfer mechanism
It is particularly preferable to satisfy it. Forster energy
-To increase the transfer efficiency, refraction near the emulsion grain surface
It is also effective to reduce the rate. Is the second layer dye chromophore?
The efficiency of energy transfer to the second layer dye chromophore is
Spectral sensitization efficiency upon excitation of eye dye chromophore / 1st eye dye chromophore
It can be obtained as spectral sensitization efficiency at the time of excitation. The meanings of terms used in the present invention are as follows:
Describe. -Dye occupation area: Occupied area per molecule of dye. Adsorption etc.
It can be determined experimentally from the temperature line. Shared connection of the present invention
If the dye has a dye chromophore linked, do not link it.
Based on the dye occupation area of each individual dye in a new state. Simple
It is 80cm². ・ Saturated coating amount: Unit particle surface area at the time of single layer coating
Amount of dye adsorption per day. Minimal pigment occupancy among added pigments
The reciprocal of the area. Multi-layer adsorption: One dye chromophore on the surface of silver halide grains
It means that more layers are stacked. One of the evaluation methods
As the adsorption amount of the dye chromophore per unit particle surface area
There is a method to evaluate by more than the saturation coverage.
is there. -Number of adsorbed layers: Dye chromophores are accumulated on the surface of silver halide grains
It means the number of layers. As one of the evaluation methods,
Dye per unit particle surface area based on the total coating amount
There is a method of evaluating from the amount of adsorption of the chromophore. For example, two
A compound in which the dye chromophores are covalently linked is a compound
2 layers as a dye chromophore
It means that it is adsorbed. Light absorption intensity of 50 or 70 or more halogen
Spectroscopy with emulsion dyes containing silver halide photographic emulsion grains.
The maximum value Amax of the absorptance and the maximum value Smax of the spectral sensitivity
The interval between the shortest wavelength and the longest wavelength, each representing 50%, is
Preferably it is 120 nm or less, more preferably 1
00 nm or less. Also shows 80% of Amax and Smax
The distance between the shortest wavelength and the longest wavelength is preferably 20 nm.
Above, preferably 100 nm or less, more preferably
80 nm or less, particularly preferably 50 nm or less. Ma
Shortest wavelength and longest wave showing 20% of Amax and Smax
The long interval is preferably 180 nm or less, more preferably
Or 150 nm or less, particularly preferably 120 nm or less,
Most preferably, it is 100 nm or less. The longest wave showing a spectral absorption rate of 50% of Amax
The length is preferably from 460 nm to 510 nm, or 56
0 nm to 610 nm, or 640 nm to 730 n
m. Longest wavelength showing 50% spectral sensitivity of Smax
Is preferably 460 nm to 510 nm, or 560
nm to 610 nm, or 640 nm to 730 nm
It is. In addition, the color development of the first layer of silver halide grains
The maximum value of spectral absorptance by the color group is A1max.
A2max is the maximum spectral absorptance due to the dye chromophore.
A1max and A2max are 400 to 500 nm or 50
0-600 nm, or 600-700 nm, or 700
It is preferable to be in the range of ˜1000 nm. Further, a dye in the first layer of silver halide grains
The maximum spectral sensitivity due to the chromophore is S1max, the colors after the second layer
S2max is the maximum spectral sensitivity due to the elementary chromophore.
1max and S2max are 400 to 500 nm, or 500 to
600 nm, or 600-700 nm, or 700-1
It is preferably in the range of 000 nm. Realizing multilayer adsorption using linking dyes
The second layer of dye chromophore in the monomer state
When adsorbed, wider than desired absorption width and spectral sensitivity width
It may be. Therefore, in the present invention, preferably
Adsorbed in the second layer to achieve high sensitivity in the desired wavelength range
This is the case where the dye chromophore that forms a J-aggregate. More
J-aggregate has a high fluorescence yield and a small Stokes shift.
As a result, the first layer of the dye chromophore with a light absorption wavelength close
Forster-type light energy absorbed by eye pigment chromophore
It is also preferable to transmit by energy transfer. In the present invention, the dye chromophore in the second layer or more
Is bound to silver halide grains, but
A dye chromophore that is not directly adsorbed to silver halide.
The In the present invention, the J-aggregate of the dye chromophore in the second layer or more
Is the absorption length exhibited by the dye chromophore adsorbed on the second and higher layers.
Absorption width on the wavelength side is a single quantity with no interaction between dye chromophores
Double the absorption width on the long wavelength side of the absorption exhibited by the dye solution in the body state
It is defined as Here, the absorption width on the long wavelength side is
Absorption maximum wavelength and absorption maximum at a wavelength longer than the absorption maximum wavelength
It represents the energy width with respect to the wavelength exhibiting 1/2 absorption. General
When J-aggregate is formed on the long wavelength side compared to the monomer state
It is known that the absorption width of is small. Monomer state
In the case of adsorption on the second layer, the adsorption position and state
Due to the uniformity, the absorption of the long wavelength side of the monomer state of the dye solution
More than twice the yield. Therefore, the above definition
Define the J-aggregates of the dye chromophore in the second layer or higher
I can do it. Spectral absorption of the dye chromophore adsorbed on the second and higher layers
From the total spectral absorption of the emulsion to the first dye chromophore.
It can be obtained by subtracting the spectral absorption. Spectral absorption by the first layer dye chromophore is linked
When only the first-layer pigment chromophore portion is added
It can be obtained by measuring the absorption spectrum. [0153] In addition, the dye in the unconnected state was devised.
If it can be adsorbed in multiple layers
Add a dye desorbing agent to desorb the second layer or more of the dye
To measure the spectral absorption spectrum of the first layer dye.
It is also possible. Do not link from the particle surface with a dye desorbent.
In the experiment to desorb the dye in the
Appropriate because it is desorbed after the second and higher layers are desorbed
Spectral absorption by the first dye
Rukoto can. As a result, the spectrum of the dye in the second layer or higher
Absorption can be determined. For those who use a depigmenting agent
The law is reported by Asanuma et al. (Journal of Physical
Chemistry B (Journal of Physi
cal Chemistry B) Vol. 101, 2149
From page 2153 (1997))
I can do it. In the present invention, additives other than the dye of the present invention are added.
However, the dye of the present invention is preferably all dyes added
50% or more of the amount, more preferably 70% or more, most preferably
Preferably, it is 90% or more. In the present invention, halogens other than sensitizing dyes
Silver halide adsorptive compounds (photographs adsorbed on silver halide grains)
Useful compounds, sometimes simply referred to as “photographic useful compounds”
Include anti-fogging agents, stabilizers, nucleating agents, etc.
It is done. Regarding anti-fogging agents and stabilizers, for example,
Research Disclosure (Research Disc)
closure) Volume 176 Item 17643 (RD1764)
3), 187 volume item 18716 (RD18716) and
Compound described in Volume 308, Item 308119 (RD308119)
Can be used. Also, as a nucleating agent, for example
U.S. Pat. Nos. 2,563,785 and 2,588,982
Hydrazines described in US Pat. No. 3,227,55
2, hydrazides, hydrazones, UK patents
1,283,835, JP-A 52-69613, 55
-138742, 60-11837, 62-2
10451, 62-291737, U.S. Pat.
615,515, 3,719,494, 3,73
4,738, 4,094,683, 4,115,1
22, 4306016, 4447104, etc.
Heterocyclic quaternary salt compounds, US Pat. No. 3,718,470
The pigment molecule has a nucleating substituent described in 1.
Sensitizing dye, U.S. Pat. No. 4,030,925, 4,0
31,127, 4,245,037, 4,255
511, 4,266,013, 4,276,36
4. Thiourine described in British Patent 2,012,443, etc.
Elementary Bonded Acylhydrazine Compounds, and US Pat.
080,270, 4,278,748, British Patent 2,
Thioamide rings and tria described in 011,391B etc.
Heterocyclic groups such as sol and tetrazole are bonded as adsorption groups.
Combined siahydrazine compounds are used. Preferred silver halide adsorption in the present invention
Is a nitrogen-containing compound such as thiazole or benzotriazole
Heterocyclic compounds, mercapto compounds, thioetherification
Compound, sulfinic acid compound, thiosulfonic acid compound,
Thioamide compounds, urea compounds, selenourea compounds and
And thiourea compounds, particularly preferably nitrogen-containing hetero
Ring compounds, mercapto compounds, thioether compounds and
And thiourea compounds, particularly preferably nitrogen-containing hetero
It is a ring compound. Nitrogen-containing heterocyclic compounds are represented by the general formula (XII)
A nitrogen-containing heterocyclic compound represented by (XIV) is preferred. [0158] Embedded image The compounds of the general formula (XII) are
A nitrogen-containing heterocyclic compound containing an imino group
The compound of general formula (XIII)
A nitrogen-containing heterocyclic compound containing a capto group, which is represented by the general formula (XI
V) Compounds containing thione groups (not compatible)
A compound of the general formula (XV)
It is a nitrogen-containing heterocyclic compound containing a monium group. Again this
May be in the form of a suitable salt. Where Q₁ , Q₂ ,
Q_Three , Q_Four Represents a nitrogen-containing heterocycle, for example, imidazole
Ring, benzimidazole ring, naphthimidazole ring,
Azole ring, benzothiazole ring, naphthothiazole
Ring, oxazole ring, benzoxazole ring, naphtho
Xazole ring, benzoselenazole ring, triazole
Ring, benzotriazole ring, tetrazole ring, azaine
Den ring (eg, diazaindene ring, triazaindene
Ring, tetrazaindene ring, pentazaindene ring), pre
Ring, thiadiazole ring, oxadiazole ring, serena
Diazole ring, indazole ring, triazine ring, pyrazo
Ring, pyrimidine ring, pyridazine ring, quinoline ring,
-Dannin ring, thiohydantoin ring, oxazolidinedio
Ring, phthalazine ring and the like. these
Of these, azaindene is preferred in general formula (XII).
Ring, (benzo) triazole ring, indazole ring, tri
These are azine ring, purine ring, tetrazole ring, etc.
In formula (XIII), a tetrazole ring, a triazole ring,
Nzo) imidazole ring, (benzo) thiazole ring,
Nzo) oxazole ring, thiadiazole ring, azainde
Ring, pyrimidine ring, etc., and in general formula (XIV),
(Benzo) thiazole ring, (benzo) imidazole ring,
(Benzo) oxazole ring, triazole ring, tetrazo
In general formula (XV), (benzo, naphth
G) thiazole ring, (benzo, naphtho) imidazole
Ring, (benzo, naphtho) oxazole ring and the like. Up
"(Benzo, naphtho) thiazole ring"
Azole ring, benzothiazole ring or naphthothiazole
"Lu ring" (the same applies to other cases). these
The heterocycle may have a suitable substituent, for example,
Droxyl group, alkyl group (methyl group, ethyl group, pen
Til group), alkenyl group (allyl group, etc.), alkyl
Len group (such as ethynyl group), aryl group (phenyl group,
Naphthyl group), aralkyl group (benzyl group, etc.),
Amino group, hydroxyamino group, alkylamino group (d
Tilamino group), dialkylamino group (dimethyla)
Mino groups), arylamino groups (such as phenylamino groups)
), Acylamino group (acetylamino group, etc.), reed
Group (acetyl group, etc.), alkylthio group (methylthio)
Group), carboxy group, sulfo group, alkoxyl group
(Such as ethoxy group), aryloxy group (phenoxy group, etc.)
), Alkoxycarbonyl group (methoxycarbonyl group)
Carbamoyl group which may be substituted, etc.
Sulfamoyl group, optionally substituted ureido group,
Group, halogen atom (chlorine atom, bromine atom, etc.), nito
In the group B, mercapto group, heterocyclic ring (pyridyl group, etc.)
is there. In the formula, R is an alkyl group (methyl group, ethyl
Group, hexyl group, etc.), alkenyl group (allyl group, 2-
Butenyl group), alkylene group (ethynyl group, etc.),
Aryl group (phenyl group, etc.), aralkyl group (benzi
Group, etc.), and these are further suitable substituents.
You may have. X − represents an anion (eg, halogen
Inorganic anions such as ON and p-toluenesulfonate
Represents an organic anion). Preferred among the above compounds
These are compounds of the general formulas (XII), (XIII), (XV).
Particularly preferred among the general formula (XII) is hydroxyl.
Substituted tetrazaindenes (compatible isomers and imino groups
Can be included). In general formula (XIII), an acidic group
Mercaptotetra having (carboxy group, sulfo group)
Sols. In general formula (XV), benzothiazole
It is a kind. Among the above compounds, the general formulas (XII) and (XIII)
These compounds combine with silver ions to form silver salts,
The solubility product of silver salt in water near room temperature is 10^-9-10
^-20 , Especially 5 × 10^-Ten -10^-18 A nitrogen-containing heterocycle
Compounds are preferred. The addition time of the photographic useful compound is determined by the sensitizing dye.
Whether it is before addition or after addition is complete
May be the period until the end of the addition, but preferably
Is the period before and after the addition of the sensitizing dye
More preferably, from the start to the end of the addition of the sensitizing dye.
This is the period until the end. The amount of photographic useful compound added is
It varies depending on the function of the additive and the type of emulsion, but typically
5 × 10^-Five~ 5 x10^-3mol / mol Ag. Next, a photographically useful compound that is adsorptive to particles is used.
A specific example is shown. Of course, the present invention is limited to these.
It is not a thing. [0162] Embedded image [0163] Embedded image [0164] Embedded image[0165] Embedded imageIn the present invention, the silver halide emulsion contains bromide.
Silver, silver chloride, silver iodobromide, silver iodochlorobromide, silver chlorobromide, chloroiodo odor
Silver chloride and the like are preferable. As the morphology of silver halide grains
May be a normal crystal such as octahedron, cube, tetrahedron
However, tabular grains are more preferred. First, halo which is the first emulsion relating to the present invention.
Chlorination in which the main plane with parallel silver halide grains is the (111) plane
Silver iodobromide or silver chloroiodobromide having a silver content of less than 10 mol%
The tabular silver halide grains formed will be described. The emulsion comprises an opposing (111) major surface and the
Consists of side surfaces connecting main surfaces. Tabular grain emulsion is iodobromide
Made of silver or silver chloroiodobromide. May contain silver chloride
However, the silver chloride content is preferably 8 mol% or less, more preferably
Or 3 mol% or less or 0 mol%. Contains silver iodide
The proportion is 40 mol% or less, preferably 20 mol.
% Or less. Silver iodide between grains irrespective of the silver iodide content
The variation coefficient of the content distribution is preferably 20% or less, particularly 1
0% or less is preferable. The silver iodide distribution has a structure within the grain.
Preferably it is. In this case, the silver iodide distribution structure is 2
Heavy structure, triple structure, quadruple structure and more
possible. In addition, the silver iodide content continuously changes inside the grain.
It may be converted. More than 50% of the total projected area has an aspect ratio of 2
Occupied by the above particles. Where tabular grain projected area
In addition to the reference latex sphere,
Electron micrograph by the carbon replica method with shadow
It can be measured from true. When tabular grains are viewed from above
In addition, it is usually in the form of a hexagon, a triangle or a circle
However, the diameter of a circle with an area equal to the projected area is divided by the thickness.
The value is the aspect ratio. Tabular grains are hexagonal
The higher the ratio, the better, and for each adjacent side of the hexagon
The length ratio is preferably 1: 2 or less. Tabular grains have a projected area diameter of 0.1 μm or more.
20.0 μm or less is preferable, 0.2 μm or more and 10.0
More preferable is μm or less. Projected area diameter is halogen
It is the diameter of a circle having an area equal to the projected area of silver halide grains. Ma
The thickness of the tabular grain is 0.01 μm or more and 0.5 μm or less.
Lower, preferably 0.02 to 0.4 μm
That's right. The thickness of the tabular grain is the distance between the two main planes.
The equivalent sphere diameter is preferably 0.1 μm or more and 5.0 μm or less.
More preferably 0.2 μm or more and 3 μm or less. Sphere
The diameter is the diameter of a sphere with a volume equal to the volume of an individual particle.
Diameter. The aspect ratio is 1 or more and 100 or less.
Is preferably 2 or more and 50 or less. Aspe
The ratio of the projected area of a particle divided by the thickness of the particle
Value. The silver halide grains of the present invention are monodisperse.
It is preferable. Spherical phase of all silver halide grains of the present invention
The coefficient of variation of this diameter is 30% or less, preferably 25% or less
is there. In the case of tabular grains, the variation coefficient of the projected area diameter
It is also important that the projected area of all silver halide grains of the present invention
The coefficient of variation in diameter is preferably 30% or less, more
Preferably it is 25% or less, more preferably 20% or less.
It is below. The variation coefficient of the thickness of the tabular grains is 30
% Or less, more preferably 25% or less,
More preferably, it is 20% or less. The coefficient of variation is individual
The standard deviation of the equivalent diameter distribution of silver halide grains is equivalent to the average
Divided by diameter or individual silver halide tabular grains
This is the standard deviation of the child thickness distribution divided by the average thickness.
The The tabular grain spacing of the present invention is determined by US patent
0.012 μm or less as described in No. 5219720
Or as described in JP-A-5-249585
(111) Main plane distance / twin plane spacing is set to 15 or more
You can choose according to your purpose. The higher the aspect ratio, the more remarkable the effect.
Therefore, the tabular grain emulsion preferably has 50% or more of the total projected area.
Preferably, it is occupied by particles having an aspect ratio of 5 or more. More
Preferably, the aspect ratio is 8 or more. aspect ratio
If the particle size becomes too large, the particle size distribution described above
As the coefficient of variation of the
The cut ratio is preferably 50 or less. The dislocation lines of tabular grains are described in, for example, J.A. F. Ha
milton, Photo. Sci. Eng. , 11, 5
7, (1967) and T.W. Shiozawa, J. et al. So
c. Photo. Sci. Japan, 35, 213,
(1972), the transmission electron microscope at low temperature is used.
Can be observed by direct methods. Snow
Do not apply enough pressure to generate dislocation lines from the emulsion to the grains.
Electron micrographs of silver halide grains taken out carefully
Damage on the mesh for mirror observation (pudding)
The permeation method with the sample cooled to prevent
Observe. At this time, the thicker the particle, the more the electron beam
High pressure type (0.25.
Those who use an electron microscope (200 kV or more for particles)
Can be observed more clearly. In this way
From the photograph of the obtained particle, the direction perpendicular to the main plane
Position and number of dislocation lines for each particle
Can be requested. The number of dislocation lines is preferably an average per particle.
10 or more. More preferably, an average of 20 per particle
More than a book. When dislocation lines are densely present, or
When dislocation lines are observed crossing each other,
Sometimes the number of dislocation lines cannot be clearly counted.
is there. However, even in these cases,
It can be counted as about 10, 20, or 30
It is possible, and clearly there are only a few
Can be separated. For the average number of dislocation lines per particle
Count the number of dislocation lines for more than 100 grains,
And ask. For example, the dislocation line is introduced near the outer periphery of the tabular grain.
You can enter. In this case, the dislocation is almost perpendicular to the outer circumference.
Yes, the length of the distance from the center of the tabular grain to the side (outer circumference)
The dislocation lines start from the position of x% and reach the outer periphery.
I'm alive. The value of x is preferably 10 or more and not 100
It is full, more preferably 30 or more and less than 99.
Also preferably, it is 50 or more and less than 98. At this time,
The shape created by connecting the position where the position line starts is the particle shape.
It is close to similarity, but it is not completely similar and may be distorted.
The This type of dislocation number is not found in the central region of the grain.
The direction of dislocation lines is crystallographically approximately (211).
Often meandering and crossing each other
There is also. Further, almost all over the outer periphery of the tabular grain.
Even if it has dislocation lines evenly,
You may have a dislocation line. That is, hexagonal flat plate halogen
Taking silver halide grains as an example, dislocations are only near the six vertices.
The line may be limited or near one of the vertices
The dislocation line may be limited only to the side. Conversely, the six peaks
It is possible that the dislocation line is limited to only the sides except near the point.
Noh. Further, the centers of two parallel principal planes of the tabular grain
Dislocation lines may be formed over a region including. main
If dislocation lines are formed over the entire plane,
The direction of the grid line is crystallographic when viewed from the direction perpendicular to the main plane.
It may be roughly (211) direction, but (110) direction
Or it may be randomly formed, and each
The length of the dislocation line is also random, and it is a short line on the main plane.
And reach the side (outer circumference) as a long line
May be observed. The dislocation line may be a straight line
It is often meandering. Also often exchange with each other
I'm not. The position of the dislocation line is as described above on the outer periphery or
It may be limited to the main plane or local position
And these may be combined and formed.
That is, it may exist on the outer periphery and the main plane at the same time.
Yes. This tabular grain emulsion contains silver iodide on the grain surface.
The content is preferably 10 mol% or less, particularly preferably
5 mol% or less. Contains silver iodide on the grain surface of the present invention
The amount is XPS (X-ray Photoelectron
  Measured using Spectroscopy. C
Used for analysis of silver iodide content near the surface of silver halide grains
As for the principle of the XPS method, Aihara et al.
"Light" (Kyoritsu Library-16, Kyoritsu Shuppan Publishing, Showa 53
Year). XPS standard measurement
The method uses Mg-Kα as the excitation X-ray and an appropriate sample
Iodine (I) and silver released from silver halide in the form
(Ag) photoelectrons (usually I-3d5 / 2, Ag-3d
This is a method of observing the intensity of 5/2). Find iodine content
Several standard samples with known iodine content.
Intensity ratio (strength of photoelectrons of iodine (I) and silver (Ag))
(I) / Intensity (Ag)) calibration curve was created, and this calibration curve
Can be found from. Halo in silver halide emulsions
Proteolytic enzyme from gelatin adsorbed on the surface of silver halide grains
XPS measurement must be performed after disassembly and removal
I have to. The silver iodide content on the grain surface is 10 mol%
The following tabular grain emulsions are the emulsion grains contained in one emulsion.
The silver iodide content was 10 moles when analyzed by XPS.
% Or less. In this case, clearly two or more
When emulsions are mixed, do not centrifuge or filter.
Analyzes of the same type of emulsion after appropriate pretreatment
It is necessary to do. The structure of the tabular grain emulsion of the present invention is, for example, bromide.
Triple structure grains composed of silver / silver iodobromide / silver bromide and
Higher order structures are also preferred. Of silver iodide content between structures
Even if the boundary is clear, it changes smoothly and continuously
Any of them may be used. Usually powder
In the measurement of silver iodide content using the X-ray diffraction method, it contains silver iodide.
There is no such thing as showing two distinct peaks with different amounts, high silver iodide
X-ray diffraction profile with a skirt in the direction of content
Indicate. The silver iodide content of the layer inside the surface is the surface
Preferably higher than the silver iodide content of
The silver iodide content of the inner layer is preferably at least 5 mol%
More preferably, it is 7 mol% or more. Next, the second emulsion, the second emulsion relating to the present invention, is used.
Row principal plane is (111) plane and has minimum length
The ratio of the length of the side having the maximum length to the length of the side is 2
The apex of hexagonal silver halide grains, and / or
Or less per particle on the side and / or main plane
For particles with at least one epitaxial junction
explain about. Epitaxially bonded particles are
In addition to the main body of the silver halide grain, the crystal part joined with the grain
In other words, it is a particle with an epitaxial part)
The crystal part usually protrudes from the silver halide grain body.
The Total amount of grains in the bonded crystal part (epitaxial part)
The ratio to is preferably 2% to 30%, preferably 5% or less
The upper 15% or less is more preferable. The epitaxial part is particles
It may exist in any part of the main body, but the particle main surface part, grains
A child edge part and a particle | grain corner part are preferable. Epitaxia
As for the number of the at least one or more, it is preferred. Also,
The halogen composition of the epitaxial part is AgCl, AgBr.
Cl, AgBrClI, AgBrI, AgI, AgSC
N and the like are preferable. If an epitaxial part exists,
Dislocation lines may exist inside the child, but even if they do not exist
good. Next, the first emulsion relating to the present invention and
A method for preparing the second emulsion silver halide grains will be described.
The The preparation process of the present invention includes (a) base grains
Child forming step and subsequent particle forming step ((b)
About). Basically (b) construction following (a) process
It is more preferable to perform the process, but only the step (a) may be performed.
Yes. Step (b) consists of (b1) dislocation introduction step, (b2) step
-Inner dislocation limited introduction process, or (b3) epitaxy
Any of the bonding processes, at least one of which
If you like, you may combine two or more. First, (a) the base particle forming step is explained.
Light up. The base part is based on the total amount of silver used for grain formation.
Preferably at least 50% or more, more preferably 6
0% or more. In addition, the iodine of the base part silver amount
The average content is preferably 0 to 30% mol
More preferably 0 mol% or more and 15 mol% or less.
Yes. The base part has a core-shell structure if necessary.
May be. At this time, the core part of the base part is the total silver amount of the base part.
50% or more and 70% or less is preferable, and the core
The average iodine composition is 0 mol% or more and 30 mol% or less
0 mol% or more and 15 mol% or less is more preferable.
Good. The iodine composition of the shell is 0 mol% or more and 3 mo
It is preferably 1% or less. As a method for preparing a silver halide emulsion,
After the formation of silver halide nuclei, further silver halide grains were formed.
A general method is to obtain particles of a desired size by extending the length.
Thus, the present invention is not changed. Flat plate
As for the formation of particle-like particles, at least nucleation, ripening,
A long process is included. This process is described in U.S. Pat. No. 4,945,037.
It is described in detail in the issue. 1. Nucleation Tabular grain nucleation generally holds an aqueous solution of gelatin
In a reaction vessel, a silver salt aqueous solution and an alkali halide aqueous solution
Double-jet method with addition of liquid or halo
Add silver salt solution to gelatin solution containing alkali genide
Single jet method is used. Also, if necessary
Alkaline halide aqueous solution in gelatin solution containing silver salt
A method of adding a liquid can also be used. In addition, it is necessary
Depending on the condition, the mixer disclosed in JP-A-2-44335
Add latin solution, silver salt solution and alkali halide aqueous solution
Add and immediately transfer it to the reaction vessel
Particle nucleation can also be performed. Also, U.S. Pat.
As disclosed in 04786, alkali halides
And pass the aqueous solution containing the protective colloid solution through the pipe
Nucleation can be performed by adding an aqueous silver salt solution.
Yes. In addition, the chlorine-containing composition described in US Pat. No. 6,226,681 is also included.
The amount is 10 mol% or more with respect to the amount of silver used for nucleation.
Some nucleation may be used. Nucleation is gelatin
Is used as a dispersion medium, and the dispersion medium is formed under the conditions of pBr of 1 to 4.
It is preferable. The types of gelatin include alkaline treatment.
Physical gelatin, low molecular weight gelatin (molecular weight: 3000-4
US Pat. No. 4,713,320 and US Pat.
942,120 oxidation-treated gelatin, and low
Molecular weight oxidized gelatin may be used. Especially small molecules
It is preferred to use an amount of oxidized gelatin. Dispersion medium
The concentration of is preferably 10% by mass or less, and more preferably 1% by mass
The following is more preferable. The temperature during nucleation is 5 to 60 ° C.
Although preferred, the fine particle tabular grains having an average particle diameter of 0.5 μm or less
When making a child, 5-48 degreeC is more preferable. P of dispersion medium
H is preferably 1 or more and 10 or less, but 1.5 or more and 9 or less.
Is more preferable. U.S. Pat. No. 5,147,77.
No. 1, No. 5,147,772, No. 5,147,7
73, 5,171,659, 5,210,
No. 013, No. 5,252,453, and Patent No. 3
Polyalkylene oxide compounds described in 089578
Nucleation process or later ripening process and growth
It is possible to add as much as possible. 2. Aging 1. In nucleation, fine particles other than tabular grains (special
To octahedral and single twin grains). Next
Eliminate grains other than tabular grains before entering the growing process.
Therefore, a nucleus that has a shape that should become tabular grains and has good monodispersity
Need to get. To make this possible, nucleation
It is well known to continue Ostwald ripening
The Adjust pBr immediately after nucleation, then increase temperature
Aging is performed until the hexagonal tabular grain ratio reaches the maximum. this
Sometimes a gelatin solution may be additionally added. Distribution at that time
The concentration of gelatin relative to the medium solution is 10% by mass or less
It is preferable. The additional gelatin used at this time is
Alkali-treated gelatin, modified with 95% or more amino groups
Like succinated gelatin or trimellitated gelatin
Amino group-modified gelatin described in JP-A-11-143002
Imidazole group described in JP-A-11-143003
Modified gelatin and oxidized gelatin are used. Special
Succinylated gelatin and trimellitated gelatin
It is preferable. Aging temperature is preferably 40-80 ° C
It is 50-80 degreeC, and pBr is 1.2-3.0.
is there. The pH is preferably 1.5 or more and 9 or less. Ma
At this time, grains other than tabular grains disappear quickly.
Therefore, a silver halide solvent may be added. in this case
The concentration of the silver halide solvent is 0.3 mol / liter or less
Is preferable, and 0.2 mol / liter or less is more preferable. Direct anti
When used as a diverting emulsion, use a silver halide solvent.
NH used on the alkaline side_Three More neutral, acidic
Silver halide solution such as thioether compound used on the side
An agent is preferred. Aged like this, almost ~ 100
% Tabular grains only. After ripening, the next growth
If a silver halide solvent is not required during the process:
Remove the silver halide solvent.   NH_Three In the case of alkaline silver halide solvents such as
HNO_Three An acid with a large solubility product with Ag + such as
In addition, disable it.   In the case of a thioether-based silver halide solvent,
H as described in 60-136736₂ O₂ Add oxidizing agents such as
And disable it. 3). growth PBr in the crystal growth period following the ripening process is 1.4-3.5
It is preferable to keep. In dispersion medium solution before entering the growth process
When gelatin concentration is low (1% by mass or less)
May be added. At that time, the
The latin concentration is preferably 1 to 10% by mass.
The gelatin used at this time is alkali-processed gelatin or aluminum.
Succinated gelatin or trio modified with 95% or more of mino group
Using merit gelatin and oxidized gelatin
The In particular, succinylated gelatin and trimellitated gelatin
Is preferably used. PH during growth is 2 or more and 10
Hereinafter, it is preferably 4 or more and 8 or less. However, Kaku
5 when gelatinized or trimellitated gelatin is present
8 or less is preferable. Ag during crystal growth⁺,
And the addition rate of halogen ions is the critical growth rate of the crystal.
20-100% crystal growth, preferably 30-100% crystal growth
It is preferable to make the speed. In this case, crystal formation
Addition rate of silver ion and halogen ion with length
In this case, the Japanese Patent Publication No. 48-36890, 52
-16364 as described in silver salt and halogen salt aqueous solution
The rate of addition may be increased, increasing the concentration of the aqueous solution.
May be. Add silver salt solution and halogen salt solution simultaneously
Can be performed by the double jet method.
4,672,027 and 4,693,964
A silver nitrate aqueous solution and a halogen aqueous solution containing bromide
It is preferable to add the silver iodide fine grain emulsion simultaneously. This
In this case, the growth temperature is preferably 50 ° C. or higher and 90 ° C. or lower.
Further, 60 ° C. or more and 85 ° C. or less is more preferable. Also added
AgI fine grain emulsion
It may be added while preparing continuously. At this time
The preparation method can be referred to JP-A-10-43570.
The average grain size of the added AgI emulsion is 0.005μm or more
0.1 μm or less, preferably 0.007 μm or more and 0.08
It is below μm. The iodine composition of the base particles is A
It can be changed depending on the amount of gI emulsion. Further, an aqueous silver salt solution and an aqueous halogen salt solution
It is preferable to add silver iodobromide fine grains instead of addition.
Good. At this time, the base particle for which the iodine amount of the fine particles is desired
The amount of iodine of the desired iodine composition
Disc particles are obtained. Silver iodobromide fine particles prepared in advance
If you want to add while continuously preparing
Is preferred. The size of the silver iodobromide fine particles to be added is 0.00.
005 μm or more and 0.1 μm or less, preferably 0.01 μm
It is 0.08 μm or less. Growth temperature is 50 ° C or higher
90 ° C or lower, preferably 60 ° C or higher and 85 ° C or lower
The Next, step (b) will be described. Ma
First, the step (b1) will be described. (B1) Step
It consists of a 1 shell process and a second shell process. Base mentioned above
A first shell is provided. The ratio of the first shell is preferably
1% or more and 30% or less of the total silver amount, and the average
The silver iodide content is 20 mol% or more and 100 mol% or less.
More preferably, the ratio of the first shell is 1% with respect to the total amount of silver.
20% or less, and the average silver iodide content is 25%.
% Or more and 100 mol% or less. The first shell to the base
Basically, the growth of silver nitrate solution contains iodide and bromide.
Add the aqueous halogen solution by double jet method. if
Or double the silver nitrate aqueous solution and the halogen aqueous solution containing iodide.
Add by Ludgett method. Or halogen containing iodide
Add aqueous solution by single jet method. In any of the above methods, a combination of them
It can be used. From the average silver iodide content of the first shell
However, in addition to the silver iodobromide mixed crystal when the first shell is formed,
Silver iodide can precipitate. In any case, usually the next
During the formation of the two shells, the silver iodide disappears and all is silver iodobromide
Change to mixed crystal. As a preferred method for forming the first shell, iodine is used.
Add silver bromide or silver iodide fine grain emulsion, ripen and dissolve
There is a way to do it. Further, as a preferable method, silver iodide fine
Add a grain emulsion and then add an aqueous silver nitrate solution.
There is a method to add silver nitrate aqueous solution and halogen aqueous solution.
The In this case, the silver iodide fine grain emulsion is dissolved in a silver nitrate aqueous solution.
The silver iodide fine particle milk added is accelerated by the addition of the solution.
The amount of silver in the agent is used as the first shell, and the silver iodide content is 100.
Mole%. Then add the aqueous silver nitrate solution to the second shell.
Calculate as The silver iodide fine grain emulsion is added rapidly.
It is preferable. The rapid addition of silver iodide fine grain emulsion is:
The silver iodide fine grain emulsion is preferably added within 10 minutes.
Say. More preferably, it should be added within 7 minutes
Yeah. These conditions are the temperature of the system to be added, pBr, pH, gel
Types and concentrations of protective colloids such as tin, silver halide soluble
It may vary depending on the presence, type, concentration, etc. of the agent.
The shorter one is preferable. Nitric acid when added
It is preferable not to add an aqueous silver salt solution such as silver.
The temperature of the system at the time of addition is preferably 40 ° C. or higher and 90 ° C. or lower,
50 ° C. or more and 80 ° C. or less is particularly preferable. The silver iodide fine grain emulsion should be substantially silver iodide.
As long as it can be a mixed crystal, silver bromide and / or
Alternatively, it may contain silver chloride. Preferably 100%
It is silver iodide. Silver iodide has β-form and γ-form in its crystal structure.
As described in US Pat. No. 4,672,026.
As shown, there can be an α-form or an α-form-like structure. Book
In the invention, the crystal structure is not particularly limited,
A mixture of β-form and γ-form, more preferably β-form is used.
The Silver iodide fine grain emulsion is disclosed in US Pat. No. 5,004,679.
It may be formed just before the addition described in No.
Any of those that have undergone a normal washing process may be used.
In the light, it is preferable to use those that have undergone a normal washing process.
I can. A silver iodide fine grain emulsion is disclosed in US Pat.
It can be easily formed by the method described in No. 2,026. grain
Silver salt water that forms particles with a constant pI value during child formation
Double jet addition method of solution and iodide salt aqueous solution is preferred
Yes. Where pI is the I of the system^-Is the logarithm of the inverse of the ion concentration.
The Protective colloid agent such as temperature, pI, pH, gelatin
Type, concentration, presence / absence of silver halide solvent, type, concentration, etc.
Although there is no particular limitation, the particle size is 0.1 μm or less.
More preferably, 0.07 μm or less is convenient for the present invention.
The particle shape cannot be completely specified because it is a fine particle.
The variation coefficient of the particle size distribution is preferably 25% or less.
In particular, when it is 20% or less, the effect of the present invention is remarkable. This
Here, the size and size distribution of the silver iodide fine grain emulsion are
Silver fine particles are placed on a mesh for electron microscope observation
Observe directly by transmission method, not Bon replica method
Ask. This is because of the small particle size,
This is because the measurement error increases when observing with the Preca method.
The The particle size has a projected area equal to the observed particle.
It is defined as the diameter of the circle to be. About particle size distribution
Is also determined using this equal projected area circle diameter. The present invention
The most effective silver iodide fine grain in the
6 μm or less and 0.02 μm or more, and the particle size distribution
The coefficient of variation is 18% or less. The silver iodide fine grain emulsion is preferably used after the above grain formation.
More preferably, as described in U.S. Pat. No. 2,614,929.
Ordinary water washing and protective colloid such as pH, pI, gelatin
Agent concentration adjustment and silver iodide concentration adjustment
The The pH is preferably 5 or more and 7 or less. pI value of silver iodide
PI value at which solubility is lowest or p higher than that value
It is preferable to set to I value. As protective colloid agent
Is preferably normal gelatin having an average molecular weight of about 100,000
Used. Low molecular weight gelatin with an average molecular weight of 20,000 or less
Preferably used. Gelatin with different molecular weight
It may be convenient to use a mixture. Emulsion 1k
The amount of gelatin per g is preferably 10g or more and 100g
It is as follows. More preferably, it is 20 g or more and 80 g or less.
The The silver amount in terms of silver atoms per kg of emulsion is preferably
It is 10 g or more and 100 g or less. More preferably 20g
It is 80 g or less. Gelatin amount and / or silver amount
Select a value suitable for abrupt addition of silver iodide fine grain emulsion.
It is preferable to select. The silver iodide fine grain emulsion is usually dissolved in advance.
However, at the time of addition, the stirring efficiency of the system is sufficiently increased.
It is necessary to Preferably, the stirring speed is higher than usual.
Set to Defoaming to prevent foam generation during agitation
The addition of the agent is effective. Specifically, US Pat. No. 5,
An antifoaming agent described in Examples of No. 275,929
Used. As a more preferable method for forming the first shell,
Conventional iodide ion supply method (free iodide ion
In place of US Pat. No. 5,496,6
Using the iodide ion releasing agent described in No. 94,
Halogenation containing silver iodide while rapidly generating on
A silver phase can be formed. The iodide ion releasing agent is an iodide ion releasing agent.
Iodine by reaction with a nodule (base and / or nucleophile)
, Which is a nucleophile used in this case.
Preferably, the following chemical species are mentioned. For example, water
Oxide ion, sulfite ion, hydroxylamine,
Osulfate ion, metabisulfite ion, hydroxamic acid
, Oximes, dihydroxybenzenes, mercapta
, Sulfinates, carboxylates, ammonia, amines
Mines, alcohols, ureas, thioureas, pheno
Hydrazines, hydrazides, semicarbazides
, Phosphines, sulfides. Bases and
Control nucleophile concentration, addition method, and reaction temperature.
Iodide ion release rate by rolling, time
Can be controlled. Preferred as a base
Alternatively, alkali hydroxide is used. Iodide ion suddenly
Iodide ion release agents and iodine used for intense production
The preferred concentration range of the fluoride ion release regulator is 1 × 10^-7
~ 20M (mole), more preferably 1 x 10^-Five~
10M, more preferably 1 × 10^-Four~ 5M, especially preferred
Or 1 × 10^-3~ 2M. Concentration exceeds 20M
High molecular weight iodide ion releaser and iodide ion
The amount of release agent added is large relative to the capacity of the particle formation container.
It is not preferable because it is too much. Further, 1 × 10^-7Below M, iodide Io
The ion release reaction rate slows down and the iodide ion releasing agent
It is not preferable because it is difficult to generate the selenium. A preferred temperature range is 30 to 80 ° C.
More preferably, it is 35-75 degreeC, Most preferably, it is 35-6.
0 ° C. Iodination generally at high temperatures above 80 ° C
The product ion release reaction rate becomes extremely fast, and
In general, iodide ion release kinetics are extremely low at lower temperatures.
Each of which is preferable due to limited usage conditions.
Yes. Where a base is used in releasing iodide ions
In this case, a change in liquid pH may be used. At this time, iodide Io
Preferred for controlling release rate and timing
The correct pH range is 2-12, more preferably 3-12.
11, particularly preferably 5-10, most preferably after adjustment
PH is 7.5-10.0. pH 7 under neutral conditions
But the hydroxide ion determined by the ion product of water is the regulator.
Acts as Further, a nucleophile and a base may be used in combination,
At this time, the pH is controlled within the above range,
You can control the on-release speed and timing.
Yes. An iodide atom is released from an iodide ion releasing agent.
When releasing in the form of ions, release all iodine atoms.
Or some of them may remain without being disassembled. A flat having the base and the first shell described above.
A second shell is provided on the plate particles. Second shell ratio is good
Preferably it is 10 mol% or more and 40 mol% or less with respect to the total silver amount.
The average silver iodide content is 0 mol% or more and 5 mol
% Or less. More preferably the ratio of the second shell is all silver
15 mol% or more and 30 mol% or less with respect to the amount,
The average silver iodide content is 0 mol% or more and 3 mol% or less.
The Second on a tabular grain having a base and a first shell
The growth of the shell tends to increase the aspect ratio of the tabular grains
However, it may be lowered. Basically silver nitrate aqueous solution and odor
Add halogen aqueous solution containing fluoride by double jet method
As a result, the second shell grows. Or
After adding an aqueous halogen solution containing bromide, aqueous silver nitrate solution
The liquid may be added by a single jet method. System temperature,
pH, type and concentration of protective colloids such as gelatin, halo
Presence, type, concentration, etc. of silver halide solvent will vary widely
The For pBr, in the present invention, the formation of the layer is completed.
The pBr at the end is higher than the pBr at the initial stage of the formation of the layer.
It is preferable. Preferably pBr at the initial stage of formation of the layer
Is 2.9 or less, and the pBr at the end of formation of the layer is 1.7.
That's it. More preferably, pBr in the initial stage of formation of the layer
Is 2.5 or less, and pBr at the end of formation of the layer is 1.9.
That's it. Most preferably, the initial pBr of the layer is
2.3 or less and 1 or more. Most preferably at the end of the layer
PBr is 2.1 or more and 4.5 or less. (B1) Dislocation lines exist in the part of step
It is preferable. Dislocation lines exist near the edge of tabular grains.
Preferably present. The vicinity of the edge is the tabular grain
The outer periphery (edge) of the six sides and its inner part, ie
(B1) A portion grown in the process. Edge part
The average number of dislocation lines present in each particle is 10 or more.
Yes. More preferably, the average number is 20 or more per particle.
When dislocation lines are densely present, or dislocation lines are
Number of dislocation lines per particle when crossed
May not be clearly counted. But
However, in these cases, approximately 10 or 20
It is possible to count as many as 30 books.
It can be distinguished from the case where there are only a few. Dislocation line
The average number of particles per particle is over 100 particles
Then, the number of dislocation lines is counted and obtained as a number average. The tabular grain of the present invention has a dislocation dose distribution between grains.
Is desirable to be uniform. The emulsion of the present invention is equivalent to one grain.
All silver halide grains containing 10 or more dislocation lines
It is preferable to occupy 100 to 50% (number) of children
More preferably 100 to 70%.
Or 100 to 90%. [0211] Below 50%, good in terms of homogeneity between particles.
It ’s not good. In the present invention, the ratio of particles containing dislocation lines and
When determining the number of dislocation lines, at least 100 particles
It is preferable to directly observe the dislocation line for
More preferably 200 particles or more, particularly preferably 300 particles.
Observe over particles. Next, step (b2) will be described. one
The second mode is to use iodide ions only near the top.
The method of more dissolution, the second aspect is a silver salt solution and
A method of simultaneously adding an iodide salt solution, a third embodiment and
Use a silver halide solvent,
Dissolution method, the fourth aspect is halogen conversion
There is a way through. According to the iodide ion which is the first embodiment
A method of dissolving will be described. Iodide on base particles
By adding ON, the vicinity of each vertex of the base particle dissolves.
Rounded. Continue with silver nitrate and bromide solutions.
Or a mixture of silver nitrate solution, bromide solution and iodide solution
When added simultaneously, the grains grow and dislocations near the top
Is introduced. Regarding this method, Japanese Patent Laid-Open No. 4-149.
541 and JP-A-9-189974
come. Iodide ions added in this embodiment
The total amount of iodide ions is the total number of moles of iodide ions,
The value obtained by dividing the value divided by the number of moles by 100 is I2 (mol
%), The silver iodide content of the base grain I1 (mol)
%)), (I2-I1) satisfies 0 or more and 8 or less
Is preferred for obtaining effective dissolution according to this embodiment,
More preferably, it is 0 or more and 4 or less. Iodide ions added in this embodiment
The concentration of is preferably low, specifically 0.2 mol / liter.
It is preferable that the concentration is not more than a tuttle, more preferably
Is 0.1 mol / liter. Also, when iodide ion is added
The pAg is preferably 8.0 or more, more preferably 8.
5 or more. By addition of iodide ions to the base particles
Following dissolution of the apex of the base particle, the silver nitrate solution alone
Addition, silver nitrate solution and bromide solution, or glass
Simultaneously mix a mixture of silver acid solution, bromide solution and iodide solution
To further grow the grains and introduce dislocations near the top
The The silver salt solution and iodide salt which are the second embodiment
The method by simultaneous addition with a solution is demonstrated. Base grain
Add silver salt solution and iodide salt solution rapidly to the child
Of silver iodide or silver iodide content at the top of the grain
It is possible to epitaxially produce high silver halide.
come. At this time, preferred addition of the silver salt solution and the iodide salt solution.
The acceleration is from 0.2 minutes to 0.5 minutes, more preferably
0.5 to 2 minutes. Regarding this method,
Since it is described in detail in No. 4-149541, reference
Can be made. . By addition of iodide ions to the base particles
Following dissolution of the apex of the base particle, the silver nitrate solution alone
Addition, silver nitrate solution and bromide solution, or glass
Simultaneously mix a mixture of silver acid solution, bromide solution and iodide solution
To further grow the grains and introduce dislocations near the top
The Using the silver halide solvent of the third embodiment
Explain the method. In the dispersion medium containing the base particles
After adding silver halide solvent, silver salt solution and iodide salt solution
Are added together with the group dissolved by the silver halide solvent.
High silver iodide or silver iodide content at the top of the disc grain
Silver halide will grow preferentially. On this occasion,
Silver salt solution and iodide salt solution need to be added quickly
Absent. With respect to this method, JP-A-4-149541
It can be referred to because it is described in detail. By adding iodide ions to the base particles
Following dissolution of the apex of the base particle, the silver nitrate solution alone
Addition, silver nitrate solution and bromide solution, or glass
Simultaneously mix a mixture of silver acid solution, bromide solution and iodide solution
To further grow the grains and introduce dislocations near the top
The Next, halogen conversion which is the fourth embodiment is performed.
The method to be described will be described. Epitaxia for base particles
Growth site support (hereinafter referred to as site director)
E.g., sensitizing color described in JP-A-58-108526
Top of base particles by adding elemental or water-soluble iodide
After forming silver chloride epitaxial on
To add silver chloride to silver iodide or silver iodide
It is a method of converting halogen to silver halide with a high content
The Site director is sensitizing dye, water-soluble thiocyan
Acid ions and water-soluble iodide ions can be used
However, iodide ions are preferred. Iodide ions are base grains
0.0005 to 1 mol%, preferably 0.0
01-0.5 mol% is preferable. Optimal amount of iodide Io
Add silver salt solution and chloride salt solution at the same time.
Then, silver chloride epitaxial is formed at the top of the base grain
it can. Halogen change by iodide ion of silver chloride
The replacement will be described. Highly soluble silver halide is soluble
Halogens capable of forming silver halides with lower resolution
By adding on, the less soluble halogen
Converted to silver chloride. This process is called halogen conversion
For example, as described in US Pat. No. 4,142,900
The Silver chloride epitaxially grown on the top of the substrate
By selectively halogen-converting with an arsenide ion,
A silver iodide phase is formed at the top of the disk grain. For details, see
No. 4-149541. [0224] Epitaxially grown on top of the base particles.
Silver chloride into the silver iodide phase by the addition of iodide ions
Following halogen conversion, single addition of silver nitrate solution, or
Is a silver nitrate solution and bromide solution, or a silver nitrate solution and
Add a mixture of bromide solution and iodide solution simultaneously to add grains
The child is further grown and a dislocation is introduced near the apex. (B2) Dislocation lines exist in the part of step
It is preferable. Dislocation lines are near the corners of tabular grains
Preferably it is present. Near the corner is the particle
Is it a point at x% from the center of the straight line connecting the center and each vertex?
When a perpendicular line is drawn on the edge that makes each vertex,
It is a three-dimensional part surrounded by the sides. This x
The value is preferably 50 or more and less than 100, more preferably 75.
It is less than 100. The dislocation line at the edge is 1
An average of 10 or more per particle is preferred. More preferably 1
An average of 20 or more per particle. Dislocation lines are densely present
Or when dislocation lines are observed crossing each other
The number of dislocation lines per particle should be clearly counted.
May not be possible. However, in these cases
However, about 10, 20, 30
Can count, and obviously there are only a few
It can be distinguished from the case of no. The number of dislocation lines per particle
For the average number, the number of dislocation lines is the number of 100 grains or more.
It is calculated as a number average. The tabular grain of the present invention has a dislocation dose distribution between grains.
Is desirable to be uniform. The emulsion of the present invention is equivalent to one grain.
All silver halide grains containing 10 or more dislocation lines
It is preferable to occupy 100 to 50% (number) of children
More preferably 100 to 70%.
Or 100 to 90%. Below 50%, good in terms of homogeneity between particles.
It ’s not good. In the present invention, the ratio of particles containing dislocation lines and
When determining the number of dislocation lines, at least 100 particles
It is preferable to directly observe the dislocation line for
More preferably 200 particles or more, particularly preferably 300 particles.
Observe over particles. Next, the step (b3) will be described. Base
On the epitaxial formation of silver halide on disc grains.
As described in U.S. Pat. No. 4,435,501.
In addition, iodide ions and amino acids adsorbed on the surface of the base particles
Sitedirector such as Zainden or spectral sensitizing dye
Where silver salt epitaxial is selected by the
For example, it can be formed at the edge or corner of the base particle
It has been shown. Also, Japanese Patent Laid-Open No. 8-69069
Is silver salt epitaxy at selected sites of ultrathin tabular grain base
This epitaxial phase is optimally chemically amplified.
Sensitivity has been achieved. In this aspect
However, these methods are used to enhance the sensitivity of the base particles of this embodiment.
It is highly preferred. Site director
Noazaindene or spectral sensitizing dyes may be used
Use iodide ion or thiocyanate ion
Can be used according to the purpose
And may be combined. Sensitizing dye amount, iodide Io
And the amount of thiocyanate ion added can be changed.
Then, the formation site of the silver salt epitaxial is
Can be limited to wedges or corners. Attendant
The amount of iodide ion added is relative to the amount of silver in the base grain.
0.0005 to 1.0 mol%, preferably 0.001
-0.5 mol%. The amount of thiocyanate ion
Is 0.01 to 0.2 mol relative to the silver content of the base particles
%, Preferably 0.02 to 0.1 mol%. this
After adding the site director, silver salt solution and halogen salt
The solution is added to form a silver salt epitaxial. On this occasion
The temperature is preferably 40 to 70 ° C and 45 to 60 ° C.
Further preferred. In this case, the pAg is preferably 7.5 or less.
More preferably, it is 6.5 or less. Site director
By using the
A silver salt epitaxial layer is formed in the wedge portion. Thus
The obtained emulsion was subjected to epitaxy as described in JP-A-8-69069.
It may be enhanced by selectively chemically sensitizing the char phase.
However, following the silver salt epitaxial formation,
A halogen salt solution may be added simultaneously for further growth.
The halogen salt aqueous solution added at this time is a bromide salt solution,
Alternatively, a mixture of bromide salt solution and iodide salt solution is preferred.
Good. The temperature at this time is preferably 40-80 ° C.
Furthermore, 45-70 degreeC is still more preferable. In addition, pA at this time
g is preferably 5.5 or more and 9.5 or less, and 6.0 or more and 9.
0 or less is preferable. (B3) Epitaxy formed in step
Char is basically outside the base particles formed in step (a).
A halogen composition different from the base particle is formed
It is characterized by that. The epitaxial composition is AgC
l, AgBrCl, AgBrClI, AgBrI, Ag
I, AgSCN and the like are preferable. Also epitaxial layer
In Japanese Patent Application Laid-Open No. 8-69069.
It is even more preferable to introduce “pant (metal complex)”
Yes. Epitaxial growth is at the corner of the base particle
Part, edge part, or at least part of the main plane part,
It may span multiple locations. Only in the corner, if
Or only the edge, or corner and edge
It is preferable to take the form of (B3) There is no dislocation line in the part of the step.
It is better to have dislocation lines.
Yes. The dislocation line is the junction between the base particle and the epitaxial growth part.
It is preferable to exist in the part or epitaxial part
Yes. Dislocations present at the junction or epitaxial part
The average number of lines per particle is preferably 10 or more. More preferred
Or an average of 20 or more per particle. Dislocation lines are dense
Or dislocation lines cross each other and are observed
The number of dislocation lines per particle is clearly counted.
It may not be possible. However, these
In some cases, about 10, 20, or 30
It is possible to count as much as possible, obviously only a few
It can be distinguished from the case where it does not exist. One particle per dislocation line
The average number of dislocation lines for 100 grains or more
Count the numbers and find the number average. In the formation of the epitaxial part, 6 cyano metal
It is preferred that the complex is doped. 6 cyano metal complex
Of the body, iron, ruthenium, osmium, cobalt,
Those containing palladium, iridium or chromium are preferred.
Yes. The amount of metal complex added is 1 per mole of silver halide.
0^-910^-2Preferably in the molar range, halo
10 per mole of silver halide^-810^-FourIn the range of moles
More preferably. Metal complexes can be water or organic
It can be added by dissolving in a medium. Organic solvent mixed with water
It is preferable to have compatibility. Examples of organic solvents include al
Coles, ethers, glycols, ketones, S
Tells and amides are included. The metal complex is represented by the following formula (I):
The 6-cyano metal complex is particularly preferred. 6 cyano metal complex
Provides a high-sensitivity light-sensitive material and a longer life of light-sensitive material.
Effect of suppressing the occurrence of covering even when stored for a period
Have (I) [M (CN)₆]^n- (Wherein M is iron, ruthenium, osmium, cobalt,
Rhodium, iridium or chrome, n is 3 or
Is 4. ) Specific examples of 6-cyano metal complexes are shown below. (I-1) [Fe (CN)₆ ]^Four- (I-2) [Fe (CN)₆ ]^3- (I-3) [Ru (CN)₆ ]^Four- (I-4) [Os (CN)₆ ]^Four- (I-5) [Co (CN)₆ ]^3- (I-6) [Rh (CN)₆ ]^3- (I-7) [Ir (CN)₆ ]^3- (I-8) [Cr (CN)₆ ]^Four-. The counter cation of the 6 cyano complex is miscible with water.
It is easy to use and is suitable for silver halide emulsion precipitation.
It is preferable to use ON. Examples of counter ions include Al
Potassium metal ions (eg, sodium ion, potassium ion)
, Rubidium ion, cesium ion, lithium ion
), Ammonium ions and alkylammonium
Ions are included. The tabular grain of the present invention has a dislocation dose distribution between grains.
Is desirable to be uniform. The emulsion of the present invention is equivalent to one grain.
All silver halide grains containing 10 or more dislocation lines
It is preferable to occupy 100 to 50% (number) of children
More preferably 100 to 70%.
Or 100 to 90%. Below 50%, good in terms of homogeneity between particles.
It ’s not good. In the present invention, the ratio of particles containing dislocation lines and
When determining the number of dislocation lines, at least 100 particles
It is preferable to directly observe the dislocation line for
More preferably 200 particles or more, particularly preferably 300 particles.
Observe over particles. The protective copolymer used in the preparation of the emulsion of the present invention.
As a Lloyd and other hydrophilic colloid layer vine
It is advantageous to use gelatin as a catalyst, but
Other hydrophilic colloids can also be used. example
For example, gelatin derivatives, graphs of gelatin and other polymers
Proteins such as polymers, albumin, casein;
Droxyethyl cellulose, carboxymethyl cellulose
Cellulose derivatives such as cellulose sulfates
Body, sugar derivatives such as sodium alginate, starch derivatives;
Polyvinyl alcohol, polyvinyl alcohol partial ace
Tar, poly-N-vinylpyrrolidone, polyacryl
Acid, polymethacrylic acid, polyacrylamide, polyvinylidene
Such as ruimidazole and polyvinylpyrazole
Or use various synthetic hydrophilic polymer materials such as copolymers.
Can be. As gelatin, lime-processed gelatin
In addition to acid-treated gelatin and Bull. Soc. Sci.
Photo. Japan. No. 16. P30 (196
Enzyme-treated gelatin as described in 6) may be used.
In addition, gelatin hydrolyzate and enzyme degradation product are also used.
be able to. Preferably, the amino group is 95% or more modified
Succinated gelatin and trimellitated gelatin
Or low-molecular-weight gelatin
Tin, and low molecular weight oxidized gelatin
preferable. In addition, 3 components with a molecular weight distribution of 280,000 or more
Gelatin containing 0% or more, preferably 35% or more
It may be used. Lime-processed gelatin is based on its molecular weight.
Sub α (low molecular weight), α (molecular weight about 100,000), β
(Molecular weight about 200,000), γ (molecular weight about 300,000) and Otaka
It consists of a molecular part (void: molecular weight greater than 300,000). So
The ratio of each component, ie the molecular weight distribution, is internationally
It is measured by the prescribed PAGI method. More detailed theory
The details and the manufacturing method are described in JP-A-11-237704.
Has been described. The emulsion of the present invention was washed with water for desalting and fresh.
It is preferable to prepare a protective colloid dispersion prepared in advance. This
The protective colloids used in this case are the hydrophilic colloids and
Latin can be used. At this time, the molecular weight distribution is 2
Contains more than 80,000 components over 30%, preferably over 35%
It is preferable to use gelatin. Washing temperature
Can be selected according to the purpose, but is selected in the range of 5 ° C to 50 ° C.
It is preferable. The pH at the time of washing can be selected according to the purpose, but 2
It is preferable to select between -10. More preferably 3
It is the range of ~ 8. The pAg at the time of washing can also be selected according to the purpose
Is preferably selected between 5 and 10. As a method of washing with water
Noodle washing, dialysis using semipermeable membrane, centrifugation
Method, coagulation sedimentation method, ion exchange method
be able to. In the case of coagulation sedimentation, use of sulfate
Method, using organic solvent, using water-soluble polymer
Method, method using gelatin derivatives, etc.
Yes. Silver halide of the third emulsion relating to the present invention
The main plane in which the grains are parallel has a (100) plane silver chloride content of 10
Flat plate made of less than mol% silver iodobromide or silver chloroiodobromide
The silver halide grains will be described below. The {100} tabular grains relating to the present invention are all
50-100% of the projected area, preferably 70-100%, more preferred
Or 90 to 100% of the average aspe
It consists of tabular grains having a cut ratio of 2 or more. Particle thickness is 0.01
~ 0.10μm, preferably 0.02 ~ 0.08μm, more preferably
0.03 ~ 0.07μm, aspect ratio is 2 ~ 100, preferable
Or 3 to 50, more preferably 5 to 30. Change in particle thickness
Dynamic coefficient (100 minutes of “standard deviation of distribution / average particle thickness”)
Rate, hereinafter referred to as COV.) Is 30% or less, preferably 25% or less
Lower, more preferably 20% or less. This COV is small
As shown, the monodispersity of the particle thickness is high. The equivalent-circle diameter and thickness of the tabular grains are:
Take a transmission electron microscope (TEM) photo by the replica method
To determine the equivalent circle diameter and thickness of each particle. in this case,
The thickness is calculated from the length of the shadow of the replica.
The measurement of COV. In the present invention is at least 600 or more.
It is the result measured about particle | grains. A set of {100} tabular grains relating to the present invention
The composition is silver chloroiodobromide having a silver chloride content of less than 10 mol% or
Silver iodobromide. Other silver salts such as rodin
Silver, silver sulfide, silver selenide, silver telluride, silver carbonate, phosphoric acid
Silver, organic acid silver, etc. as separate grains or silver halide
It may be included as part of the particles. Method for examining halogen composition in AgX crystal
As the X-ray diffraction method, the X-ray diffraction method is known. About X-ray diffraction
Are described in detail in Basic Analytical Chemistry Course 24 “X-ray diffraction” etc.
It is. Typically, AgX using Cu Kβ radiation as the source
The diffraction angle of the (420) plane is determined by the powder method. When the diffraction nucleus 2θ is obtained, it is determined from the black equation.
The child constant a is obtained as follows. 2 d sinθ = λ d = a / (h2 + k2 + l2) 1/2 Where 2θ is the diffraction angle of the (h k l) plane, λ is the X-ray wavelength,
d is the (h k l) plane spacing. Silver halide solid solution
The relationship between the halogen composition and the lattice constant a is already known
So (for example, “The Theory of Photograp
hic Process. 4thEd. "Described in Macmillian New York"
If the lattice constant is known, the halogen composition can be determined.
Yes. {100} Tabular grains related to the present invention
The rogen composition structure may be anything. For example
A and shell have different halogen composition (core / shell) 2
Many having a structured particle or core and two or more shells
An example is a particle having a heavy structure. As the composition of the core
Silver bromide is preferred but not limited to this. Ma
The shell composition should have a higher silver iodide content than the core.
preferable. The {100} tabular grains relating to the present invention are:
Average silver iodide content of 2.3 mol or more and average surface iodide
The silver content is preferably 8% or more. Also
Coefficient of variation between grains of silver halide content should be less than 20%
Is more preferable. For the surface silver iodide content, use the XPS described above.
Can be measured. [0250] Shape {100} tabular grains according to the present invention.
The following 6 can be enumerated when classified by state.
(1) Particles whose main plane is a right-angled parallelogram. (2)
One or more of the four corners of the right-angled parallelogram, preferably
1 to 4 particles missing non-equivalently. Ie [(maximum missing part
Area / minimum missing area = particles with K1 of 2 to ∞)]
(3) Particles in which the four corners are equivalently missing (K1 is 2
Small particles), (4) 5-100% of the area of the side surface of the missing part,
Preferably 20-100% of the particles are {111} faces. (Five)
At least two of the four sides that make up the principal plane
(6) the right parallel four
One or more of the four corners of the side, preferably 1-4
Particles missing in the shape of a square parallelogram. These are electron microscopes
This can be confirmed by the observation used. Table of {100} tabular grains relating to the present invention
The ratio of {100} faces to the crystal habit of faces is 80% or more, preferably
It is more than 90%, but it is about the electron microscope of particles.
Statistical estimates can be made using microscopic photographs. emulsion
The ratio of {100} tabs in the AgX grains is almost 100%.
If it is close, check the above estimate using the following method.
You can also. The method is the Chemical Society of Japan paper 1984, N
o.6, 942p, with a certain amount of the {1
00} Change the amount of benzothiocyanine dye in tabular grains
Adsorbed at 40 ° C for 17 hours, and unit milk from light absorption at 625 nm
Total surface area of all particles per agent (S) and {100}
Find the total area of the surface (S1), and based on these values,
Formula: Calculate {100} face ratio by S1 / S × 100 (%)
It is a method. The flatness of {100} tabular grains according to the present invention
The equivalent sphere diameter is preferably less than 0.35 μm. grain
The child size is estimated by the replica method and the projected area.
It can be determined by measuring the thickness. {100} tabular grains relating to the present invention are grains.
Electron trapping zones by doping with polyvalent metal ions during the formation of children.
Is preferably introduced. Contains polyvalent metal ions
Concentration is 1 × 10^-Five1 x 10 from moles / mole topical silver^-3Mo
Lu / mol local silver occupies 5% or more and 30% or less of the particle volume
Say the part you want. Concentration of polyvalent metal ions is 5x
10^-Five5 x 10 mol / mol topical silver^-FourMol / mol topical
Silver is more preferable. The concentration of polyvalent metal ions is uniform.
is required. To be uniform is into the metal ion particles.
Is introduced at a constant amount per unit silver amount, and for grain formation
At the same time as the silver nitrate used, polyvalent metal ions are used to form particles.
Introducing into a container. At this time, halogen solution
It may be added at the same time. Including the polyvalent metal ion of the present invention
The compound may be added as an aqueous solution or a polyvalent metal ion.
Preparation of fine particles doped or adsorbed with compounds
And may be added. The electron capture zone is located anywhere in the particle.
May be. There are two or more electron capture zones in the particle.
It's okay. Silver halide of the fourth emulsion relating to the present invention
The main plane with parallel particles is the (111) plane or (100)
Surface with an aspect ratio of 2 or more and at least 8
About tabular grains containing 0 mol% or more of silver chloride
I will explain below. To produce (111) grains with high silver chloride
Need special ingenuity. Wey's US Patent No. 43
No. 99215 High silver chloride tabular grains using ammonia
A manufacturing method may be used. Maskasky United States
Patent No. 5061617 uses thiocyanate
Alternatively, a method of producing high silver chloride tabular grains may be used. After
In the high silver chloride grains shown below, the (111) plane is the outer surface.
In order to form the particles, the additive (crystal phase
A method of adding a control agent) may be used. It is shown below. Patent Number Crystal Phase Control Agent Inventor   US Patent No. 4400463 Azaindenes + Muscasky                               Thioether peptizer   U.S. Pat. No. 4,783,398 2-4-dithiazolidinone   US Pat. No. 4,713,323 Aminopyrazolopyrimidine Muscasky   US Pat. No. 4,983,508 Bispyridinium salt Ishiguro, etc.   US Pat. No. 5,185,239 Triaminopyrimidine Muscasky   U.S. Pat. No. 5,178,997 7-azaindole compounds Muscasky   US Pat. No. 5,178,998 Xanthine Muscasky   JP-A 64-70741 Dye Nishikawa etc.   JP-A-3-212439 Aminothioether Ishiguro   JP-A-4-283742 Thiourea derivative Ishiguro   JP-A-4-335632 Triazolium salt Ishiguro   JP-A-2-32 Bispyridinium salt Ishiguro, etc.   Japanese Patent Application No. 7-146891 Monopyridinium salt Ozeki etc. The (111) tabular grain formation is described in the table above.
As is known, methods using various crystal phase control agents are known.
However, the compounds described in JP-A-2-32 (compounds)
Examples 1-42 are preferred, and Japanese Patent Application No. 6-333780 is preferred.
Are particularly preferred.
However, the present invention is not limited to these.
Yes. (111) Tabular grains consist of two parallel twins.
It is obtained by forming a surface. Twin plane formation is warm
Depends on temperature, dispersion medium (gelatin), halogen concentration, etc.
These appropriate conditions must be set.
Yes. If a phase control agent is present during nucleation,
The concentration is preferably 0.1% to 10%. Chloride concentration is
0.01 mol / liter or more, preferably 0.03 mol
/ L or more. Also to monodisperse the particles
For nucleation, it is preferable not to use a crystal phase control agent.
JP-A-8-184931 discloses this.
Gelatin concentration if no phase control agent is used during nucleation
0.03% to 10%, preferably 0.05% to 1.0
%. Chloride concentration is 0.001 mol / liter to 1
Mol / liter, preferably 0.003 mol / liter
~ 0.1 mol / liter. Nucleation temperature is 2 ° C ~ 9
Any temperature can be selected up to 0 ° C, but 5 ° C to 80 ° C is preferred
In particular, 5 ° C to 40 ° C is preferable. In the first nucleation stage, tabular grain nuclei are formed.
However, immediately after nucleation, the reaction vessel contains other than tabular grains.
Many nuclei are included. Therefore, after nucleation, ripening,
It is necessary to have technology that leaves only tabular grains and eliminates others.
The When normal Ostwald ripening is performed, tabular grain nuclei also dissolve.
As the solution disappears, the number of tabular grain nuclei decreases, resulting in
The size of the tabular grains to be increased. Prevent this
Therefore, a crystal phase controlling agent is added. Especially phthalated gelatin
In combination, the effect of the crystal phase control agent is enhanced and the tabular grains
The dissolution of the child can be prevented. Aging pAg is particularly important
60-130 mV is preferred for silver-silver chloride electrodes
Yes. Next, physical ripening of the formed nucleus and halogenation with silver salt
It is grown in the presence of a crystal phase controlling agent by adding the product. this
The chloride concentration is 5 mol / liter or less, preferably
Is 0.05 to 1 mol / liter. Temperature during grain growth
The degree can be selected in the range of 10 ° C to 90 ° C, but 30 ° C to 8 ° C.
A range of 0 ° C. is preferred. The total amount of crystal phase control agent used is finished milk
6 x 10 per mole of silver halide in the agent^-FiveMole or less
Above, especially 3x10^-FourMol ~ 6 × 10^-2Mole is preferred.
The timing of addition of the crystal phase controlling agent is the core of the silver halide grains.
Any time from formation to physical ripening and grain growth
Yes. Formation of the (111) plane starts after the addition. Crystal phase system
The agent may be added to the reaction vessel in advance, but the small size flat
When plate particles are formed, the inside of the reaction vessel
It is preferable to increase the concentration. The amount of the dispersion medium used at the time of nucleation depends on the growth.
If it is insufficient, it is necessary to compensate by addition. For growth
10g / liter to 100g / liter of gelatin exists
Preferably present. Phthalate is used as supplemental gelatin
Latin or trimellit gelatin is preferred. particle
The pH during formation is arbitrary, but neutral to acidic regions are preferred
Yes. Next, (100) tabular grains will be described.
The The (100) tabular grains have the (100) plane as the main plane.
Tabular grains. The shape of the main plane is a right-angled parallelogram
The shape or one corner of the right parallelogram is missing
3 to 5 square shapes (The missing shape is the corner
And a right triangle formed by the corners
Min), or there are 2 or more and 4 or less missing parts 4
There are ~ octagonal shape. Right angle parallel to compensate for the missing part
If the quadrilateral shape is a supplementary quadrilateral, the right-angled parallelogram
And the ratio of adjacent sides of the supplemental quadrilateral (long side length / short side
Length) is 1-6, preferably 1-4, more preferably 1-2
is there. (100) Tabular halogen having main plane
As a method of forming silver halide emulsion grains, an aqueous gelatin solution is used.
An aqueous silver salt solution and an aqueous halide salt solution in a simple dispersion medium
While adding and mixing while
For example, JP-A-6-301129 and JP-A-6-347929.
No. 9-34045 and 9-96881
Silver or iodide ions, or silver bromide or
Contains bromide ions and the size of the crystal lattice with silver chloride
The difference in height causes the nucleus to be distorted, making it anisotropic like a screw dislocation.
Disclosed is a method for introducing crystal defects that impart growth properties.
Yes. When this screw dislocation is introduced, it will be under low supersaturation conditions.
Since the formation of two-dimensional nuclei on the surface of
By introducing crystallization on the surface and introducing screw dislocations
Tabular grains are formed. Here, the low supersaturation condition is
Preferably at the time of boundary addition 35% or less, more preferably 2
20%. The crystal defect is determined to be a screw dislocation.
Although not necessarily, the direction in which the dislocation was introduced or the grain
Possible to be a screw dislocation because anisotropic growth is imparted to the child
It is thought that the nature is high. To make tabular grains thinner
However, it is preferable that the introduced dislocations be retained.
122954 and 9-189777.
The Japanese Patent Laid-Open No. 6-347928 discloses an
Using dazoles and 3,5-diaminotriazoles
JP-A-8-339044 discloses polyvinyl alcohol.
(100) surface formation accelerator added by using
And a method of forming (100) tabular grains is disclosed.
The However, the present invention is not limited to these.
There is no. High silver chloride grains have a silver chloride content of 80 mol%.
The above-mentioned grains, but 95 mol% or more is silver chloride.
Are preferred. The particles of the present invention surround the core part and the core part.
It has a so-called core / shell structure consisting of shell parts.
Preferably it is. 90 mol% or more of the core is silver chloride
It is preferable that The core further has a halogen composition
It may consist of two or more different parts. shell
Part is preferably 50% or less of the total particle volume.
It is particularly preferably 0% or less. Shell part is iodine salt
Silver chloride or silver iodobromochloride is preferred. shell
Part contains 0.5 mol% to 13 mol% iodine.
And preferably 1 to 13 mol%
Is particularly preferred. Content of silver iodide in all grains is 5 mol
% Or less is preferable, and 1 mol% or less is particularly preferable. Bromide
Silver content is preferably higher in the shell than in the core
Yes. The silver bromide content is preferably 20 mol% or less, preferably 5 mol%.
% Or less is particularly preferable. Average grain size (volume) of silver halide grains
There is no particular limitation on the equivalent sphere diameter, but preferably 0.
1 μm to 0.8 μm, particularly preferably 0.1 μm to 0.
6 μm. Tabular grains of silver halide have an equivalent circle diameter
Is preferably 0.2 to 1.0 μm. Here is the halogene
The diameter of silver halide grains is the size of the grains in electron micrographs.
The diameter of a circle with an area equal to the projected area. The thickness is
0.2 μm or less, preferably 0.1 μm or less, particularly preferred
It is 0.06 μm or less. Yellow pigmented cap
50% or more of the projected area of all silver halide grains containing
Above, average aspect ratio (ratio of diameter / thickness) is 2 or more
Is more preferable, and more preferably 5 or more and 20 or less. one
In general, tabular grains are tabular with two parallel faces.
Therefore, in the present invention, “thickness” means tabular grains.
It is represented by the distance between the two parallel surfaces that constitute it. C of the present invention
The particle size distribution of silver halide grains is simple even in polydisperse
Although it may be dispersed, it is more preferably monodispersed. In particular
Equivalent circle diameter of tabular grains occupying 50% or more of the total projected area
The variation coefficient is preferably 20% or less. Ideally 0%
is there. The crystal phase controlling agent exists on the particle surface even after the particle formation.
This will affect the adsorption and development of sensitizing dyes. That
Therefore, it is preferable to remove the crystal phase control agent after forming the particles.
Yes. However, when the crystal phase controlling agent is removed, high silver chloride (1
11) Tabular grains maintain (111) faces under normal conditions
Difficult to do. Therefore, sensitizing dyes etc.
It is preferable to retain the particle morphology by substituting with useful compounds.
That's right. Regarding this method, JP-A-9-80656,
JP-A-9-106026, US Pat. No. 5,221,6
No. 02, No. 5,286,452, No. 5,2
98,387, 5,298,388, 5,
176,992 and the like. By the above method, the crystal phase controlling agent is desorbed from the particles.
However, the desorbed crystal phase control agent is removed from the emulsion by washing with water.
It is preferable to do this. As washing temperature, protective colloid and
At a temperature that does not solidify normally used gelatin.
You can. As a washing method, flocculation method
And various known techniques such as ultrafiltration can be used.
The The washing temperature is preferably 40 ° C. or higher. Crystal phase control
The agent is more desorbed than particles at low pH. Therefore, washing with water
The pH of the process is low as long as the particles do not aggregate excessively.
preferable. The silver halide grains contain a metal of group VIII of the periodic table.
Genus: osmium, iridium, rhodium, platinum, le
Choose from Tenium, Palladium, Cobalt, Nickel, Iron
Metal ions or complex ion compounds (metal ions
ON-providing compounds) alone or in combination
Can do. Further, a plurality of these metals may be used. The metal ion donating compound is a halogenated compound.
Halogen in an aqueous gelatin solution that becomes a dispersion medium during silver particle formation
In aqueous solution, silver salt solution, or other aqueous solution
Or add metal ions in advance.
Added to silver halide emulsion in the form of fine silver halide grains
Then, the method of the present invention is performed by means such as dissolving the emulsion.
It can be contained in silver halide grains. Also gold
In order to incorporate the genus ions in the particles, before forming the particles,
Can be performed either during grain formation or immediately after grain formation
However, during this addition period, the metal ion is moved to which position of the particle.
It can be changed depending on whether or not it is contained. Silver halide grains contain metal ions to be used.
50 mol% or more, preferably 80 mol of the provided compound
% Or more, more preferably 100 mol% is silver halide.
Table from particle surface to equivalent to 50% or less of particle volume
It is preferable to be localized in the face layer. The volume of this surface layer is
Preferably it is 30% or less. Metal ions on the surface layer
To suppress the increase in internal sensitivity and obtain high sensitivity.
This is advantageous. Surface layer of such silver halide grains
To contain the metal ion donating compound
For example, silver halide grains in the portion excluding the surface layer (co
A) After forming the water-soluble silver salt to form the surface layer
Metal ions with the addition of solution and aqueous halide solution
This can be done by supplying a provided compound. Silver halide emulsions other than Group VIII metals
In the process of emulsion grain formation or physical ripening
Various polyvalent metal ion impurities can be introduced.
The amount of these compounds added varies widely depending on the purpose.
Is 10 to 1 mole of silver halide.^-9-10^-2Mole
Is preferred. The following relates to all the emulsions relating to the present invention.
The contents will be described. Reduction sensitization preferably used in the present invention
Is a method of adding a reduction sensitizer to silver halide,
In a low pAg atmosphere of pAg1-7 called silver ripening
Method for growing or ripening silver halide grains, high pH
Growing in a high pH atmosphere called aging, pH 8-11
Or you can choose one of the aging methods
The Also, two or more of these methods should be used in combination
You can also. In particular, the method of adding a reduction sensitizer is a reduction enhancement.
This is a preferable method in that the level of feeling can be finely adjusted.
The As a reduction sensitizer, stannous salt, ascorbine
Acid and its derivatives, hydroquinone and its derivatives
Body, catechol and its derivatives, hydroxylamine
And its derivatives, amines and polyamines, hydra
Gin and its derivatives, paraphenylenediamine and
Its derivative, formamidinesulfinic acid (thiodioxide
Urea), silane compounds, and borane compounds.
Yes. These reduction sensitizers are selected for the reduction sensitization of the present invention.
Can be used, and two or more compounds can be used in combination.
You can also. Regarding the method of reduction sensitization, US Pat.
No. 518,698, No. 3,201,254, No.
3,411,917, 3,779,777,
The method disclosed in US Pat. No. 3,930,867 and the reducing agent
Regarding the method of use, JP-B-57-33572, 58
-1410, those disclosed in JP-A-57-179835
The method can be used. Cateco as a reduction sensitizer
And its derivatives, hydroxylamine and its derivatives
Conductor, formamidine sulfinic acid (thiouric dioxide)
Element) is a preferred compound. The amount of reduction sensitizer added is
Since it depends on the emulsion production conditions, it is necessary to select the addition amount
Is 10 per mole of silver halide.^-7-10^-1Molar range
Is appropriate. Reduction sensitizers are water or alcohols,
Soluble such as recalls, ketones, esters, amides
It is dissolved in a medium and added during particle growth. Silver halide that can be used in the present invention
As the solvent, US Pat. No. 3,271,157,
3,531,289, 3,574,628, JP,
Described in Sho 54-1019, 54-1558917, etc.
(A) Organic thioethers, JP-A-53-824
08, 55-77737, 55-2982, etc.
(B) Thiourea derivatives described in JP-A-53-14
(C) oxygen or sulfur atom and nitrogen described in No. 4319
Halogen having a thiocarbonyl group sandwiched between elemental atoms
Silver halide solvent, described in JP-A-54-100717
(D) Imidazoles, (e) Ammonia, (f) Thio
Examples include cyanate. Particularly preferred solvents are thiocyanates.
And ammonia and tetramethylthiourea. Ma
The amount of solvent used varies depending on the type.
In the case of thiocyanate, the preferred amount is silver halide 1
1 x 10 per mole^-Four1 x 10 moles or more^-2Less than or equal to
The During the preparation of the emulsion of the present invention, for example, during grain formation,
During the desalting process, chemical sensitization, there is a metal ion salt before coating.
It is preferable depending on the purpose. Dope particles
In some cases, during particle formation, particle surface modification or chemical sensitization
When used as an agent, added after grain formation and before chemical sensitization
It is preferable to do. As mentioned earlier, the entire particle is
And only the core part of the particle or the shell part
Or doping the epitaxial part only
You can choose. For example, Mg, Ca, Sr, Ba, Al, S
c, Y, La, Cr, Mn, Fe, Co, Ni, Cu,
Zn, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Can be used. These metals are ammonium
Salt, acetate, nitrate, sulfate, phosphate, hydrochloride or
6-coordination complex salt, 4-coordination complex salt, etc. dissolved during particle formation
It can be added if it is in the form of a salt that can For example, CdB
r₂ , CdCl₂ , Cd (NO_Three )₂ , Pb (NO_Three )
₂ , Pb (CH_Three COO)₂ , K_Three [Fe (CN)
₆ ], (NH_Four )_Four [Fe (CN)₆ ], K_Three IrCl
₆ , (NH_Four )_Three RhCl₆ , K_Four Ru (CN)₆ There
I can get lost. As ligands for coordination compounds, halo, ako, and shi
Ano, cyanate, thiocyanate, nitrosyl, thio
Choose from nitrosyl, oxo, carbonyl
it can. These may use only one kind of metal compound.
May be used in combination of two or more. Metal compounds are water, methanol, aceto
It is preferable to add it in a suitable organic solvent such as
That's right. Hydrogen halide aqueous solution to stabilize the solution
(Eg HCl, HBr) or halogenated alk
(For example, KCl, NaCl, KBr, NaBr)
The method of adding can be used. Also acid if necessary
・ Alkali may be added. Metal compounds form particles
Even if it is added to the previous reaction vessel, it must be added in the middle of particle formation.
You can also. In addition, water-soluble silver salt (for example, AgNO_Three)is there
Or an aqueous alkali halide solution (for example, NaCl, K
Br, KI) added continuously during silver halide grain formation
It can also be added. Further water-soluble silver salt, halogenated
Prepare a solution independent of the alkali at an appropriate time during particle formation
You may add continuously in a period. Furthermore, various addition methods
It is also preferable to combine them. Described in US Pat. No. 3,772,031.
Add chalcogen compounds such as those mentioned during emulsion preparation
This method may be useful. In addition to S, Se, Te
Ansalt, thiocyanate, selenocyanic acid, carbonate, phosphorus
Acid salts and acetate salts may be present. The silver halide grains of the present invention are sulfur sensitized,
Ren sensitization, gold sensitization, palladium sensitization or noble metal sensitization, return
At least one of the original sensitization processes for producing silver halide emulsions
Can be applied in any step. Two or more sensitization methods
It is preferable to combine. Chemical sensitization in any process
Different types of emulsions can be prepared depending on
The Type that embeds chemical sensitization nucleus inside particle, particle table
Type that embeds in a shallow position from the surface, or chemical on the surface
There are types that make sensitization nuclei. The emulsion of the present invention can be used depending on the purpose.
Can choose the location of chemical sensitization nuclei, but is generally preferred
What is new is creating at least one chemical sensitization nucleus near the surface
This is the case. Chemical sensitization that can be preferably performed in the present invention
One is chalcogen sensitization and noble metal sensitization alone or in combination.
Yes, by TH James, The Fo
To graphic process, 4th edition, published by Macmillan,
1977, (TH James, The Theo
ry of the Photographic Pr
ocess, 4th ed, McCillan, 19
77) Active gelatin as described on pages 67-76
Can also be used and research and disclosure
Jar, 120, April 1974, 12008;
Search Disclosure, 34, 1975 6
Moon, 13452, US Pat. No. 2,642,361, ibid.
No. 3,297,446, No. 3,772,031,
3,857,711, 3,901,714,
4,266,018, and 3,904,4
15 and British Patent 1,315,755
PAg 5-10, pH 5-8 and temperature 30-
Sulfur, selenium, tellurium, gold, platinum, para at 80 ° C
Palladium, iridium or multiple combinations of these sensitizers
It can be. For precious metal sensitization, gold, white
Use noble metal salts such as gold, palladium and iridium
In particular, gold sensitization, palladium sensitization and both
Is preferred. For gold sensitization, chloroauric acid, potassium
Umchloroaurate, potassium aurithiocyanate
Using known compounds such as gold sulfide, gold selenide
Can. Palladium compound is palladium divalent salt
Or a tetravalent salt is meant. Preferred palladium compounds
Is R₂ PdX₆ Or R₂ PdX_Four It is represented by here
Where R is a hydrogen atom, an alkali metal atom or ammonium
Represents a group. X represents a halogen atom and represents chlorine, bromine or iodine.
Represents an elementary atom. Specifically, K₂ PdCl_Four , (NH_Four )
₂ PdCl₆ , Na₂ PdCl_Four , (NH_Four )₂ PdC
l_Four , Li₂ PdCl_Four , Na₂ PdCl₆ Or K₂
PdBr_Four Is preferred. Gold compounds and palladium compounds
Use in combination with thiocyanate or selenocyanate
It is preferable. Hypo, thiourine as sulfur sensitizer
Elemental compounds, rhodanine compounds and US Pat. No. 3,8
57,711, 4,266,018, and
Sulfur-containing compounds described in US Pat. No. 4,054,457
Can be used. In the presence of so-called chemical sensitization aids
It can also be chemically sensitized. Useful chemical sensitization aid
Of azaindene, azapyridazine, azapyrimidine
In the process of chemical sensitization, fog is suppressed and sensitivity is increased.
Compounds known to increase are used. Chemistry
Examples of sensitizing aid modifiers are described in US Pat. No. 2,131,038.
No. 3,411,914 No. 3,554,75
No. 7, Japanese Patent Laid-Open No. 58-126526 and the above-mentioned daffine
The book “Photo Emulsion Chemistry”, pages 138-143
The The emulsion of the present invention is preferably used in combination with gold sensitization.
The preferred amount of gold sensitizer is 1 per mole of silver halide.
× 10^-Four~ 1x10^-7Mole, and more preferred
1 × 10^-Five~ 5x10^-7Is a mole. Palladium compound
The preferred range of 1 × 10^-3To 5 × 10^-7It is. H
Preferred of ocyanine compound or selenocyan compound
The range is 5x10^-2To 1 × 10^-6It is. The halo of the present invention
The preferred amount of sulfur sensitizer used for the silver halide grains is
1 x 10 per mole of silver halide^-Four~ 1x10^-7In moles
Yes, more preferably 1 × 10^-Five~ 5x10^-7Mole
It is. As a preferred sensitizing method for the emulsion of the present invention,
There is a Ren sensitization. Known instability in selenium sensitization
Using selenium compounds, specifically, colloidal metal
Ni, selenoureas (for example, N, N-dimethylsel
Nourea, N, N-diethylselenourea), selenoketone
Selenium compounds such as selenoamides
Can do. Selenium sensitization is sulfur sensitization or noble metal sensitization.
Or in combination with both.
is there. An acid for silver during the production process of the emulsion of the present invention
It is preferable to use an agent. What is an oxidizing agent for silver?
Acts on metallic silver and converts it to silver ions
Refers to a compound. Especially the formation process of silver halide grains and
Very fine silver particles by-produced during chemical sensitization
A compound capable of converting to silver ions is effective. here
The silver ions produced in
It may form a slightly soluble silver salt in water such as silver or silver selenide
It is also possible to form a readily soluble silver salt in water such as silver nitrate.
Yes. The oxidizing agent for silver is organic, even if it is inorganic.
There may be. Examples of inorganic oxidizing agents include ozono
, Hydrogen peroxide and its adducts (eg NaBO₂
・ H₂ O₂ ・ 3H₂ O, 2NaCO_Three ・ 3H₂ O₂ , N
a_Four P₂ O₇ ・ 2H₂ O₂ 2Na₂ SO_Four ・ H₂ O₂
・ 2H₂ O), peroxyacid salts (eg K₂ S₂ O
₈ , K₂ C₂ O₆ , K₂ P₂ O₈ ), Peroxy complexation
Compound (eg K₂ [Ti (O₂ ) C₂ O_Four ] 3H₂
O, 4K₂ SO_Four ・ Ti (O₂ ) OH / SO_Four ・ 2H₂
O, Na_Three [VO (O₂ ) (C₂ H_Four )₂ ] 6H₂
O), permanganate (eg KMnO)_Four ),chromium
Acid salts (eg K₂ Cr₂ O₇) Oxygenate salt such as
Halogen elements such as elemental and bromine, perhalogenates (eg
Eg potassium periodate), high valent metal salts (eg
For example, potassium hexacyanoferric acid) and thiosulfur
There is oxalate. Further, as an organic oxidizing agent, p-quinone is used.
Quinones, such as peracetic acid and perbenzoic acid.
Oxides, compounds that release active halogens (eg N-
Bromsuccinimide, chloramine T, chloramine B)
Is given as an example. Preferred oxidizing agents of the present invention are ozone and peracid.
Hydrogen fluoride and its adducts, halogen elements, thiosulfo
Inorganic oxidizers of phosphates and organic oxidants of quinones.
It is preferable to use the aforementioned reduction sensitization in combination with an oxidizing agent for silver.
This is a new aspect. Apply reduction sensitization after using an oxidizing agent
Method, the reverse method, or both
You can choose from among them. These methods are
Select and use in both particle formation process and chemical sensitization process
it can. The photographic emulsion used in the present invention contains a photosensitive material.
Prevents fogging during the production process, storage, or photo processing
To stop or stabilize photographic performance,
Compounds can be included. Ie thiazole
Such as benzothiazolium salt, nitroimidazole
, Nitrobenzimidazoles, chlorobenzimi
Dazoles, bromobenzimidazoles, mercapto
Thiazoles, mercaptobenzothiazoles, merca
Putobenzimidazoles, mercaptothiadiazoles
, Aminotriazoles, benzotriazoles, di
Trobenzotriazoles, mercaptotetrazoles
(Especially 1-phenyl-5-mercaptotetrazole);
Mercaptopyrimidines; mercaptotriazines; examples
For example, a thioketo compound such as oxadrine thione;
Zaindenes, such as triazaindenes, tetraa
Zaindenes (especially 4-hydroxy-substituted (1,3,3
a, 7) Chitraazaindene), Pentaazaindene
Known as antifoggants or stabilizers, such as
Many compounds can be added. For example, US patents
3,954,474, 3,982,947,
Use the one described in Japanese Patent Publication No. 52-28660.
You can. One preferred compound is disclosed in JP-A-63-21.
There are compounds described in No. 2932. Antifogging agent
And stabilizers before and during particle formation, after particle formation,
During the washing process, after dispersion with water, before chemical sensitization, during chemical sensitization,
After sensitization, add according to purpose at various times before application
can do. Add to the original fog during emulsion preparation
In addition to preventing and stabilizing,
Control, reduce particle size, reduce particle solubility
Control, chemical sensitization, control dye sequence
It can be used for various purposes. US Pat. Nos. 5,747,235 and 57472
36, European Patent Nos. 786692A1 and 893731A
1, 893732A1, and WO99 / 05570.
Organics consisting of electron donating groups and leaving groups, as described in
It is also preferred to sensitize with an electron donating compound. The silver halide emulsion light-sensitive layer is formed on the support.
One or more layers can be provided. Also support
It can be provided not only on one side of the body but on both sides. Photosensitive layer
Is a black-and-white silver halide photographic material (for example, X-ray sensation)
Materials, squirrel-type sensitive materials, negative films for black and white photography, etc.) and color
-Photosensitive materials (eg color negative film, color
Reversal film, color paper, etc.)
The Furthermore, diffusion transfer photosensitive materials (for example, color diffusion)
Transfer element, silver salt diffusion transfer element), photothermographic material (black)
(White, color) and the like. In the following, the color photographic light-sensitive material will be described in detail.
Although explained, it is not limited to these. The light-sensitive material has a blue color-sensitive layer and a green color on the support.
At least of the silver halide emulsion layer of the color layer and the red color sensitive layer
It is sufficient that one layer is provided, and the silver halide emulsion layer and
There are no particular limitations on the number of layers and the layer order of the non-photosensitive layers. Typical
As a typical example, the color sensitivity is substantially the same on the support.
It consists of multiple silver halide emulsion layers with different sensitivities.
Silver halide photographic sensitivity having at least one color-sensitive layer
A light material, the photosensitive layer comprising blue light, green light, and red light
It is a unit photosensitive layer that has color sensitivity to any of the colored lights.
In a layered silver halide color photographic light-sensitive material,
The arrangement of unit photosensitive layers is a red color-sensitive layer in order from the support side,
The green color-sensitive layer and the blue color-sensitive layer are installed in this order. But eyes
Even if the installation order is reversed, the same color sensitivity
The order of installation is as if different photosensitive layers were encased in the layers.
obtain. Between the above silver halide photosensitive layers and the
Provide a non-photosensitive layer such as an intermediate layer for each layer on the upper and lower layers.
Also good. In the intermediate layer, JP-A 61-43748 is disclosed.
Nos. 59-113438, 59-113440
No. 61-20037, 61-20038
Couplers and DIR compounds as listed
Well, it contains anti-color mixing agents as usual
Also good. A plurality of halogens constituting each unit photosensitive layer
For silver halide emulsion layers, see German Patent 1,121,470.
Is highly sensitive as described in British Patent No. 923,045
A two-layer structure consisting of an emulsion layer and a low sensitivity emulsion layer is preferably used.
You can. Normally, the photosensitivity decreases gradually toward the support.
It is preferable to arrange so that
A non-photosensitive layer may be provided between the layers. Also,
JP-A-57-112751 and 62-200350
No. 62-206541, 62-206543
Low sensitivity milk on the side away from the support as described in
A high-sensitivity emulsion layer may be installed on the side close to the agent layer and support.
Yes. As a specific example, from the side farthest from the support,
For example, low sensitivity blue photosensitive layer (BL) / high sensitivity blue photosensitive layer
(BH) / High-sensitivity green photosensitive layer (GH) / Low-sensitivity green photosensitive layer
Layer (GL) / high sensitivity red light sensitive layer (RH) / low sensitivity red light sensitive
Order of functional layer (RL), or BH / BL / GL / GH / R
H / RL order or BH / BL / GH / GL / RL /
It can be installed in the order of RH. Also described in Japanese Patent Publication No. 55-34932.
As shown, blue sensitive from the side farthest from the support
It can also be arranged in the order of layer / GH / RH / GL / RL
The JP-A-56-25738 and 62-6393.
As described in No. 6, the farthest from the support
Set in order of blue photosensitive layer / GL / RL / GH / RH
It can also be placed. Also described in Japanese Examined Patent Publication No. 49-15495.
As the upper layer, the most sensitive silver halide emulsion
Silver halide emulsions with lower photosensitivity for layers and middle layers
Silver halide milk whose layer and lower layer have lower photosensitivity than the middle layer
The agent layer is arranged, and the photosensitivity is gradually lowered toward the support.
An array composed of three layers with different photosensitivity
The When composed of three layers with different sensitivities
However, it is described in JP-A-59-202464.
Thus, from the side away from the support in the same color-sensitive layer
Arrange in order of medium sensitivity emulsion layer / high sensitivity emulsion layer / low sensitivity emulsion layer
May be. Others, high sensitivity emulsion layer / low sensitivity emulsion layer / medium
Sensitive emulsion layer or low sensitivity emulsion layer / medium sensitivity emulsion layer / high
They may be arranged in the order of the sensitivity emulsion layer. Also, in the case of four or more layers, the arrangement is as described above.
You may change the column. As described above, the purpose of each photosensitive material
Various layer configurations and arrangements can be selected according to the above. The light-sensitive material according to the present invention includes the above-mentioned various materials.
Other additives, but other than these,
Various additives can be used. These additives are more specifically researched.
Disclosure Item 17643 (1978)
December), Item 18716 (1979 1
January) and Item 308119 (1989)
December), and the corresponding locations are listed in the table below.
Shown together. [0303]     Additive type RD17643 RD18716 RD308119    1 Chemical sensitizer page 23 page 648 right column page 996    2 Sensitivity increasing agent Same as above    3 Spectral sensitizer, pages 23 to 24, page 648, right column to 996, right to 998, right       Supersensitizer 649, right column on page 649    4 Brightener 24 pages 647 right column 998 right    5 Antifoggant, 24-25 pages 649, right column 998 right-1000 right       And stabilizer    6 Light absorber, pages 25-26, page 649, right column-1003 left-1003 right       Filter dye, page 650, left column       UV absorber    7 Stain inhibitor Page 25 Right column 650 Left to right column 1002 Right    8 Dye image stabilizer 25 page 1002 right    9 Hardener page 26 page 651 left column 1004 right to 1005 left   10 Binder page 26 Same as above 1003 right to 1004 right   11 Plasticizer, Lubricant 27 pages 650 right column 1006 left to 1006 right   12 Application aid, pages 26-27 Same as above 1005 left-1006 left       Surfactant   13 Static 27 pages Same as above 1006 Right to 1007 Left       Anti-blocking agent   14 Matting agent 1008 left to 1009 left It also prevents photographic performance deterioration due to formaldehyde gas.
To stop, U.S. Pat. No. 4,411,987 and
Formaldehyde described in US Pat. No. 4,435,503
A compound that can react and be immobilized is added to the photosensitive material.
Are preferred. In the present invention, various color couplers are used.
An example of this can be found in the previous research disc.
Roger No. 17643, VII-CG, and N
o. 307105, described in the patents described in VII-CG
It is listed. As the yellow coupler, for example,
Allowed 3,933,501, 4,022,620
No. 4,324,024 No. 4,401,75
No. 2, No. 4,248,961, JP-B 58-107
No. 39, British Patent No. 1,425,020, No. 1,4
76,760, US Pat. No. 3,973,968, the same
No. 4,314,023, No. 4,511,649,
Preferred are those described in European Patent No. 249,473A, etc.
That's right. As a magenta coupler, 5-pyrazolone
And pyrazoloazole-based compounds are preferred.
Allowed 4,310,619, 4,351,897
No., European Patent No. 73,636, US Patent No. 3,06
No. 1,432, No. 3,725,067, Research
Disclosure No. 24220 (1984, 6
Moon), JP-A-60-33552, Research Disc
Roger No. 24230 (June 1984), JP
60-43659, 61-72238, 60-
35730, 55-118034, 60-18
No. 5951, US Pat. No. 4,500,630, No.
No. 4,540,654, No. 4,556,630, country
Particularly preferred are those described in International Publication WO88 / 04795.
That's right. Examples of cyan couplers include phenolic and cyan couplers.
Naphthol couplers, US Pat. No. 4,0
No. 52,212, No. 4,146,396, No. 4,
No. 228,233, No. 4,296,200, No.
2,369,929, 2,801,171,
Nos. 2,772,162, 2,895,826,
No. 3,772,002, No. 3,758,308
No. 4,334,011, No. 4,327,17
3, West German Patent Publication No. 3,329,729, European Patent
121,365A, 249,453A, US
Patents 3,446,622 and 4,333,999
Nos. 4,775,616, 4,451,55
9, No. 4,427,767, No. 4,690,8
89, 4,254,212, 4,296,
No. 199, JP-A 61-42658, etc.
preferable. Typical of polymerized dye-forming couplers
Examples are U.S. Pat. Nos. 3,451,820 and 4,084.
No. 0, 211, No. 4,367, 282, No. 4, 4
09,320, 4,576,910, British patent
No. 2,102,137, European Patent No. 341,188A
In the issue. Couplers in which coloring dyes have appropriate diffusibility
US Patent 4,366,237, British Patent
No. 2,125,570, European Patent No. 96,570,
Those described in West German Patent (Public) No. 3,234,533
Is preferred. Color for correcting unwanted absorption of coloring dyes
Coupler is a Research Disclosure No.
No. 17643, VII-G, no. 307105 VII-
G, U.S. Pat. No. 4,163,670, JP-B 57-
No. 39413, US Pat. No. 4,004,929, No.
No. 4,138,258, British Patent No. 1,146,368
Are preferred. U.S. Pat.
Fluorescence emitted during coupling described in No. 4,181
Couplers that correct unnecessary absorption of coloring dyes with dyes,
The developing agent described in US Pat. No. 4,777,120
A dye precursor group capable of forming a dye in response to a leaving group
It is also preferable to use a coupler having Residues that are photographically useful upon coupling
Compounds that release can also be preferably used in the present invention.
The DIR coupler that releases the development inhibitor is the RD1 described above.
7643, VII-F and No. 307105, VII −
Patents described in Section F, Japanese Patent Application Laid-Open No. 57-151944,
57-154234, 60-184248,
63-37346, 63-37350, US Patent
Nos. 4,248,962 and 4,782,012
What has been described is preferred. [0312] Nucleating agent or development acceleration in image form during development
As a coupler for releasing the agent, British Patent No. 2,09
7,140, 2,131,188, JP 59
-157638, 59-170840
Is preferred. JP-A-60-107029, the same as above.
60-252340, JP-A-1-44940, 1
-Redox with an oxidized form of the developing agent described in No. -45687
Depending on the reaction, fogging agent, development accelerator, silver halide dissolved
Also preferred are compounds that release agents and the like. In addition, it can be used for the light-sensitive material of the present invention.
Possible compounds include US Pat. No. 4,130,427.
Competitive couplers described in US Pat. No. 4,283,4
No. 72, No. 4,338,393, No. 4,310,
Multi-equivalent couplers described in No. 618, etc., JP-A-60-18
DI described in No. 5950, JP-A No. 62-24252, etc.
R redox compound release coupler, DIR coupler release
Coupler, DIR coupler release redox compound
Is a DIR redox release redox compound, European Patent No.
173,302A and 313,308A
A coupler that releases a dye that recovers color after release, RD. No. 1
1449, 24241, JP-A-61-2012247
Bleach accelerator releasing couplers described in US Pat.
Patent application title: Ligand-releasing coupler described in Japanese Patent No. 55,477
A leuco dye releasing agent described in JP-A-63-75747
Fluor, described in US Pat. No. 4,774,181
Examples include couplers that release a dye. There are various known couplers used in the present invention.
It can be introduced into the light-sensitive material by the dispersion method. Oil-in-water dispersion
Examples of high boiling solvents used in the process are, for example, U.S. Pat.
No. 2,322,027. Oil-in-water dispersion
High boiling point of 175 ° C or higher at normal pressure
Specific examples of organic solvents include phthalates (for example,
Dibutyl phthalate, dicyclohexyl phthalate
, Di-2-ethylhexyl phthalate, decyl phthalate
And bis (2,4-di-tert-amylphenyl)
Phthalate, bis (2,4-di-tert-amylphe)
Nyl) isophthalate, bis (1,1-diethylpropiyl)
Phthalate); esters of phosphoric acid or phosphonic acid
(Eg triphenyl phosphate, tricresyl
Phosphate, 2-ethylhexyl diphenyl phosphate
, Tricyclohexyl phosphate, tri-2-eth
Tylhexyl phosphate, tridodecyl phosphate
, Tributoxyethyl phosphate, trichloropro
Pyrphosphate, di-2-ethylhexylphenylphosphate
Benzoates); benzoates (eg 2-ethyl)
Ruhexyl benzoate, dodecyl benzoate, 2-
Ethylhexyl-p-hydroxybenzoate);
(E.g., N, N-diethyldodecanamide, N,
N-diethyllaurylamide, N-tetradecylpyrrole
Don); alcohols or phenols (eg
Sostearyl alcohol, 2,4-di-tert-amino
Ruphenol); aliphatic carboxylic acid esters (eg
For example, bis (2-ethylhexyl) sebacate, diocti
Ruazelate, glycerol tributyrate, isostere
Allyl lactate, trioctyl citrate); anili
Derivatives such as N, N-dibutyl-2-butoxy-
5-tert-octylaniline); hydrocarbons (eg
Paraffin, dodecylbenzene, diisopropyl na
Phthalene). Also as an auxiliary solvent
For example, the boiling point is about 30 ° C. or higher, preferably 50 ° C.
An organic solvent having a temperature of about 160 ° C or lower can be used.
For example, ethyl acetate, butyl acetate, propio
Ethyl acetate, methyl ethyl ketone, cyclohexanone,
2-Ethoxyethyl acetate, dimethylformamide
Is mentioned. Latex dispersion process steps, effects and impregnation
Specific examples of latexes for use are, for example, U.S. Pat. No. 4,19.
9,363, West German Patent Application (OLS) No. 2,541
274 and 2,541,230.
ing. In the color light-sensitive material of the present invention, phenethyl is used.
Alcohol, JP-A 63-257747, 62-
Described in No. 272248 and JP-A-1-80941
Of, for example, 1,2-benzisothiazoline-3-
N-butyl-p-hydroxybenzoate, phenol
4-chloro-3,5-dimethylphenol, 2-
Phenoxyethanol, 2- (4-thiazolyl) benzo
Add various preservatives or antifungal agents such as imidazole
It is preferable to add. The present invention is applied to various color light-sensitive materials.
be able to. For example, general or movie colors
Color film for negative film, slide or TV
Transfer film, color paper, color positive film and
And color reversal paper
The The present invention is also particularly preferred for color duplication films.
Can be used. Suitable supports that can be used in the present invention are, for example,
RD. No. 17643, page 28, ibid.
18716, page 647, right column to page 648, left column, and
No. 307105, page 879. The light-sensitive material of the present invention has an emulsion layer side.
The total thickness of all hydrophilic colloid layers is 28 μm or less
Is preferably 23 μm or less, more preferably 18 μm.
m or less is more preferable, and 16 μm or less is particularly preferable.
In addition, membrane swelling speed T_1/2 Is preferably 30 seconds or less, 20 seconds
The following is more preferable. The film thickness here is 25 ° C relative humidity
It means the film thickness measured under 55% humidity control (2 days). Ma
Membrane swelling speed T_1/2 Is a hand known in the art.
For example, A Green
(A. Green) et al.
Ens and Engineering (Photogr.
Sci. Eng. ), Vol. 19, No. 2, pp. 124-129
Use a spherometer of the type described in
Can be measured. T_1/2 Is a color developer 30
9 of the maximum swollen film thickness reached when treated at 3 ° C for 3 minutes 15 seconds
0% is assumed to be a saturated film thickness, until it reaches 1/2 of the saturated film thickness
Is defined as the time. Film swelling speed T_1/2 As a binder
Add hardener to gelatin or time after coating
It can be adjusted by changing the conditions. The light-sensitive material of the present invention has the emulsion layer side.
On the opposite side, hydrophilicity with a total dry film thickness of 2 μm to 20 μm
It is preferable to provide a colloid layer (called back layer)
Yes. The back layer includes, for example, the above-described light absorber and fibre.
Luther dye, UV absorber, antistatic agent, dura
Agent, binder, plasticizer, lubricant, coating aid, surface activity
It is preferable to contain an agent. Swell rate of this back layer
Is preferably 150 to 500%. A color photographic light-sensitive material according to the present invention has
RD. No. 17643, pp. 28-29, ibid.
No. 18716, page 651, left column to right column; 30
7105, pages 880-881 in the usual way
Therefore, it can be developed. Coloring used in the development processing of the light-sensitive material of the present invention
The developer is preferably an aromatic primary amine color developer
It is an alkaline aqueous solution mainly composed of a medicine. This color development
Aminophenol compounds are also useful as image agents.
However, p-phenylenediamine compounds are preferably used.
As a typical example, 3-methyl-4-amino-
N, N diethylaniline, 3-methyl-4-amino-N
-Ethyl-N-β-hydroxyethylaniline, 3-methyl
Tyl-4-amino-N-ethyl-N-β-methanesulfo
N-amidoethylaniline, 3-methyl-4-amino-N
-Ethyl-β-methoxyethylaniline, and these
Sulfate, hydrochloride or p-toluenesulfonate
Is mentioned. Among these, in particular, 3-methyl-4-
Amino-N-ethyl-N-β-hydroxyethylanily
Sulfate is preferred. These compounds can be used depending on the purpose.
More than one species can be used in combination. The color developer is, for example, an alkali metal charcoal.
PH buffering agents such as acid salts, borates or phosphates,
Chloride salt, bromide salt, iodide salt, benzimidazole
Benzothiazoles or mercapto compounds
Such development inhibitors or antifogging agents are generally included.
is there. If necessary, hydroxylamine, diethyl
Hydroxylamine, sulfite, N, N-biscarbo
Hydrazines such as xylmethylhydrazine, phenyl
Micarbazides, triethanolamine, catechols
Various preservatives such as sulfonic acids; ethylene glycol, di
Organic solvents such as ethylene glycol; benzyl alcohol
, Polyethylene glycol, quaternary ammonium salt,
Development accelerators such as amines; dye-forming couplers, competition
Couplers such as 1-phenyl-3-pyrazolidone
Auxiliary developing agent; Viscosifier; Aminopolycarboxylic acid, amino
Nopolyphosphonic acid, alkylphosphonic acid, phosphonocar
Use various chelating agents as represented by boric acid
Can do. Examples of chelating agents include ethylene dia
Mine tetraacetic acid, nitrile triacetic acid, diethylenetriamine five
Acetic acid, cyclohexanediaminetetraacetic acid, hydroxyethyl
Louisinodiacetic acid, 1-hydroxyethylidene-1,1-
Diphosphonic acid, nitrilo-N, N, N-trimethylene
Sphonic acid, ethylenediamine-N, N, N, N-tetra
Methylenephosphonic acid, ethylenediamine-di (o-hydride)
Roxyphenylacetic acid) and their salts are typical examples.
I can make it. [0325] When reversal processing is performed, it is usually black.
Color development is performed after white development. In this black and white developer
For example, dihydroxybens such as hydroquinone
Zens such as 1-phenyl-3-pyrazolidone
Such as 3-pyrazolidones or, for example, N-methyl-
Publicity of aminophenols such as p-aminophenol
Use known black and white developing agents alone or in combination
be able to. P of these color developers and black-and-white developers
H is generally 9-12. Also this
The replenishment amount of these developers is the color photographic material to be processed.
However, generally 3 liters per square meter of photosensitive material
Torr or less, reducing bromide ion concentration in the replenisher
You can make it less than 500ml
The When reducing the replenishment amount, contact the processing solution with air.
By reducing the area, liquid evaporation and air oxidation are prevented.
It is preferable to stop. Contact area between photographic processing solution and air in processing tank
Can be expressed by the aperture ratio defined below. That is, Opening ratio = [contact area between treatment liquid and air (cm² )] ÷ [Process
Capacity of scientific liquid (cm^Three ]] The opening ratio is preferably 0.1 or less, more
Preferably it is 0.001-0.05. Open like this
As a method of reducing the percentage, the photographic processing liquid level of the processing tank
In addition to providing a shield such as a floating lid
Using the movable lid described in JP-A-1-82033
The method described in Japanese Patent Application Laid-Open No. 63-2106050
Can be mentioned. Reduces aperture ratio
If only the color development and black-and-white development processes
And subsequent processes such as bleaching, bleach-fixing, fixing, water
It is preferable to apply in all steps of washing and stabilization.
Yes. Means to suppress accumulation of bromide ions in the developer
The amount of replenishment can also be reduced by using. The color development processing time is usually between 2 and 5 minutes.
Set at high temperature, high pH, and high color developing agent
By using it for concentration, the processing time is further shortened.
You can also The photographic emulsion layer after color development is usually bleached.
It is. The bleaching process may be performed simultaneously with the fixing process.
(Bleaching and fixing treatment) may be performed individually. Further processing
In order to speed up the process, a bleach-fix process is performed after the bleach process.
It may be a rational method. In addition, two continuous bleach-fixing baths
Processing, fixing processing before bleach-fixing processing,
Depending on the purpose, it is also possible to perform bleaching after bleach-fixing.
Can be implemented arbitrarily. Examples of bleaching agents include iron (III)
Polyvalent metal compounds such as peracids (especially sodium persulfate)
Is suitable for color negative films for movies), quinones,
Toro compounds are used. Typical bleach is iron
(III) organic complex salts, such as ethylenediaminetetraacetic acid,
Diethylenetriaminepentaacetic acid, cyclohexanediamine
Tetraacetic acid, methyliminodiacetic acid, 1,3-diaminopropa
Like tetraacetic acid, glycol ether diamine tetraacetic acid
Complex salts with aminopolycarboxylic acids or, for example,
Complex salts with enoic acid, tartaric acid, malic acid can be used
The Of these, ethylenediaminetetraacetic acid iron (III) complex
Salt and 1,3-diaminopropanetetraacetic acid iron (III) complex salt
And other aminopolycarboxylic acid iron (III) complex salts
It is preferable from the viewpoint of rapid processing and prevention of environmental pollution. further,
Aminopolycarboxylic acid iron (III) complex salt
Are also particularly useful in bleach-fixing solutions. These a
Bleaching solution or drift using iron (III) complex salt of minopolycarboxylate
The pH of the white fixer is usually from 4.0 to 8, but the processing is quick
It can also be processed at a lower pH for conversion. For bleaching solutions, bleach-fixing solutions and their pre-baths
If necessary, a bleaching accelerator can be used.
Specific examples of useful bleach accelerators are described in the following specification:
For example: US Pat. No. 3,893,858, West Germany
Patent Nos. 1,290,812 and 2,059,988
, JP-A-53-32736, 53-57831
No., 53-37418, 53-72623,
53-95630, 53-95311, 53-
104232, 53-124424, 53-1.
41623, 53-18426, Research D
Closure No. No. 17129 (July 1978)
Having a mercapto group or disulfide group as described in
Compound: thiazolid described in JP-A No. 51-140129
Derivatives: Japanese Examined Patent Publication No. 45-8506, Japanese Unexamined Patent Publication No. 52-20
No. 832, No. 53-32735, US Pat. No. 3,70
A thiourea derivative described in US Pat. No. 6,561, West German Patent 1,
127,715, described in JP-A-58-16235
Iodide salt; West German Patent No. 966,410, No. 2,74
Polyoxyethylene compounds described in No. 8,430;
A polyamine compound described in JP-A-45-8836;
Other JP-A-49-40943, 49-59644,
53-94927, 54-35727, 55
-26506 and 58-163940
Bromide ions can be used. Among them, mercap
A compound having a thio group or a disulfide group has an accelerating effect
Preferred from a large standpoint, especially US Pat. No. 3,893,8
58, West German Patent 1,290,812, JP 53
The compound described in -95630 is preferable. In addition, the United States
The compounds described in Japanese Patent No. 4,552,884 are also preferred.
Yes. These bleach accelerators may be added to the light-sensitive material. Shoot
When bleach-fixing color light-sensitive materials for shadows, these
Bleach accelerators are particularly effective. In the bleaching solution and bleach-fixing solution, in addition to the above compounds
To contain organic acid for the purpose of preventing bleach stain
It is preferable. Particularly preferred organic acids are acid dissociation constants.
A compound having (pKa) of 2 to 5, specifically,
For example, acetic acid, propionic acid, hydroxyacetic acid
Can do. Fixing agents used in fixing solutions and bleach-fixing solutions
For example, thiosulfate, thiocyanate, thioe
List of ether compounds, thioureas, and large amounts of iodide salts
be able to. Of these, the use of thiosulfate is common
In particular, ammonium thiosulfate is the most widely used
Yes. Also, thiosulfate and, for example, thiocyanate,
A combined use of a thioether compound and thiourea is also preferred. Constant
Preservatives for landing and bleach-fixing solutions include sulfites and bisulfites.
Acid salt, carbonyl bisulfite adduct or European Patent No. 2
94,769A is preferred sulfinic acid compound
Yes. In addition, fixing solutions and bleach-fixing solutions have the purpose of stabilizing the solutions.
Of various aminopolycarboxylic acids and organic phosphonic acids
Addition is preferred. In the present invention, a fixing solution or a bleach-fixing solution
Has a pKa of 6.0 to 9.0 for pH adjustment.
Products, preferably imidazole, 1-methylimidazole
1-ethylimidazole, 2-methylimidazole
0.1 to 10 mol / liter of imidazole such as
It is preferable to add. The total time of the desilvering process is the result of defective desilvering.
It is preferable that the length is as short as possible. Preferred time is 1 minute to 3
Minutes, more preferably 1 to 2 minutes. Also processing temperature
Is 25 ° C to 50 ° C, preferably 35 ° C to 45 ° C.
In the preferred temperature range, the desilvering rate is improved and
Stain generation after treatment is effectively prevented. In the desilvering process, stirring is as strong as possible.
It is preferable that Specific method of strengthening stirring
As a photosensitive material described in JP-A-62-183460.
A method in which a jet of processing liquid collides with the emulsion surface
Use the rotating means in No. 62-183461 to increase the stirring effect
The method to get off is mentioned. Furthermore, a wire provided in the liquid
Move photosensitive material while contacting par blade and emulsion surface
And more stirring effect by making the emulsion surface turbulent
Increase the circulation flow rate of the entire processing solution
Method. Such a stirring improving means is bleaching
Effective in any of solution, bleach-fixing solution and fixing solution
The Stirring is improved by bleaching agent and fixing agent in emulsion film.
To speed up the supply of silver and consequently increase the desilvering speed
It is done. Also, the above stirring improvement means uses a bleach accelerator.
It is more effective when the
Or to eliminate fixing problems with bleach accelerators
Can do. Automatic used for development of the light-sensitive material of the present invention
Developing machines are disclosed in JP-A-60-191257 and 60-19.
Photosensitive materials described in Nos. 1258 and 60-191259
It is preferable to have a conveying means. The above-mentioned JP-A-6
Such a carrier as described in 0-191257
The stage significantly reduces the amount of processing solution brought from the pre-bath to the post-bath.
Therefore, the effect of preventing the performance deterioration of the processing liquid is high. like this
The main effects are shortening of processing time and replenishment of processing solution in each process.
This is particularly effective for reducing the amount. Silver halide color photographic light-sensitive material of the present invention
After desilvering, it is recommended to go through water washing and / or stabilization process.
It is common. The amount of water washed in the washing process is a characteristic of the photosensitive material.
(For example, depending on the material used such as coupler), application,
Furthermore, for example, the washing water temperature, the number of washing tanks (number of stages),
Depending on replenishment methods such as counterflow and forward flow, and other various conditions
Can be set widely. Of these, the multistage countercurrent method
The relationship between the number of washing tanks and the amount of water is Journal of
  the Society of Motion Pi
cute and Television Engi
neers vol. 64, p. 248-253 (1955
In May). According to the multi-stage countercurrent system described in the above-mentioned document,
Although the amount of washing water can be greatly reduced, the water in the tank
Increased residence time causes bacteria to grow and
There arises a problem that the play material adheres to the photosensitive material.
In the processing of the color light-sensitive material of the present invention, such a problem.
As a solution to the problem, described in JP-A-62-288838
Reduces calcium and magnesium ions
The method can be used very effectively. In addition,
For example, isothiazolonation described in No. 57-8542
Compounds, siabendazoles, chlorinated isocyanuric acid
Chlorine disinfectants such as sodium, etc.
Horiguchi Hiroshi “Non-Triazole”
Science (1986) Sankyo Publishing, Hygienic Technology Society
Sterilization, sterilization and fouling technology "(1982) Japan Industrial Technology Association, Japan
This edition of the Society for Antibacterial and Antifungal Studies, “Encyclopedia of Antibacterial and Antifungal Agents” (1986)
The described fungicides can also be used. P of washing water in the processing of the light-sensitive material of the present invention
H is 4-9, preferably 5-8. Washing water temperature and
Depending on the characteristics and application of the photosensitive material,
Generally, it can be set, but in general, it is 20 seconds to 1 at 15 to 45 ° C.
0 minutes, preferably 25-40 ° C for 30 seconds to 5 minutes
Selected. Further, the light-sensitive material of the present invention can be used in place of the above water washing.
Alternatively, it can be treated directly with a stabilizing solution. this
In such stabilization treatment, JP-A-57-8543
No. 58-14834, 60-220345
All known methods described can be used. Further, following the water washing treatment, further stabilization
Sometimes it is processed. An example of this is color photography for photography.
Dye stabilizers and surface activity used as the final bath of materials
Mention may be made of a stabilizing bath containing a sexing agent. Dye stability
Examples of the agent include formalin and glutaraldehyde.
Aldehydes, N-methylol compounds, hex
Samethylenetetramine or aldehyde sulfite addition
You can list things. In this stable bath,
Toning agents and fungicides can be added. The above-mentioned washing with water and / or replenishment with a stabilizing solution.
-The bar flow solution can be reused in other processes such as the desilvering process.
It can also be used. For example, in processing using an automatic processor,
When each of the above treatment solutions is concentrated by evaporation, water is added.
In addition, it is preferable to correct the concentration. Silver halide color photographic light-sensitive materials include
Color developer is built in for the purpose of simplifying and speeding up the process.
May be. In order to incorporate it, various types of color developing agents are used.
It is preferable to use a precursor. For example, US Patent No.
Indoaniline compounds described in 3,342,597,
For example, No. 3,342,599, Research Disc
Closure No. 14,850 and No. 15,1
59, the Schiff base type compound described in No. 59. 13,92
4, an aldol compound, U.S. Pat. No. 3,719,
No. 492, a metal salt complex described in JP-A-53-13562
The urethane type compound as described in No. 8 can be mentioned. Silver halide color light-sensitive materials can be used as needed.
For the purpose of accelerating color development, various 1-phenyls
-3-Pyrazolidones may be incorporated. Typical compound
For example, JP-A-56-64339 and 57-1
44,547 and 58-115438
It is. In the present invention, various processing solutions are used at 10 ° C. to 5 ° C.
Used at 0 ° C. Usually a temperature between 33 ° C and 38 ° C
Is standard, but at higher temperatures, the process is accelerated and processed.
To improve the image quality and process
An improvement in the stability of the liquid can be achieved. In addition, the silver halide photosensitive material of the present invention is
U.S. Pat. No. 4,500,626, JP-A-60-133
449, 59-218443, 61-2380
56, European Patent No. 210,660A2, etc.
The present invention can also be applied to photothermographic materials. Further, the silver halide color photographic feeling of the present invention is used.
The optical materials are Japanese Patent Publication No. 2-32615 and Japanese Utility Model Publication 3-397.
Film unit with lens described in No. 84 etc.
When applied to the
The [0347] The following examples are provided to further illustrate the present invention.
However, the present invention is not limited to these examples.
There is no. Example 1 (Emulsion preparation) In the same manner as in Example 2 of JP-A-2001-312022
Silver halide emulsions A-1 and BP were prepared. However,
Emulsion A-1 was replaced as follows. (Emulsion A-5) 4.50 × 10^-Fourmol / mol Ag
After adding D-1, C-5, potassium thiocyanate,
Chloroauric acid, sodium thiosulfate and N, N-dimethyl
Selenourea was added for optimal chemical sensitization. D
-1 to 0.51 × 10^-Four60 mol / mol Ag added
Stir for minutes. (Emulsion A-6) 2.25 × 10^-Fourmol / mol Ag
D-1 and 2.25 × 10^-FourMol / molAg 15
And added after mixing, C-5, potassium thiocyanate
, Chloroauric acid, sodium thiosulfate and N, N-dimethyl
Chilselenourea was added for optimal chemical sensitization. More
0.26 × 10^-Fourmol / mol Ag D-1;
0.25 × 10^-FourAfter mixing mol / mol Ag D-2
And stirred for 60 minutes. (Emulsion A-7) Emulsion using D-3 instead of D-2
Chemical sensitization was performed in the same manner as A-6. (Emulsion A-8) Emulsion using D-6 instead of D-2
Chemical sensitization was performed in the same manner as A-6. (Emulsion A-9) Emulsion using D-4 instead of D-2
Chemical sensitization was performed in the same manner as A-6. (Emulsion A-10) Using D-5 instead of D-2, milk
Chemical sensitization was performed in the same manner as Agent A-6. JP 2001-312022
A coated sample was prepared and evaluated in the same manner as in Example 2. Result
The results are shown in Table 1. [0349] [Table 1] The length of La was determined by the method shown in the text.
As an example, a method for calculating the length of D-1 La will be described. D-1
La is La-1 and D₁ -3 to the nitrogen atom
And D₂ Bonded to N atoms of -3. Therefore C
6 -C bonds, 4 C-N bonds, 4 C-O bonds
Thus, the distance values 1.54, 1.48, 1..
Using the value of 43 cm, it was determined to be 20.9 cm. From Table 1, two dyes having different structures were used.
In some cases, it was found that the sensitivity could be improved. Also different
A dye having a dye chromophore and a length difference of 7 mm or more
When using 2 types, it is found that the sensitivity is further enhanced.
It was. Example 2 (Preparation of seed emulsion a) KBr 0.017 g, average molecular weight 2
Aqueous solution 11 containing 0.4 g of 0000 oxidized gelatin
64 ml was kept at 35 ° C. and stirred. AgNO_Three (1.6
g) An aqueous solution, an aqueous KBr solution and an acid having an average molecular weight of 20000
Triple Jet of Gelatinized Gelatin (2.1g) Aqueous Solution
For 48 seconds. At this time, the silver potential is
It was kept at 13 mV to the romell electrode. KBr aqueous solution
In addition, after setting the silver potential to -66 mV, the temperature was raised to 60 ° C.
It was. 21 g of succinylated gelatin with an average molecular weight of 100,000
After adding an aqueous solution of NaCl (5.1 g)
It was. AgNO_Three (206.3 g) Aqueous solution and KBr aqueous solution
For 61 minutes while accelerating the flow rate with the double jet method
Added. At this time, the silver potential is set to the saturated calomel electrode.
And kept at -44 mV. After desalting, the average molecular weight is 100
000 succinylated gelatin and add a pH of 5.
8 and adjusted to pAg 8.8 to prepare a seed emulsion. This kind
Emulsions are 1 mol of Ag and 8 g of gelatin per kg of emulsion.
Contains 0g, average equivalent circle diameter 1.46μm, equivalent circle diameter
Coefficient of variation 28%, average thickness 0.046μm, average asphalt
It was a tabular grain having a pect ratio of 32. (Formation of core) 134 g of the above seed emulsion a,
KBr 1.9g, average molecular weight 100,000
Keep 1200 ml of aqueous solution containing 22 g of latin at 75 ° C.
Stir. AgNO_Three (43.9 g) Aqueous solution and KBr water
A solution and an aqueous gelatin solution having a molecular weight of 20000
Magnetic coupling induction stirrer described in No.-43570
25 minutes after mixing just before addition in another chamber with
Added in between. At this time, silver potential is saturated with calomel electrode
Against -40 mV. (Formation of first shell) Formation of the core particles
After, AgNO_Three (43.9 g) an aqueous solution and an aqueous KBr solution
Gelatin aqueous solution with a molecular weight of 20000
Mix immediately before addition in the bar and add over 20 minutes
It was. At this time, the silver potential is −40 with respect to the saturated calomel electrode.
It was kept at mV. (Formation of second shell) Shape of the first shell
After the formation, AgNO_Three (42.6 g) Aqueous solution and KBr aqueous solution
And an aqueous gelatin solution with a molecular weight of 20000.
And add for 17 minutes.
It was. At this time, the silver potential is −20 with respect to the saturated calomel electrode.
It was kept at mV. Thereafter, the temperature was lowered to 55 ° C. (Formation of third shell) Shape of the second shell
After the formation, the silver potential is adjusted to -55 mV and AgNO_Three (7.
1 g) Aqueous solution and KI (6.9 g) aqueous solution and molecular weight 200
00 aqueous gelatin solution added in a separate chamber
Mixed just prior to addition over 5 minutes. (Formation of fourth shell) Shape of the third shell
After the formation, AgNO_Three (66.4g) Aqueous solution and KBr aqueous solution
At a constant flow rate over 30 minutes using the double jet method
did. In the middle, potassium iridium hexachloride and yellow blood salt were added.
did. At this time, the silver potential is 30 with respect to the saturated calomel electrode.
It was kept at mV. Perform normal water washing, add gelatin,
The pH was adjusted to 5.8 and pAg 8.8 at 40 ° C. This milk
The agent was Emulsion b. Emulsion b has an average equivalent circular diameter of 3.3 μm,
Variation coefficient of equivalent circle diameter 21%, average thickness 0.090 μm,
The tabular grains had an average aspect ratio of 37. All throws
70% or more of the shadow area is 3.3 μ or more in equivalent circle diameter, and the thickness is 0.
It was occupied by tabular grains of 090 μm or less. Dye
80 square meters² The saturated coating amount is 1.4.
5 × 10^-3mol / molAg. Comparative Example 1 Emulsion b was heated to 56 ° C. and D
-1 is 12.0 × 10^-Fourmol / mol Ag was added
After, C-5, potassium thiocyanate, chloroauric acid, thiosulfur
Sodium acid and N, N-dimethylselenourea added
Optimal chemical sensitization was applied. Furthermore, D-1 is 2.5 × 1
0^-FourMol / mol Ag was added and stirred for 60 minutes. (Invention 1) Emulsion b was heated to 56 ° C. and 1.2 × 10^-Four
mol / mol Ag D-1 and 10.8 × 10^-Fourmol
/ MolAg D-5 was added, and then C-5, thio
Potassium cyanate, chloroauric acid, sodium thiosulfate and
Optimum chemical sensitization by adding N, N-dimethylselenourea
Was given. 0.25 x 10^-Fourmol / molAg
D-1 and 2.25 × 10^-Fourmol / mol Ag D-
5 was mixed and stirred for 10 minutes. (Invention 2) Emulsion b was heated to 56 ° C. and 3.0 × 10^-Four
mol / mol Ag D-1 and 9.0 × 10^-Fourmol /
After mixing and adding molAg D-5, C-5,
Potassium annate, chloroauric acid, sodium thiosulfate and
Optimum chemical sensitization by adding N, N-dimethylselenourea
gave. 0.63 × 10^-Fourmol / mol Ag
D-1 and 1.9 × 10^-Fourmol / mol Ag D-5
The mixture was added and stirred for 10 minutes. (Invention 3) The temperature of emulsion b is raised to 56 ° C. to 6.0 × 10^-Four
mol / mol Ag D-1 and 6.0 × 10^-Fourmol /
After mixing and adding molAg D-5, C-5,
Potassium annate, chloroauric acid, sodium thiosulfate and
Optimum chemical sensitization by adding N, N-dimethylselenourea
gave. 1.2 × 10^-Fourmol / mol Ag D
-1 and 1.2 × 10^-FourMixed with mol / mol Ag D-5
They were added together and stirred for 10 minutes. In addition, gelatin emulsion hardener, and
A coating aid is added, and the coating silver amount is 3.0 g-Ag / m.² In
On the cellulose acetate film support
And simultaneously coated with a gelatin protective layer. Obtained
Film against tungsten bulb (color temperature 2854K)
For 1 second through a continuous wedge color filter.
For minus blue exposure to excite the dye side as a color filter
Fuji Gelatin Filter SC-50 (Fuji Film
Sample) to block light of 500 nm or less.
Irradiated. The exposed sample is the following surface developer MAA
-1 and developed at 20 ° C for 10 minutes. Surface developer MAA-1 formulation Metol 2.5g 10g of L-ascorbic acid Nabox (FUJIFILM Corporation) 35g Potassium bromide 1g 1 liter with water pH 9.8 After development, fixing with the following fixing solution at 20 ° C.
Went. Fixer formulation 170g ammonium thiosulfate Sodium sulfite (anhydrous) 15g 7g of boric acid Glacial acetic acid 15ml Potash alum 20g Ethylenediaminetetraacetic acid 0.1g Tartaric acid 3.5g 1 liter with water Optical density of processed film is measured with Fuji automatic densitometer
Sensitivity required to give an optical density of +0.2
Indicated by the reciprocal of the amount of light, the sensitivity of Comparative Example 1 is represented as 100.
It was. The gradation is the difference in density between fog + 0.2 and fog + 1.2.
Expressed by the reciprocal of the ratio of the amount of light required to give
The gradation is expressed as 100. The results are shown in Table 2. [0362] [Table 2] From Table 2, two dyes having different structures were used.
In some cases, when two types are mixed in equal proportions, the sensitivity is increased.
I knew it was possible. [0364] According to the embodiment of the present invention, two types having different structures are provided.
By using the above multilayer adsorbing dyes, high sensitivity halo
A silver halide photographic material can be obtained.

Claims (1)

[Patent Claims 1. A compound represented by the following formula (I), halogenated, characterized in that it comprises at least two of D _1, D _2, or different compounds of structure L _a, Silver photographic material. General formula (I) In the formula, D ₁ and D ₂ represent a dye chromophore. La represents a linking group. q and r each represent an integer of 1 to 100. M represents a charge-balanced counter ion, and m represents the number necessary to neutralize the charge of the molecule.