JP2003241332A - Silver halide photographic sensitive material, silver halide emulsion composition and mercapto-containing polymer compound used in these - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stably producible silver halide photographic sensitive material having high sensitivity and excellent planeness. <P>SOLUTION: The silver halide photographic sensitive material contains at least one synthetic polymer having a nitrogen-containing aromatic ring having a mercapto group represented by Z-SH (Z is a nitrogen-containing aromatic ring) as a partial structure. Preferably the silver halide photographic sensitive material contains at least one homopolymer or copolymer of an ethylenically unsaturated bondcontaining monomer having a mercapto group represented by SH-Z-L<SP>1</SP>- (L<SP>1</SP>is a divalent linking group or a single bond) in at least one end. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel polymer containing a nitrogen-containing aromatic ring having a mercapto group. The present invention further provides a silver halide emulsion composition comprising the above-mentioned polymer and silver halide grains, a silver halide photographic light-sensitive material containing the above-mentioned polymer, and particularly the aggregation stability of silver halide in the silver halide photographic light-sensitive material. And a silver halide photographic light-sensitive material having improved

[0002]

2. Description of the Related Art Water-soluble polymers have been used for a long time in the photographic chemical industry, and the roles of water-soluble polymers in photographic systems are diverse. The reason why the water-soluble polymer has various roles is that the water-soluble polymer has excellent properties such as excellent protective colloidal property, sol-gel conversion property, ion permeability, moderate moisture absorption, and water retention property. . In particular, gelatin, which is one of the water-soluble polymers, is extremely excellent in the dispersion stability of silver halide in addition to the above characteristics, and is still used in large quantities as a dispersion stabilizer and binder for photographic light-sensitive materials. There is.

However, since gelatin is a material derived from natural products extracted from bones and skins of cattle and pigs, it is very difficult to keep its quality constant, and synthetic polymers are used as silver halide dispersion stabilizers. There have been many attempts to use it as. For example, US Pat. Nos. 3,615,624, 3,860,428 and 3,70.
Thioether group-containing polymers described in 6,564; U.S. Pat. Nos. 4,030,929 and 4,1.
52,161, the hydroxyquinoline-containing polymer; US Pat. Nos. 2,541,474, 3,284,207, 3,713,834, and 3,746. , 548, German Patent 3,28
4,207, acrylamide polymers described in JP-B-45-14031; U.S. Pat. No. 4,131,47
No. 1, the polyacrylic acid-containing polymer; US Pat. Nos. 3,345,346 and 3,706,56.
No. 4, No. 3,425,836, No. 3,51
1,818, 4,350,759, 3,832,185, and 3,852,073 amine-containing polymers described in U.S. Pat.
No. 0,741, No. 3,236,653, No. 2,579,016, No. 3,479,189, polyvinyl alcohol-containing polymers described in JP-B-43-7561 The copolymers of acrylamide, vinylimidazole, acrylic acid, etc. described in the official gazette may be mentioned. However, although silver halide grains are formed, there is a decrease in sensitivity, poor dispersion, rounded grains, and size distribution of grains. A dispersant superior to gelatin has not been found because of its harmful effects such as large size.

In recent years, there has been a demand for higher sensitivity of silver halide photographic light-sensitive materials, and it has become necessary to prepare a silver halide emulsion having a high aspect ratio and excellent flatness. On the other hand, as the aspect ratio becomes higher, agglomeration of the silver halide emulsion, which cannot be prevented by gelatin alone when preparing the silver halide emulsion, has become a problem. Therefore, attempts have been made to suppress the agglomeration of silver halide grains by using modified gelatin in which the functional part is modified to gelatin which is originally excellent in dispersion ability. As such modified gelatin, gelatin covalently bonded to latex (Japanese Patent Laid-Open No. 7-1521).
No. 03) has been proposed, but the effect cannot be said to be sufficient, and development of a dispersant for suppressing aggregation of silver halide grains having a high aspect ratio has been strongly desired.

[0005]

SUMMARY OF THE INVENTION The first object of the present invention is to provide a highly sensitive halogenated compound which can suppress aggregation of silver halide grains having a high aspect ratio and high sensitivity and excellent flatness. It is to provide a novel polymer useful for preparing a silver emulsion. A second object of the present invention is to provide a high-sensitivity silver halide emulsion which contains silver halide grains having a high aspect ratio stably without agglomeration. A third object of the present invention is to provide a silver halide photographic light-sensitive material which has high sensitivity, excellent flatness, pressure resistance and can be stably manufactured.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polymer having a nitrogen-containing aromatic ring having a mercapto group introduced does not aggregate silver halide grains. As a result of obtaining knowledge that it can be suppressed, and further studying based on this finding, it is possible to realize stable production of a photographic light-sensitive material having high sensitivity and excellent flatness by using the polymer. Heading out, the present invention has been completed.

That is, means for solving the above problems are as follows. [1] A silver halide photographic light-sensitive material containing at least one synthetic polymer having a mercapto group represented by the following general formula (1). General formula (1) Z-SH (In the formula, Z represents a nitrogen-containing aromatic ring.) [2] The synthetic polymer is a water-soluble polymer [1].
The silver halide photographic light-sensitive material described in. [3] The synthetic polymer has an average of two mercapto groups represented by the general formula (1) / (one polymer chain).
The silver halide photographic light-sensitive material according to [1] or [2], which is contained below. [4] A silver halide photographic light-sensitive material containing at least one synthetic polymer represented by the following general formula (2).

General formula (2)

[Chemical 2]

In the formula, X represents a homopolymer or copolymer group of a monomer having an ethylenically unsaturated bond. Y ¹
And Y ² are terminal groups of X, at least one of which is SH
-Z-L ¹ - represents a. Z represents a nitrogen-containing aromatic ring, and L ¹ represents a divalent linking group or a single bond.

[5] The number average molecular weight of the synthetic polymer represented by the general formula (2) is 5,000 or more [4].
The silver halide photographic light-sensitive material described in.

[6] A silver halide emulsion composition containing at least one synthetic polymer having a mercapto group represented by the above general formula (1) and silver halide grains. [7] The synthetic polymer is a water-soluble polymer [6]
The silver halide emulsion composition described in 1. [8] The synthetic polymer has an average of 2 mercapto groups represented by the general formula (1) / (1 polymer chain).
The silver halide emulsion composition according to [6] or [7], which is contained below. [9] The silver halide emulsion composition according to any one of [6] to [8], wherein the synthetic polymer is a polymer represented by the general formula (2).

[10] A mercapto group-containing polymer compound represented by the above general formula (2). [11] A mercapto group-containing polymer compound represented by the following general formula (2-A).

[0013]

[Chemical 3]

In the formula, R ¹¹ represents a hydrogen atom or a methyl group, and R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent. X ¹ represents a monomer unit having an ethylenically unsaturated bond, and may be one kind or plural kinds. m and n represent the mass ratio of the monomer units, m
+ N = 100. In addition, the copolymerization form of the monomer unit contained in the formula may be any form of random copolymerization, block copolymerization and alternating copolymerization. Y
¹ and Y ² are terminal groups, and at least one of Y ¹ and Y ² represents a mercapto group represented by SH-Z-L ^1- . Z represents a nitrogen-containing aromatic ring, and L ¹ represents a divalent linking group or a single bond.

[12] A mercapto group-containing polymer compound represented by the following general formula (2-B).

[0016]

[Chemical 4]

In the formula, X ¹ , R ¹¹ , m and n have the same meanings as those in formula (2-A). Y ¹¹ and Y
¹² is a terminal group, and at least one of Y ¹¹ and Y ¹² represents a group represented by the following general formula (3).

[0018]

[Chemical 5]

In the formula, L ^1A represents a divalent linking group or a single bond, and Q represents N, CH or C-SH.

[13] A mercapto group-containing polymer compound represented by the following general formula (2-C).

[0021]

[Chemical 6]

In the formula, Y ¹¹ , Y ¹² and R ¹¹ have the same meanings as those in formula (2-B). R ²¹ represents a hydrogen atom or a methyl group, and L ² represents a single bond or a divalent linking group. m ² and n ² represent the mass ratio of the monomer units, and m ² + n ² = 100. M represents a hydrogen atom or a cation. )

[14] A silver halide photographic light-sensitive material containing at least one silver halide emulsion composition described in any of [6] to [9] above. [15] A silver halide photographic light-sensitive material containing at least one kind of the polymer described in any of [11] to [13].

[0024]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a method for carrying out the present invention and an embodiment will be described in detail. In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. First, the mercapto group-containing polymer used in the present invention will be described. The mercapto group-containing polymer used in the present invention is a mercapto group-containing synthetic polymer represented by the following general formula (1). General formula (1) Z-SH

In the general formula (1), the nitrogen-containing aromatic ring represented by Z is, specifically, a monocyclic or condensed ring nitrogen-containing aromatic heterocycle, preferably 5 to 7-membered. A nitrogen-containing aromatic heterocycle, more preferably a 5- or 6-membered nitrogen-containing aromatic heterocycle. Specifically, imidazole, pyrazole, triazole, tetrazole, thiazole,
Oxazole, selenazole, benztriazole, benzthiazole, benzoxazole, benzselenazole, thiadiazole, oxadiazole, naphthothiazole, naphthoxazole, azabenzimidazole, purine, pyridine, pyrazine, pyrimidine, pyridazine, triazine, triazaindene, tetra The inden etc. are mentioned. More preferably, it is a 5-membered nitrogen-containing aromatic heterocycle, and specific examples thereof include imidazole, pyrazole, triazole, tetrazole, thiazole, oxazole, benztriazole, benzthiazole, benzoxazole, thiadiazole and oxadiazole. Particularly preferred are triazole and tetrazole, and most preferred is tetrazole.

The polymer of the present invention is preferably a water-soluble polymer. In the present specification, the “water-soluble polymer” refers to a polymer that is soluble in water at 0.5% by mass or more, preferably 1.0% by mass or more, and more preferably 2.0. It is a polymer that dissolves by mass% or more, and more preferably a polymer that dissolves by 4.0 mass% or more.

The polymer of the present invention has an average of 2 mercapto groups represented by the above-mentioned general formula (1) / (polymer chain 1
It is preferable to contain the following). On average per polymer chain, more preferably 0.01 to 1.5, even more preferably 0.1 to 2, and even more preferably 0.1.
˜1.8, particularly preferably 0.2 to 1.5, and most preferably 1 or less. Here, the number of mercapto groups per polymer chain is the molar concentration A _{Mn of} the water-soluble synthetic polymer aqueous solution obtained from the number average molecular weight Mn of the polymer when GPC measurement is performed using polyethylene oxide as a reference substance, and the polymer Molar concentration Qu determined from UV absorbance of nitrogen-containing aromatic ring having mercapto group in aqueous solution
v is measured and is obtained as the value of Quv / A _Mn . That is, the polymer of the present invention preferably has a Quv / A _Mn of 2 or less, more preferably 1 or less. When the introduction amount of the mercapto group is within the above range, it is possible to further suppress an increase in fog density without lowering the sensitivity of the silver halide photographic light-sensitive material, and further to suppress the occurrence of silver halide grains after the emulsion is dissolved. More effective in suppressing aggregation. as a result,
The deterioration of photographic performance during coating is improved, and it becomes possible to prepare a silver halide emulsion having more excellent production suitability.

In the polymer of the present invention, the mercapto group represented by the general formula (1) is preferably introduced at one end of the polymer.

A preferred embodiment of the polymer of the present invention is a polymer represented by the following general formula (2).

[0030]

[Chemical 7]

In the formula, Y ¹ and Y ² are terminal groups of X, and at least one of them represents SH-Z-L ^1- . Z has the same meaning as that represented in formula (1), and the preferred range is also the same. When only ^one of Y ¹ and Y ² represents HZL ^1- , the other may be any group introduced in the polymer synthesis process, and examples thereof include a hydrogen atom, a polymerization initiator, and a solvent. Besides the molecule or monomer derivative, the additive derivative at the time of synthesis can be the other end group.

L ¹ represents a divalent linking group or a single bond,
There is no particular limitation as long as it is a divalent linking group or a single bond,
L ¹ is preferably a divalent linking group having 0 to 20 carbon atoms. Specifically, an alkylene group having 1 to 20 carbon atoms (for example, methylene, ethylene, propylene, butylene, xylylene, etc.), an arylene group having 6 to 20 carbon atoms (for example, phenylene, naphthylene, etc.), -C (= O)-, -S
(= O) _2- , -S (= O)-, -S-, -O-, -P
^{(= O) O - -,} - P (= O) O - -, - P (= O) OR
^a −, —NR ^a — (R ^a represents a hydrogen atom or a substituent,
As the substituent, those exemplified as the substituent T described later can be applied), -N =, an aromatic heterocyclic group, or a divalent linking group having 0 to 20 carbon atoms obtained by combining two or more kinds of them. Is. A specific example is shown below.

[0033]

[Chemical 8]

These may be bonded to Z in either the right or left direction, but it is preferable that the left side is bonded to Z.

If possible, L ¹ may further have a substituent T, and examples of the substituent T include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 carbon atom).
To 12 and particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, iso-propyl, tert-butyl, n
-Octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 20 carbon atoms,
More preferably, it has 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, such as vinyl, allyl, 2-butenyl,
3-pentenyl and the like) and alkynyl groups (preferably having 2 to 20 carbon atoms, more preferably having 2 to 1 carbon atoms).
2, particularly preferably having 2 to 8 carbon atoms, for example, propargyl, 3-pentynyl and the like), an aryl group (preferably having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably carbon number) 6-12, for example, phenyl, p-methylphenyl, naphthyl, etc.), a substituted or unsubstituted amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and particularly preferably carbon). Number 0 to 6, for example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like), alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably It has 1 to 8 carbon atoms, and examples thereof include methoxy, ethoxy, butoxy, etc.) and aryloxy groups (preferably having carbon atoms). 20, more preferably 6 carbon atoms
To 16 and particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyloxy and 2-naphthyloxy),

Acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 carbon atoms)
To 12 and, for example, acetyl, benzoyl, formyl, pivaloyl and the like), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms) ,
For example, methoxycarbonyl, ethoxycarbonyl and the like), aryloxycarbonyl group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, for example phenyloxycarbonyl etc. And an acyloxy group (preferably having a carbon number of 2 to 20, more preferably having a carbon number of 2).
To 16, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy, and acylamino groups (preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, and particularly preferably carbon atoms). 2 to 10 and examples thereof include acetylamino and benzoylamino), alkoxycarbonylamino groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms,
Particularly preferably, it has 2 to 12 carbon atoms, and examples thereof include methoxycarbonylamino and the like, aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, and particularly preferably 7 carbon atoms). ~
12 and examples thereof include phenyloxycarbonylamino and the like, a sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example methanesulfonyl). Amino, benzenesulfonylamino and the like), a sulfamoyl group (preferably having a carbon number of 0 to 20,
It preferably has 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms, and examples thereof include sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, and the like, carbamoyl group (preferably having carbon atoms). 1 to 20, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like),

Alkylthio group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methylthio and ethylthio.), An arylthio group (preferably 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms). 16, particularly preferably 6 to 12 carbon atoms, such as phenylthio, etc.), a sulfonyl group (preferably 1 to 2 carbon atoms).
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl), sulfinyl groups (preferably 1 to 2 carbon atoms).
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl), ureido groups (preferably 1 to 20 carbon atoms, and more preferably carbon atoms). 1-1
6, particularly preferably 1 to 12 carbon atoms, and examples thereof include ureido, methylureido, phenylureido and the like), phosphoric acid amide group (preferably 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, and examples thereof include diethylphosphoric acid amide, phenylphosphoric acid amide, etc.), hydroxy group, mercapto group, halogen atom (eg, fluorine atom, chlorine). Atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, imino group, heterocyclic group (preferably 1 to 30 carbon atoms, more preferably 1 And the hetero atom is, for example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl and the like. ), A silyl group (preferably having 3 to 40 carbon atoms,
More preferably, it has 3 to 30 carbon atoms, and particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl and triphenylsilyl). These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to each other to form a ring.

In the general formula (2), X represents a homopolymer or copolymer group of a monomer having an ethylenically unsaturated bond, and in the case of a copolymer, a random copolymer or a block copolymer. It may be in any form of a coalesced product, an alternating copolymer and a graft copolymer. Further, when X is a copolymer, there is no particular limitation as to which monomer forms a covalent bond with L ¹ .

X contains at least one monomer unit having an ethylenically unsaturated bond (hereinafter referred to as a monomer).
The monomer is not particularly limited as long as it is a polymerizable monomer, and any monomer that can be polymerized by radical polymerization or ionic polymerization can be used. As the monomer for X, a monomer whose homopolymer is water-soluble is preferable. X may be a copolymer of a plurality of monomers as long as the water solubility of X is not impaired.

Examples of the monomer that makes the homopolymer water-soluble include the following monomer group (k), and all of them are preferably used as the monomer of X. (K) Acrylic acid, methacrylic acid, acrylamide, N-methylacrylamide, Nn-propylacrylamide, N-isopropylacrylamide, N, N-dimethylacrylamide, N-acryloylmorpholine, N-acryloylpiperidine, methacrylamide, N- Methylmethacrylamide, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylacetamide, diacetone acrylamide, ω-methoxypolyethylene glycol acrylate (addition mol number n = 9), ω-methoxypolyethylene glycol acrylate (addition mol number n = Two
3), N-methoxyethylacrylamide and the like.

When X is a copolymer, the above-mentioned (k)
Copolymers of at least one of any of the above monomer groups and at least one of any of the following monomer groups (a) to (j) are preferred. It should be noted that even among the monomers belonging to the above-mentioned (k) monomer group, those belonging to the (a) to (j) monomer groups are listed in duplicate.

-Monomer groups (a) to (i)-(a) conjugated diene: 1,3-butadiene, isoprene,
1,3-pentadiene, 2-ethyl-1,3-butadiene, 2-n-propyl-1,3-butadiene, 2,3-
Dimethyl-1,3-butadiene, 2-methyl-1,3-
Butadiene, 1-phenyl-1,3-butadiene, 1-
α-naphthyl-1,3-butadiene, 1-β-naphthyl-1,3-butadiene, 2-chloro-1,3-butadiene, 1-bromo-1,3-butadiene, 1-chloro-1,
3-butadiene, 2-fluoro-1,3-butadiene,
2,3-Dichloro-1,3-butadiene, 1,1,2-trichloro-1,3-butadiene, 2-cyano-1,3-butadiene, cyclopentadiene, etc. (b) Olefin: ethylene, propylene, vinyl chloride, chloride Vinylidene, 6-hydroxy-1-hexene,
4-pentenoic acid, methyl 8-nonenate, vinylsulfonic acid, trimethylvinylsilane, trimethoxyvinylsilane, 1,4-divinylcyclohexane, 1,2,5-trivinylcyclohexane, etc.

(C) α, β-unsaturated carboxylic acid esters: alkyl acrylates (eg, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, etc.), substituted alkyl acrylates (eg, 2-chloroethyl acrylate, benzyl acrylate, 2-cyanoethyl acrylate, etc.), alkyl methacrylate (eg, methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, dodecyl methacrylate, etc.), substituted alkyl methacrylate (eg, 2-hydroxyethyl methacrylate). , Glycidyl methacrylate, glycerin monomethacrylate, 2-acetoxyethyl methacrylate, tetrahydro Le frills methacrylate, 2
-Methoxyethyl methacrylate, polypropylene glycol monomethacrylate (polyoxypropylene added mol number = 2 to 100), 3-N, N-dimethylaminopropyl methacrylate, chloro-3-
N, N, N-trimethylammoniopropyl methacrylate, 2-carboxyethyl methacrylate, 3-sulfopropyl methacrylate, 4-oxysulfobutyl methacrylate, 3-trimethoxysilylpropyl methacrylate, allyl methacrylate, 2-isocyanatoethyl methacrylate, etc.) , Derivatives of unsaturated dicarboxylic acids (eg, monobutyl maleate, dimethyl maleate, monomethyl itaconate, dibutyl itaconate, etc.),
Polyfunctional esters (eg ethylene glycol diacrylate, ethylene glycol dimethacrylate, 1,4
-Cyclohexane diacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, trimethylolpropane triacrylate, trimethylolethane triacrylate, dipentaerythritol pentamethacrylate, pentaerythritol hexaacrylate, 1,2,4-cyclohexanetetramethacrylate, etc.)

(D) Amides of β-unsaturated carboxylic acids: for example, acrylamide, methacrylamide, N-methylacrylamide, N, N-dimethylacrylamide, N-methyl-N-hydroxyethylmethacrylamide, N-tertbutylacrylamide. , N-tert
Octyl methacrylamide, N-cyclohexyl acrylamide, N-phenyl acrylamide, N- (2-acetoacetoxyethyl) acrylamide, N-acryloylmorpholine, diacetone acrylamide, itaconic acid diamide, N-methyl maleimide, 2-acrylamido-methyl propane Sulfonic acid, methylenebisacrylamide, dimethacryloylpiperazine, etc. (e) Unsaturated nitriles: acrylonitrile, methacrylonitrile, etc. (f) Styrene and its derivatives: styrene, vinyltoluene, p-tert-butylstyrene, vinylbenzoic acid, vinylbenzoic acid Methyl acid, α-methylstyrene, p-
Chloromethylstyrene, vinylnaphthalene, p-hydroxymethylstyrene, p-aminomethylstyrene, 1,
4-divinylbenzene, etc. (g) Vinyl ethers: methyl vinyl ether, butyl vinyl ether, methoxyethyl vinyl ether, etc. (h) Vinyl esters: vinyl acetate, vinyl propionate, vinyl benzoate, vinyl salicylate vinyl chlorovinyl acetate, etc.

(I) Acid group-containing monomer: acrylic acid, sodium acrylate, potassium acrylate, lithium acrylate, ammonium acrylate, methacrylic acid, sodium methacrylate, potassium methacrylate,
Lithium methacrylate, ammonium methacrylate, itaconic acid, potassium itaconic acid, maleic acid, CH ₂ =
CHCOOCH ₂ CH ₂ COOH, CH ₂ = CHCONH
CH ₂ CH ₂ COOH, CH ₂ = CHC ₆ H ₅ COOH
_{(P), CH 2 = CHCOOCH} 2 CH 2 CH 2 COOH,
α-Chloroacrylic acid, sodium styrenesulfonate, ammonium styrenesulfonate, lithium styrenesulfonate, 2-acrylamido-2-methyl-propanesulfonic acid, 2-acrylamido-2-methyl-sodiumpropanesulfonate, 2-acrylamide -2
-Ammonium methyl-propane sulfonate, 3-acryloyloxy-sodium propane sulfonate, 3-
Methacryloyloxy-propane sulfonate,
Isoprenesulfonic acid and the like, sodium 3-acryloyloxy-ethylphosphonate and the like (j) Other polymerizable monomers: N-vinylimidazole, 4-vinylpyridine, N-vinylpyrrolidone, 2-
Examples thereof include vinyl oxazoline, 2-isopropenyl oxazoline, divinyl sulfone and the like.

X is one homopolymer or two or more copolymers selected from the above-mentioned (k) monomer group,
Alternatively, a copolymer of at least one selected from the (k) monomer group and at least one selected from the (i) acid group-containing monomer group is preferable, and one copolymer selected from the (k) monomer group is preferable. A homopolymer or a copolymer of two or more kinds is more preferable. A further preferred embodiment of X is
Homopolymer of monomer having carboxylic acid group or 2
It is a copolymer of one or more kinds, and a more preferable embodiment is
Acrylic acid, methacrylic acid, CH ₂ = CHCOOCH ₂ C
H ₂ COOH, CH ₂ = CHCONHCH ₂ CH ₂ COOH
Or a homopolymer of CH ₂ ═CHCOOCH ₂ CH ₂ CH ₂ COOH or a copolymer of two or more of these, and particularly preferred embodiments are homopolymers of acrylic acid or methacrylic acid, or acrylic acid or methacrylic acid with these. , CH ₂ = CHCOOCH ₂ CH ₂ COOH, CH ₂ = C
HCONHCH ₂ CH ₂ COOH or CH ₂ = CHC
OOCH ₂ CH ₂ CH ₂ COOH Copolymer with other monomers.

A preferred embodiment of the polymer represented by the general formula (2) is a polymer represented by the following general formula (2-A).

[0048]

[Chemical 9]

In the formula, R ¹¹ represents a hydrogen atom or a methyl group, preferably a methyl group.

R ¹² and R ¹³ each independently represent a hydrogen atom or a substituent, and the substitution has the same meaning as the above-mentioned substituent T. R ¹² and R ¹³ are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, further preferably a hydrogen atom or a methyl group, and particularly preferably hydrogen. Is an atom.

Where X¹Has an ethylenically unsaturated bond
It represents a monomer unit of
May be. X¹Is not particularly limited as long as it can be polymerized.
Mono as exemplified as the monomer of X in the general formula (2)
Use a monomer selected from the mer groups (a) to (k)
You can Polymer represented by the general formula (2-a)
A preferred embodiment of the compound is X¹Contains the above (i) acid group
At least one selected from the group of monomers
¹Is not present (that is, n = 0). Yo
A more preferred embodiment is X¹Mono containing a carboxylic acid group
More preferably, it is at least one kind of mer.
The mode is X¹Is acrylic acid, methacrylic acid, CH₂= C
HCOOCH₂CH₂COOH, CH₂= CHCONHC
H₂CH₂COOH or CH₂= CHCOOCH ₂CH₂
CH₂A preferred embodiment is COOH, and a particularly preferred embodiment
Is X¹In the embodiment of acrylic acid or methacrylic acid
It

In the formula, m and n represent the mass ratio of the monomer units, and m + n = 100. m is preferably 50 to 100, more preferably 70 to 100, and further preferably 80 to 100. n is preferably 0
-50, more preferably 0-30, still more preferably 0
~ 20. When X ¹ contains two or more kinds of monomer units, the total mass ratio of the monomer units is n.

Y ¹ and Y ² are terminal groups, but at least one of them represents SH-Z-L ^1- . At least Y ¹ is SH
-Z-L ¹ - is preferably. Z represents a nitrogen-containing aromatic ring, has the same meaning as Z in the general formula (1), and the preferred range is also the same. L ¹ represents a divalent linking group or a single bond, has the same meaning as L ¹ in the general formula (2), and the preferred range is also the same.

A more preferred embodiment of the polymer represented by the general formula (2) is a polymer represented by the following general formula (2-B).

[0055]

[Chemical 10]

In the formula, X ¹ , R ¹¹ , m and n have the same meanings as those in formula (2-A), and the preferred ranges are also the same. Y ¹¹ and Y ¹² are terminal groups, and at least one of them represents a group represented by the following general formula (3).

[0057]

[Chemical 11]

In the formula, L ^1A represents a divalent linking group or a single bond. There is no particular limitation as long as it is a divalent linking group or a single bond, but L ^1A is preferably a divalent linking group having 0 to 14 carbon atoms. Specifically, an alkylene group having 1 to 14 carbon atoms (for example, methylene, ethylene, propylene, butylene,
Xylylene), an arylene group having 6 to 14 carbon atoms (for example, phenylene, naphthylene, etc.) -C (= O)-,-
S (= O) _2- , -S (= O)-, -S-, -O-,-
^{P (= O) O - -} , - P (= O) O - -, - P (= O) O
R ^a −, —NR ^a — (R ^a represents a hydrogen atom or a substituent, and the substituent may be any of those mentioned above as the substituent T), —N =, an aromatic heterocyclic group or these. Is a divalent linking group having 0 to 14 carbon atoms, which is obtained by combining two or more of the above. A specific example is shown below.

[0059]

[Chemical 12]

In the formula, Q represents N, CH or C-SH, preferably N or CH, and more preferably N.
Is.

A more preferred embodiment of the polymer represented by the general formula (2) is a polymer represented by the following general formula (2-C).

[0062]

[Chemical 13]

In the formula, Y ¹¹ and Y ¹² are represented by the general formula (2
-Synonymous with those in B). That is, at least one of Y ¹² and Y ¹² represents a group represented by the general formula (3), and the preferred range is also the same. In the formula, R ¹¹ has the same meaning as R ¹¹ in formula (2-B), and the preferred range is also the same.

In the formula, R ²¹ represents a hydrogen atom or a methyl group, preferably a hydrogen atom.

Where L²Is a single bond or a divalent linking group
Any single bond or divalent linking group may be used.
But L²Is preferably a single bond or 0 to 20 carbon atoms.
Is a divalent linking group, more preferably a single bond or charcoal.
A divalent linking group having a prime number of 0 to 10, specifically, a single bond
Or an alkylene group having 1 to 10 carbon atoms (for example, methyl
Ethylene, propylene, butylene, xylylene
Etc.), an arylene group having 6 to 10 carbon atoms (for example, phenyle
, Naphthylene, etc.) -C (= O)-, -S (= O)₂
-, -S (= O)-, -S-, -O-, -P (= O) O
^--, -P (= O) O ^--, -P (= O) ORa-, -N
R^a-(R^aRepresents a hydrogen atom or a substituent,
The above-mentioned examples of the substituent T can be applied),
-N =, an aromatic heterocyclic group, or a combination of two or more of these.
A divalent linking group having 0 to 10 carbon atoms, which is also obtained.
More preferably a single bond or

[0066]

[Chemical 14]

It is These may be bonded to the polymer main chain in either the right or left direction, but the left side is preferably bonded to the polymer main chain.

In the formula, m ² and n ² represent the mass ratio of the monomer units, and m ² + n ² = 100. m ² is preferably 50 to 100, more preferably 70 to 100,
More preferably, it is 80-100. n ² is preferably 0 to 50, more preferably 0 to 30, and further preferably 0 to 20.

In the formula, M represents a hydrogen atom or a cation. Preferably, a hydrogen atom, an alkali metal ion, an alkaline earth metal ion or an ammonium ion,
Particularly preferred are hydrogen atom, lithium ion, sodium ion, potassium ion or ammonium ion.

The number average molecular weight of the polymer of the present invention is preferably 5,000 or more, more preferably 10,000.
0 or more, more preferably 30,000 or more, particularly preferably 50,000 or more, and most preferably 100,
It is more than 000.

Next, an example of a general method for synthesizing the polymer of the present invention will be shown, but the invention is not limited thereto. The polymer of the present invention is obtained by reacting a polymer obtained by a polymerization reaction in advance with a compound containing a nitrogen-containing aromatic ring having a mercapto group and capable of forming a covalent bond with a reactive group in the polymer to introduce the mercapto group. Or a compound having a nitrogen-containing aromatic ring having a mercapto group may be polymerized with a monomer. The monomer unit includes radical polymerization, ionic polymerization,
Polymerization may be carried out by any polymerization reaction such as polycondensation, ring-opening polymerization and polyaddition.

Below, the general formulas (2), (2-A),
Specific examples of the polymer represented by (2-B) or (2-C) are shown below, but the present invention is not limited to the following specific examples.

[0073]

[Chemical 15]

[0074]

[Chemical 16]

[0075]

[Chemical 17]

Next, the silver halide photographic light-sensitive material of the present invention will be described. The silver halide photographic light-sensitive material of the present invention contains the polymer of the present invention in at least one of hydrophilic colloid layers (for example, a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer). A preferred embodiment of the silver halide photographic light-sensitive material of the present invention is an embodiment in which the polymer of the present invention is contained in at least one of the silver halide emulsion layer and its adjacent hydrophilic colloid layer, and a particularly preferred embodiment is silver halide. In this embodiment, the emulsion layer contains the polymer of the present invention.

The polymer of the present invention can be contained in the layer forming composition when forming the hydrophilic colloid layer of the silver halide photographic light-sensitive material. When the polymer of the present invention is contained in the silver halide emulsion layer, it is used during the preparation of the silver halide emulsion. The timing of addition of the polymer of the present invention is the silver halide grain forming process, the chemical ripening process, and the completion of chemical ripening. It may be at any later timing. Most preferably, it is added during the grain formation process. Further, the synthetic polymer of the present invention may be dissolved in water or a hydrophilic organic solvent (for example, methanol, N, N-dimethylformamide) and added.

The silver halide photographic light-sensitive material of the present invention comprises
A material that is sensitive to light, laser or X-ray irradiation. Black-and-white reversal film, black-and-white negative film, color negative film, color reversal film, film in which photosensitive photographic components are digitally scanned, black-and-white reversal paper, black-and-white paper, color It may be in the form of paper, reversal color paper, or paper in which the photosensitive photographic element is exposed by laser irradiation from a digital database. A color negative film is preferred as the silver halide photographic light-sensitive material,
As an embodiment thereof, for example, JP-A-11-30539
No. 6 publication and the like can be mentioned.

The shape of the silver halide grain emulsion used in the present invention has regular crystals such as cubes, octahedra and tetradecahedrons, and irregular crystals such as spheres and plates. And those having crystal defects such as twin planes, or a composite form thereof. In particular, tabular grains are more preferable. In the tabular grain emulsion, 50% or more of the total projected area is preferably occupied by grains having an aspect ratio of 3 or more. Here, the projected area and aspect ratio of the tabular grains can be measured from an electron micrograph by a carbon replica method in which a shadow is cast together with a latex sphere for reference. When viewed in a direction perpendicular to the principal plane, tabular grains usually have a hexagonal, triangular or circular shape, but have a diameter (circular equivalent diameter) corresponding to a circle having an area equal to the projected area. The aspect ratio is the value divided by the thickness. The shape of tabular grains is more preferable as the ratio of hexagons is higher, and
The ratio of the lengths of adjacent sides of the hexagon is preferably 1: 2 or less.

The effect of the present invention is such that the higher the aspect ratio, the more preferable photographic performance can be obtained. Therefore, it is preferable that 50% or more of the total projected area of the tabular grain emulsion is occupied by grains having an aspect ratio of 8 or more. More preferably, the aspect ratio is 1
It is 2 or more. If the aspect ratio becomes too large, the coefficient of variation of the particle size distribution described above tends to increase, so the aspect ratio is usually preferably 50 or less.

The average grain diameter of the silver halide grains used in the present invention is 0.2 to 10.0 μm as the average equivalent circle diameter.
It is preferably m, and more preferably 0.5 to 5.0 μm. The equivalent circle diameter is the diameter of a circle having an area equal to the projected area of the parallel principal planes of the particles. The projected area of the particles can be obtained by measuring the area on an electron micrograph and correcting the photographing magnification. The average equivalent spherical diameter is preferably 0.1 to 5.0 μm,
It is more preferably 0.6 to 2.0 μm. These ranges have the best sensitivity / granularity relationship for photographic emulsions. In the case of tabular grains, the average thickness is 0.0
It is preferably 5 to 1.0 μm. Here, the average equivalent circle diameter means an average value of equivalent circle diameters of 1000 or more grains arbitrarily sampled from a uniform emulsion. The same applies to the average thickness. The silver halide grains used in the present invention may be monodisperse or polydisperse.

The tabular grain emulsion preferably comprises (111) main planes facing each other and side faces connecting the main planes. It is preferable that at least one twin plane is provided between the main planes. In the tabular grain emulsion used in the present invention, it is preferable that normally two twin planes are observed. This 2
The spacing of the twin planes can be less than 0.012 μm as described in US Pat. No. 5,219,720. Further, as described in JP-A-5-249585, the value obtained by dividing the distance between (111) principal planes by the twin plane spacing can be 15 or more.

In the present invention, it is preferable that 75% or less of all side faces of the tabular grain emulsion connecting opposite (111) main planes are composed of (111) faces. Here, 75% or less of all side faces are composed of (111) faces means that crystallographic planes other than the (111) faces are present at a ratio higher than 25% of all side faces. Usually, the plane can be understood as a (100) plane, but it can also include other planes, that is, a (110) plane and a plane with a higher index. In the present invention, the effect is remarkable when 70% or less of all the side faces are composed of (111) faces.

The silver halide solvent which can be used in the present invention includes US Pat. Nos. 3,271,157, 3,531,289 and 3,574.
628, JP-A-54-1019, JP-A-54-1019
(A) organic thioethers described in JP-A-158917 and the like, JP-A-53-82408 and JP-A-55-7.
No. 7737, No. 55-2982, etc. (b) Thiourea derivatives, and (c) No. 53-144319, (c) Oxygen or sulfur atoms sandwiched between nitrogen atoms. Examples thereof include a silver halide solvent having a thiocarbonyl group, (d) imidazoles described in JP-A No. 54-100717, (e) ammonia, and (f) thiocyanate. Particularly preferred solvents are thiocyanate, ammonia and tetramethylthiourea. The amount of the solvent used varies depending on the kind, but in the case of thiocyanate, the preferable amount is 1 × 10 ⁻⁴ mol or more per 1 mol of silver halide and 1 ×.
It is 10 ^-2 mol or less.

As a method of changing the surface index of the side surface of the tabular grain emulsion, reference can be made to European Patent Publication EP515894A1. US Pat. No. 5,25
It is also possible to use the polyalkylene oxide compound described in the specification of No. 2,453. As an effective method, US Pat. Nos. 4,680,254 and 4,680,2
The surface index modifiers described in No. 55, No. 4,680, 256, No. 4,684, 607, etc. can be used. Ordinary photographic spectral sensitizing dyes can also be used as a modifier having the same surface index as above.

In the present invention, it can be prepared by various methods as long as the above-mentioned requirements are satisfied. The preparation of a tabular grain emulsion usually consists of basically three steps of nucleation, ripening and growth. In the nucleation step, use of gelatin having a low methionine content described in US Pat. Nos. 4,713,320 and 4,942,120, and described in US Pat. No. 4,914,014. Nucleation with high pBr of
Nucleation in a short time as described in JP-A-222940 is extremely effective in the nucleation step of the tabular grain emulsion used in the present invention. In the aging step, it is possible to perform the aging step in the presence of a low concentration base described in US Pat. No. 5,254,453, and at the high pH described in US Pat. No. 5,013,641. It may be effective in the ripening step of the tabular grain emulsion used in. In the growing process, US Pat. No. 4,524,858.
Growing at low temperature as described in No. 7,
The use of silver iodide fine grains described in 2,027 and 4,693,964 is particularly effective in the step of growing the tabular grain emulsion used in the present invention. Further, it is also preferable to grow by adding silver bromide, silver iodobromide or silver chloroiodobromide fine grain emulsion and ripening. It is also possible to supply the above-mentioned fine grain emulsion by using the stirring device described in JP-A-10-43570.

The emulsion used in the present invention is preferably silver iodobromide, silver iodochloride, silver bromochloride or silver iodochlorobromide.
Further, it is more preferably composed of silver iodobromide or silver iodochlorobromide. In the case of silver iodochlorobromide, it may contain silver chloride,
The silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less or 0 mol%. Regarding the silver iodide content, the variation coefficient of the grain size distribution is 25%.
Since it is preferably the following, the silver iodide content is 20 m.
It is preferably ol% or less. By reducing the silver iodide content, it becomes easy to reduce the variation coefficient of the grain size distribution of the tabular grain emulsion. In particular, the variation coefficient of the grain size distribution of the tabular grain emulsion is preferably 20% or less, and the silver iodide content is preferably 10 mol% or less. The coefficient of variation of the distribution of silver iodide content between grains is 20 regardless of the silver iodide content.
% Or less, particularly preferably 10% or less.

The emulsion used in the present invention preferably has a structure within the grain in terms of silver iodide distribution. in this case,
The silver iodide distribution structure may have a double structure, a triple structure, a quadruple structure, or a higher structure. The structure of the emulsion used in the present invention is preferably, for example, a triple structure grain composed of silver bromide / silver iodobromide / silver bromide and a higher-order structure having a higher structure. The boundary of the silver iodide content between the structures may be clear or may have a continuous and gradual change. Usually, the measurement of the silver iodide content using the powder X-ray diffraction method does not show two distinct peaks with different silver iodide contents, and the tail is drawn toward the high silver iodide content. Such an X-ray diffraction profile is shown. In the present invention, the silver iodide content of the phase inside the surface is preferably higher than the silver iodide content of the surface, and the silver iodide content of the phase inside the surface is preferably 5 mol% or more. More preferably 7 m
It is ol% or more.

When the emulsion used in the present invention is a tabular grain, it preferably has a dislocation line. The dislocation lines of tabular grains are
For example, J. F. Hamilton, Photo. Sci.
Eng. , 11, 57, (1967) and T.W. Shioz
awa, J .; Soc. Photo. Sci. Japan,
35, 213, (1972), and can be observed by a direct method using a transmission electron microscope at low temperature. In other words, the silver halide grains taken out carefully so that dislocation lines are not generated on the grains from the emulsion are placed on the mesh for electron microscope observation, and the sample to prevent damage (printout etc.) due to electron beams In the cooled state, observation is performed by the transmission method. At this time, the thicker the particles, the more difficult it is for the electron beam to pass therethrough.
It can be observed more clearly by using an electron microscope of 200 kV or more for particles having a thickness of 5 μm. From the photograph of the grain obtained by such a method, the position and number of dislocation lines for each grain when viewed from the direction perpendicular to the main plane can be obtained.

The number of dislocation lines is preferably 10 or more on average per grain. More preferably 20 on average per particle
More than a book. When dislocation lines are densely present, or when dislocation lines are observed intersecting with each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, about 10
It is possible to count the number of books, 20 or 30, and it can be clearly distinguished from the case where only a few books exist. The average number of dislocation lines per grain is 100.
The number of dislocation lines is counted for particles and above, and the number average is obtained.

The silver halide grains used in the present invention are subjected to at least one of sulfur sensitization, selenium sensitization, gold sensitization, palladium sensitization and noble metal sensitization at any step of the silver halide emulsion production process. be able to. It is preferable to combine two or more sensitizing methods. Various types of emulsions can be prepared depending on which step is chemically sensitized.
There are a type in which chemically sensitized nuclei are embedded inside the grain, a type in which a chemical sensitized nucleus is embedded at a shallow position from the grain surface, and a type in which a chemically sensitized nucleus is formed on the surface. In the emulsion used in the present invention, the location of the chemically sensitized nuclei can be selected according to the purpose, but it is preferable that at least one type of chemically sensitized nuclei is formed near the surface.

One of the chemical sensitizations which can be preferably carried out in the present invention
One is a chalcogenide sensitization and a precious metal sensitization alone or in combination.
Setaga, The Photograph by James (T.H.James)
Raffic Process, 4th Edition, published by Macmillan, 19
1977, (T.H. James, The Theory of the Photographi
c Process, 4th ed, Macmillan, 1997) 67-76.
Can be done with active gelatin as described
Rushi, Research Disclosure Volume 120, 1
April 974, 12008; Research Disclosure.
, 34, June 1975, 13452, US Patent
No. 2,642,361, 3,297,446
No. 3,772,031 No. 3,85
No. 7,711, No. 3,901,714,
4,266,018 and 3,904,
415, as well as British Patent 1,315,755.
PAg 5-10, pH 5-5
Sulfur, selenium, and tellurium at 8 and a temperature of 30 to 80 ° C.
Le, gold, platinum, palladium, iridium or their addition
There can be multiple combinations of sensitizers. For sensitizing precious metals
For precious metals such as gold, platinum, palladium, iridium, etc.
A genus salt can be used, among which gold sensitization and palladium
Sensitization and combination of both are preferred. In case of gold sensitization
Is chloroauric acid, potassium chloroaurate, potassium
-Lithiocyanate, gold sulfide, gold selenide, etc.
Compounds can be used. Palladium compound is para
It means a divalent salt or a tetravalent salt. Preferred para
Rhodium compounds₂PdX₆Or R₂PdX^FourRepresented by
It Where R is a hydrogen atom, an alkali metal atom or an
Represents a monium group. X represents a halogen atom, chlorine, odor
Represents an elementary or iodine atom. Specifically, K₂PdC
l_Four, (NH_Four)₂PdCl₆, Na₂PdCl_Four, (NH_Four) ₂
PdCl_Four, Li₂PdCl_Four, Na₂PdCl₆Or K₂
PdBr_FourIs preferred. Gold compounds and palladium compounds
Use with thiocyanate or selenocyanate
It is preferable.

As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat. No. 3,857,
The sulfur-containing compounds described in Nos. 711, 4,266,018 and 4,054,457 can be used. It is also possible to carry out chemical sensitization in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include azaindene, azapyridazine, azapyrimidine, and other compounds known to suppress fog and increase sensitivity during the chemical sensitization process. Examples of chemical sensitization aid modifiers are described in US Pat.
No. 1,038, No. 3,411,914,
No. 3,554,757, JP-A-58-1265.
No. 26 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, 1
38-143.

The emulsion used in the present invention is preferably combined with gold sensitization. The preferable amount of the gold sensitizer is 1 × 10 ⁻⁴ to 1 × 10 ⁻⁷ mol per mol of silver halide,
More preferred is 1 × 10 ^{−5 to} 5 × 10 ⁻⁷ mol. The preferable range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferable range of the thiocyan compound or the selenocyan compound is 5 × 10 ⁻² to 1 × 10 ⁻⁶ . The preferable amount of the sulfur sensitizer used for the silver halide grains used in the present invention is 1 per mol of silver halide.
It is x10 ^-4 to 1 x 10 ^-7 mol, and more preferably 1 x 10 ^{-5 to} 5 x 10 ^-7 mol.

Selenium sensitization is a preferable sensitizing method for the emulsion used in the present invention. In the selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.),
Selenium compounds such as selenoketones and selenoamides can be used. In some cases, it is preferable to use selenium sensitization in combination with sulfur sensitization, precious metal sensitization, or both. In the present invention, thiocyanate is preferably added before addition of the above-mentioned spectral sensitizing dye and chemical sensitizer. It is preferably added after grain formation, and more preferably after the desalting step. Preferably, the thiocyanate is added even during the chemical sensitization, so the addition of the thiocyanate is performed twice or more. As the thiocyanate, potassium thiocyanate, sodium thiocyanate, ammonium thiocyanate and the like are used. Usually, it is added after being dissolved in an aqueous solution or a water-soluble solvent. The addition amount is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻² mol, and more preferably 5 × 10 ⁻⁵ mol to 5 × 10 ⁻³ mol per mol of silver halide.

Gelatin is advantageously used as a protective colloid used in the preparation of the emulsion used in the present invention and as a binder for other hydrophilic colloid layers, but other hydrophilic colloids can also be used. . For example, gelatin derivatives, graft polymers of gelatin with other polymers, proteins such as albumin and casein;
Cellulose derivatives such as hydroxyethyl cellulose, carboxymethyl cellulose and cellulose sulfates, sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, poly A wide variety of synthetic hydrophilic polymeric substances such as acrylamide, polyvinyl imidazole, polyvinyl pyrazole, and other single or copolymers can be used. In addition to lime-processed gelatin, acid-processed gelatin and Bull.Soc.Sci.Photo.Japan.No.
16, enzyme-treated gelatin as described in P30 (1966) may be used, and a hydrolyzate or an enzymatic hydrolyzate of gelatin may also be used.

The emulsion used in the present invention is preferably washed with water for desalting and dispersed in a newly prepared protective colloid. The washing temperature can be selected according to the purpose, but is 5 ° C to 50 ° C.
It is preferable to select in the range of ° C. The pH at the time of washing with water can be selected according to the purpose, but it is preferably selected between pH 2 and 10. More preferably, it is in the range of pH 3-8. The pAg at the time of washing with water can be selected according to the purpose, but it is preferably selected from the range of pAg 5 to 10. As a method of washing with water, noodle washing method, dialysis method using semipermeable membrane, centrifugation method, coagulation sedimentation method,
It can be selected from the ion exchange methods and used. In the case of the coagulation sedimentation method, it can be selected from a method using a sulfate, a method using an organic solvent, a method using a water-soluble polymer, a method using a gelatin derivative and the like.

It is preferable for the purpose of preparing the emulsion used in the present invention, for example, during grain formation, desalting step, chemical sensitization, and presence of a metal ion salt before coating, depending on the purpose. When the grains are doped, they are preferably added at the time of grain formation, when the grains are modified or when used as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the entire grain, a method of doping only the core portion of the grain, only the shell portion, only the epitaxial portion, or only the base grain can be selected. Mg, Ca, Sr, Ba, Al, Sc, Y, LaC
r, Mn, Fe, Co, Ni, Cu, Zn, Ga, R
u, Rh, Pd, Re, Os, Ir, Pt, Au, C
d, Hg, Tl, In, Sn, Pb, Bi or the like can be used. These metals can be added in the form of salts such as ammonium salts, acetates, nitrates, sulfates, phosphates, hydroxides or hexacoordinated complex salts and tetracoordinated complex salts which can be dissolved at the time of grain formation. For example, CdBr ₂ , Cd
_{Cl 2, Cd (NO 3)} 2, Pb (NO 3) 2, Pb (CH 3 C
OO) ₂ , K ₃ [Fe (CN) ₆ ], (NH ₄ ) ₄ [Fe (C
N) _{6], K 3 IrCl 6, (NH} 4) 3 RhCl 6, K 4 Ru
(CN) _{6 and the} like. As a ligand of a coordination compound, halo, aco, cyano, cyanate, thiocyanate,
It can be selected from nitrosyl, thionitrosyl, oxo and carbonyl. These may use only one type of metal compound, but may use two types or a combination of three or more types.

The metal compound is preferably added by dissolving in water or a suitable solvent such as methanol or acetone.
Aqueous hydrogen halide solution (eg HC to stabilize the solution)
1, HBr, etc. or alkali halide (eg KC)
1, NaCl, KBr, NaBr, etc.) can be used. If necessary, acids and alkalis may be added. The metal compound may be added to the reaction vessel before grain formation or during grain formation. It is also possible to add a water-soluble silver salt (eg AgNO ₃ ) or an alkali halide water-soluble (eg NaCl, KBr, KI) and continuously add it during the formation of silver halide grains. Further, a solution independent of the water-soluble silver salt and the alkali halide may be prepared and continuously added at an appropriate time during grain formation. It is also preferable to combine various addition methods.

The method of adding a chalcogenide compound as described in US Pat. No. 3,772,031 during emulsion preparation may be useful. S, Se, Te
Besides, cyanate, thiocyanate, selenocyanic acid, carbonate, phosphate and acetate may be present. The emulsion used in the present invention preferably uses an oxidizing agent for silver during the production process. However, silver nuclei that contribute to the improvement in sensitivity obtained by reduction sensitization on the grain surface must remain to some extent. In particular, the extremely fine silver particles produced as a by-product in the process of forming silver halide grains and the chemical sensitization process,
Compounds that can be converted to silver ions are effective. The silver ions generated here may form a poorly soluble silver salt such as silver halide, silver sulfide, or silver selenide, or may form a readily soluble silver salt such as silver nitrate. Good. The preferred oxidant is
It is an inorganic oxidizing agent for thiosulfonates and an organic oxidizing agent for quinones.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process of the light-sensitive material, during storage or during photographic processing, or stabilizing photographic performance. . That is, thiazoles, such as benzothiazolium salts, nitroimidazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, mercaptobenzothiazoles, mercaptobenzimidazoles, mercaptothiadiazoles, aminotriazoles. , Benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), etc .; mercaptopyrimidines; mercaptotriazines; thioketo compounds such as oxadrinethione; azaindenes, for example tria Theindenes, tetraazaindenes (particularly 4-hydroxy-substituted (1,
Many compounds known as antifoggants or stabilizers such as 3,3a, 7) tetraazaindenes), pentaazaindenes, etc. can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,983.
Those described in Japanese Patent No. 2,947 and Japanese Patent Publication No. 52-28660 can be used. One of the preferred compounds is the compound described in JP-A-63-212932. Antifoggants and stabilizers are used at various times before particle formation, during particle formation, after particle formation, during the water washing step, during dispersion after water washing, before chemical sensitization, during chemical sensitization, after chemical sensitization, and before coating. It can be added depending on the purpose. Addition during emulsion preparation to exert the original antifoggant and stabilizing effect, control grain crystal wall, reduce grain size, reduce solubility of grain, control chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

Techniques such as layer arrangement which can be used in the silver halide photographic light-sensitive material to which the present invention can be applied, silver halide emulsions, dye-forming couplers, functional couplers such as DIR couplers, various additives, etc., Regarding the development processing, European Patent Publication EP0565096A1 (19
(October 13, 1993) and the patents cited therein. Below, each item and the corresponding description place are listed.

1. Layer structure: page 61, lines 23 to 35, page 61, line 41 to 62
Page 14 line 2. Middle layer: p. 61, lines 36-40, 3. Multilayer effect imparting layer: p. 62, lines 15-18, 4. 4. Silver halide halogen composition: page 62, lines 21-25, 5. Silver halide grain crystal habit: p. 62, lines 26-30, 6. Silver halide grain size: page 62, lines 31-34, 7. Emulsion production method: Page 62, lines 35-40, 8. Silver halide grain size distribution: p. 62 41-42
Line, 9. Tabular grains: Page 62, lines 43-46, 10. Internal structure of particles: p. 62, lines 47-53, 11. Emulsion latent image forming type: page 62 line 54 to page 63 5
Line, 12. Physical and chemical ripening of emulsion: page 63, lines 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, 14. Fogging emulsion: page 63, lines 14-31, 15. Non-light-sensitive emulsion: page 63, lines 32-43, 16. Amount of coated silver: p. 63, lines 49-50, 17. Photographic Additives: Research Disclosure (R
D) Item17643 (December 1978), It
em18716 (November 1979) and the Item
307105 (November 1989),
The following shows each item and the relevant description.

[0104]     Additive type RD17643 RD18716 RD308119 1. Chemical sensitizer page 23 page 648 right column page 996 2. Sensitivity enhancer Same as above 3. Spectral sensitizer, pages 23 to 24, page 648, right column, page 996, right column,     Supersensitizer page 649 right column page 998 left column 4. Whitening agent Page 24 Page 998 Right column 5. Antifoggant page 24 to 25 page 649 right column page 998 right column to     And stabilizer page 1000 right column 6. Light absorber, pages 25-26, page 649, right column ~ page 1003, left column ~     Filter dye, page 650, left column, page 1003, right column     UV absorber 7. Anti-stain agent page 25 right column 650 left-right column page 1002 right column 8. Dye image stabilizer page 25 page 1002 right column 9. Hardener 26 pages 651 left column 1004 right column ~                                                       Page 1005 Left column Ten. Binder page 26 same as above page 1003 right column ~                                                       Page 1004 Right column 11. Plasticizer, lubricant 27 pages 650 right column 1006 left column ~                                                       Page 1006 Right column 12. Coating aid, pages 26-27 ibid., Page 1005, left column-     Surfactant 1006 Page left column 13. Static page 27 same as above page 1006 right column ~     Inhibitor 100 Page 7 Left column 14. Matting agent 1008 page left column ~                                                       Page 1009 Left column

18. Formaldehyde Scavenger: 64 pages 54-5
7th line, 19. Mercapto type antifoggant: page 65, lines 1-2, 20. Release agents such as rashes: page 65, lines 3-7, 21. Dye: Page 65, lines 7-10, 22. Color couplers in general: Page 65, lines 11 to 13, 23. Yellow, magenta and cyan couplers: page 65, lines 14-25, 24. Polymer coupler: page 65, lines 26-28, 25. Diffusible dye-forming coupler: page 65, lines 29-31, 26. Colored coupler: page 65, lines 32-38, 27. Functional couplers in general: Page 65, lines 39 to 44, 28. Bleach accelerator releasing coupler: page 65 lines 45-48, 29. Development accelerator releasing coupler: p. 65, lines 49-53, 30. Other DIR couplers: page 65, line 54 to page 66, 4
Line, 31. Coupler dispersion method: Page 66, lines 5 to 28, 32. Preservatives / molds: page 66, lines 29-33, 33. Kind of photosensitive material: page 66, lines 34-36, 34. Photosensitive layer film thickness and swelling speed: page 66 line 40 to page 67 1
Line, 35. Back layer: Page 67, lines 3-8, 36. General development processing: Page 67, lines 9-11, 37. Developer and developer: Page 67, lines 12-30, 38. Developer additive: Page 67, lines 31-44, 39. Inversion processing: Page 67, lines 45-56, 40. Treatment liquid opening ratio: page 67, line 57 to page 68, line 12, 41. Development time: Page 68, lines 13-15, 42. Bleach-fix, bleach-fix, page 68, line 16 to page 69, 31.
Line, 43. Automatic developing machine: 69 pages, lines 32-40, 44. Washing, rinsing, stabilizing: page 69 line 41 to page 70 18
Line, 45. Replenishment and reuse of treatment liquid: Page 70, lines 19-23, 46. Built-in developer photosensitive material: Page 70, lines 24-33, 47. Development processing temperature: Page 70, lines 34-38, 48. Use for film with lens: Page 70, lines 39-41.

The present invention can also be applied to a silver halide color photographic light-sensitive material. The silver halide color photographic light-sensitive material may contain a color developing agent for the purpose of simplifying and accelerating the processing. To have it built in,
It is preferable to use various precursors of color developing agents. For example, indoaniline-based compounds described in US Pat. No. 3,342,597, for example, US Pat.
2,599, Research Disclosure N
o. 14, 850 and the same No. Schiff base type compounds described in No. 15,159, No. Aldol compounds described in US Pat. No. 13,924, US Pat. No. 3,71.
Metal salt complexes described in 9,492, JP-A-53-
The urethane compounds described in JP-A-135628 can be mentioned.

The silver halide color light-sensitive material to which the present invention is applied may optionally contain various 1-phenyl-3-pyrazolidones for the purpose of promoting color development. Typical compounds are, for example, JP-A-56-6433.
No. 9, gazette 57-144547, and gazette 58.
-115438. Various treatment liquids in the present invention are used at 10 ° C to 50 ° C.
Usually, a temperature of 33 ° C. to 38 ° C. is standard, but a higher temperature is used to accelerate the processing to shorten the processing time, and a lower temperature is used to improve the image quality and the stability of the processing liquid. be able to.

The silver halide photographic light-sensitive material of the present invention is described in US Pat.
0-133449, 59-218443, 61-238056, and European Patent Publication EP2.
It can also be applied to the photothermographic material described in JP-A-10-660A2. Further, the silver halide color photographic light-sensitive material to which the present invention is applied is more effective when applied to a film unit with a lens described in JP-B-2-32615 and JP-B-3-39784. It is easy to develop and effective.

[0109]

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited in any sense by the following examples.

Example 1 (Synthesis Example 1: Synthesis of WP-1) 50 g of acrylamide was previously added to a phthalate buffer solution (90 mL) having a pH of 4.7.
A solution in which 0.396 g of 2-mercaptoethylamine hydrochloride was dissolved and a solution B in which a radical generator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in a phthalate buffer solution (50 mL) were prepared.
Under a nitrogen atmosphere, a phthalate buffer solution (150 mL) was added to a 1000 mL three-necked flask, and the solution A and the solution B were separately added dropwise at 60 ° C. over 3 hours. 8 after dropping
After heating and stirring at 0 ° C. for 3 hours, the mixture was cooled to room temperature, the reaction liquid was added dropwise to 10 L of methanol, and reprecipitation operation was performed. The obtained solid content was separated by filtration and dried under reduced pressure at 40 ° C. to obtain 50 g of polyacrylamide. 20 g (0.22 mmol) of the obtained polyacrylamide was dissolved in 300 mL of water, and the pH value was adjusted to 8.0 with 5 mol / L NaOH, and then N, N-dimethylformamide 30 was previously prepared.
4- (5-mercapto-1-tetrazolyl) benzoic acid 495 mg (2.2 mmol) and N-hydroxysuccinimide (NHS) 253 mg (2.2 mmo) in mL.
1) and 422 mg of WSC (N-ethyl-N, N-dimethylaminopropylcarbodiimide hydrochloride) (2.2 m)
What was melt | dissolved and was stirred at room temperature for 3 hours, It dripped in the polyacrylamide aqueous solution over 20 minutes. After the completion of dropping, the mixture was stirred for another 30 minutes while maintaining the temperature at 40 ° C.
After the reaction was completed, the reaction solution was slowly added dropwise to 6 L of methanol, and the obtained solid content was separated by filtration. It was again dissolved in 270 mL of water and reprecipitated in 6 L of methanol, and the solid content was separated by filtration. The obtained solid content was dried under reduced pressure at 40 ° C. to obtain 20 g of WP-1a as a white solid.

By changing the amount of 2-mercaptoethylamine hydrochloride added, polyacrylamide having a controlled molecular weight was synthesized.
Polymers WP-1b to WP-1d having different molecular weights were synthesized using mol equivalents of 4- (5-mercapto-1-tetrazolyl) benzoic acid, NHS, and WSC. Table 1 shows the physical property values of the synthesized WP-1.

(Synthesis Example 2: Synthesis of polymer WP-2) 47.5 g of acrylamide, acrylic acid, 2.5 g, 2-in phthalate buffer solution (90 mL) having a pH of 4.7 in advance.
A solution in which 0.396 g of mercaptoethylamine hydrochloride was dissolved and a solution in which a radical generator V-50 manufactured by Wako Pure Chemical Industries, Ltd. was dissolved in a phthalate buffer solution (50 mL) were prepared. Under a nitrogen atmosphere, a phthalate buffer solution (150 mL) was added to a 1000 mL three-necked flask, and Solution A and Solution B were separately added dropwise at 60 ° C. over 3 hours. 3 at 80 ° C after dropping
After heating and stirring for 5 hours, the mixture was cooled to room temperature and 5 mol / lN
After adjusting the pH value to 7.8 with aOH, the reaction solution was added dropwise to 5 L of methanol for reprecipitation operation. The obtained solid content was filtered and dried under reduced pressure at 40 ° C. to obtain 50 g of an acrylamide-acrylic acid copolymer. Polymer 2 obtained
Dissolve 0 g in 70 mL of water, p with 5 mol / l NaOH
After the H value was adjusted to 8.0, N, N-dimethylformamide (70 mL) was previously charged with 4- (5-mercapto-).
1-tetrazolyl) disodium benzoate 1.43 g
(5.9 mmol) and NHS 0.68 g (5.9 m)
mol), WSC and 1.13 g (5.9 mmol) were dissolved and stirred at room temperature for 3 hours, and the mixture was added dropwise to the polymer aqueous solution over 20 minutes. After completion of the dropping, the mixture was stirred for another 3 hours while maintaining the temperature at 40 ° C. After completion of the reaction, the reaction solution was slowly added dropwise to 3 L of methanol, and the obtained solid content was separated by filtration. It was again dissolved in 50 mL of water and reprecipitated in 3 L of methanol, and the solid content was separated by filtration. The obtained solid content is dried under reduced pressure at 40 ° C. to obtain W as a white solid.
2 g of P-2a was obtained. Further, by changing the addition amount of 2-mercaptoethylamine hydrochloride, an acrylamide-acrylic acid copolymer polymer having a controlled molecular weight was synthesized, and 10 mol equivalent of 4-mol of the obtained polymer was used.
(5-Mercapto-1-tetrazolyl) benzoic acid, NH
Polymers with different molecular weights using S and WSC WP-2b
Was synthesized.

Example 3: Synthesis of Polymer WP-3 In the same manner as in Polymer WP-2, the addition amount of 2-mercaptoethylamine hydrochloride and the addition mass ratio of acrylamide and acrylic acid were set to 95: 5. By replacing, a acrylamide-acrylic acid copolymer having a controlled molecular weight was synthesized, and 10 mol equivalent of 4- (5-mercapto-1-tetrazolyl) benzoic acid was added to the obtained polymer.
Polymers with different molecular weights using NHS and WSC WP-
3a and WP-3b were synthesized. Table 1 shows the physical properties of the synthesized WP-3.

[0114]

[Table 1]

[Example 2] A silver halide emulsion was prepared by the following method. Compound 1 to compound 3 used for the preparation
Structures other than are collectively shown later. (Production Method of Emulsion Em-A1) 1300 mL of an aqueous solution containing 2.0 g of low-molecular weight gelatin having a weight average molecular weight of 15,000 and 1.1 g of KBr was kept at 45 ° C., the pH was adjusted to 9, and the mixture was vigorously stirred.

An aqueous solution containing 1.1 g of AgNO ₃ and K
An aqueous solution containing 1.1 g of Br and 1.0 g of low-molecular-weight gelatin having a mass average molecular weight of 15,000 was added by the double jet method over 30 seconds to perform nucleation. 6.6 g of KBr was added, and the temperature was raised to 75 ° C. for aging. After completion of the ripening, 20.0 g of gelatin obtained by chemically modifying alkali-treated gelatin having a mass average molecular weight of 100,000 with succinic anhydride was added, and then the pH was adjusted to 5.2 (up to this point, formation of internal core). Aqueous solution 230 containing 29.3 g of AgNO ₃
mL and an aqueous solution containing 15.8 g of KBr and 1.92 g of KI were added by the double jet method over 40 minutes. At this time, the silver potential was set to -3 with respect to the saturated calomel electrode.
It was kept at 0 mV. Furthermore, an aqueous solution containing 64.5 g of AgNO ₃ and 42.3 g of KBr and 5.14 of KI.
233 mL of an aqueous solution containing g was accelerated by the double jet method so that the final flow rate was 1.33 times the initial flow rate, and added over 57 minutes. The silver potential was kept at -25 mV during the addition (up to this point after the formation of the inner core, the formation of the first coating phase). Next, an aqueous solution containing 47.2 g of AgNO ₃ and an aqueous KBr solution were added by the double jet method over 25 minutes while maintaining the silver potential at -20 mV.

After the temperature was lowered to 40 ° C., 3.9 g of Compound 1 was added, and further 25.6 mL of 0.8 M sodium sulfite aqueous solution was added. Then, the pH was adjusted to 9.0 using an aqueous solution of NaOH and kept for 5 minutes. Temperature is 55 ℃
After the temperature was raised to, the pH was adjusted to 5.5 with H ₂ SO ₄ .
Add 1.5 mg of sodium benzenethiosulfonate and add 1 mg of lime-processed gelatin with a calcium concentration of 1 ppm.
6 g was added. After the addition was completed, 250 mL of an aqueous solution containing 94.6 g of AgNO ₃ and an aqueous KBr solution were added over 30 minutes while maintaining the silver potential at +75 mV. At this time, yellow blood salt was added at 2.0 × 10 ⁻⁵ mol per mol of silver.
And K ₂ IrCl ₆ for 1.5 mol × 10 mol / mol of silver
^-8 mol was added.

After washing with water, gelatin was added and the mixture was heated at 40 ° C.
It was adjusted to H5.6 and pAg8.8. After the temperature was raised to 56 ° C., the compound 2 and the sensitizing dyes ExS-5, ExS-6,
After adding ExS-7, ExS-8 and ExS-9, potassium thiocyanate, chloroauric acid, sodium thiosulfate,
Hexafluorophenyldiphenylphosphine selenide and compound F-11 and compound 3 were added for optimum chemical sensitization. At the end of the chemical sensitization, compound F-2 was added.

This emulsion had an average equivalent spherical diameter of 1.30 μm.
m, average circle equivalent diameter 2.74 μm, average thickness 0.20 μ
It was a tabular grain having m and an average aspect ratio of 14.0.
As a result of observing the obtained particles with a transmission electron microscope while cooling them with liquid nitrogen, 10 or more dislocation lines per particle were observed from the outer peripheral portion of the grain to the peripheral portion of the grain with a projected area of 30%.

[0120]

[Chemical 18]

(Production Method of Emulsion Em-B1) Molecular Weight 15,0
00g low molecular weight gelatin 1.0g and KBr 1.0
1200 mL of an aqueous solution containing g was kept at 35 ° C. and vigorously stirred. 30 mL of an aqueous solution containing 1.9 g of AgNO ₃ , KB
Nucleation was carried out by adding 30 g of an aqueous solution containing 1.5 g of r and 0.7 g of low molecular weight gelatin having a molecular weight of 15,000 by the double jet method over 30 seconds. At this time,
The excess concentration of KBr was kept constant. 5 g of KBr was added, and the temperature was raised to 75 ° C. for aging. After completion of aging, a molecular weight of 100 containing 35 μmol of methionine per gram,
35 g of trimellitated gelatin having a trimellitization rate of 000 of 98% was added. The pH was adjusted to 5.5. Ag
150 mL of an aqueous solution containing 30 g of NO ₃ and an aqueous KBr solution were added by the double jet method over 16 minutes. At this time, the silver potential was kept at -25 mV against the saturated calomel electrode. In addition, an aqueous solution containing 110 g of AgNO ₃ and KB
The r aqueous solution was accelerated by a double jet method so that the final flow rate was 1.2 times the initial flow rate, and the solution was added over 15 minutes. At this time, AgI fine grain emulsion having a size of 0.03 μm was simultaneously added while accelerating the flow rate so that the silver iodide content was 3.8%, and the silver potential was kept at -25 mV.
132 mL of an aqueous solution containing 35 g of AgNO ₃ and an aqueous KBr solution were added over 7 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition was −20 mV. After adjusting the temperature to 40 ° C., the following compound 16
8 g of “a” in terms of KI was added, and 64 mL of a 0.8 M sodium sulfite aqueous solution was further added. Further, an aqueous NaOH solution was added to raise the pH to 9.0 and held for 4 minutes to rapidly generate iodide ions, and then the pH was returned to 5.5. After returning the temperature to 55 ° C., 1 mg of sodium benzenethiosulfonate was added, and further 13 g of lime-processed gelatin having a calcium concentration of 1 ppm was added. After the addition was completed, 250 mL of an aqueous solution containing 70 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes while maintaining the potential at 60 mV. At this time, 1.0 × 10 ⁻⁵ mol of yellow blood salt was added to 1 mol of silver. After washing with water, add 80 g of lime-processed gelatin with a calcium concentration of 1 ppm,
The pH was adjusted to 5.8 and the pAg was adjusted to 8.7 at ℃.

Compound 16a

[Chemical 19]

When the contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy, they were 15 ppm, 2 ppm and 1 ppm, respectively. After the above emulsion was heated to 56 ° C., the compound 2 and the sensitizing dyes ExS-5, ExS-6,
After adding ExS-7, ExS-8 and ExS-9, potassium thiocyanate, chloroauric acid, sodium thiosulfate,
Hexafluorophenyldiphenylphosphine selenide and compound F-11 and compound 3 were added for optimum chemical sensitization. At the end of the chemical sensitization, compound F-2 was added. This emulsion was tabular grains having an average equivalent spherical diameter of 0.85 μm, an average equivalent circular diameter of 1.60 μm, an average thickness of 0.14 μm, and an average aspect ratio of 11.4.

The emulsions Em-A1 and Em-B1 were observed with a transmission electron microscope while being cooled with liquid nitrogen.
Ten or more dislocation lines were observed per grain.

(Production Method of Emulsion Em-K) << Preparation of seed emulsion >> Low-molecular weight-average molecular weight of 15,000
Amount of oxidized gelatin 1.0g and KBr 0.9g
1200 mL of the aqueous solution was kept at 35 ° C. and vigorously stirred.
AgNO ₃  40 mL of an aqueous solution containing 1.05 g and KB
r 1.02 g and low molecular weight 15,000
Double jet 35 mL of aqueous solution containing 1.2 g of ratin.
And added for 30 seconds to form nuclei. End of addition
Immediately after the completion, 5.4 g of KBr was added and the temperature was raised to 75 ° C.
Aged. After aging, the mass average molecular weight of 100,000
Zera chemically modified with Lucari-treated gelatin with succinic anhydride
35 g of Chin was added and then the pH was adjusted to 5.5.
AgNO₃  250 mL of an aqueous solution containing 36 g and KBr
  Aqueous solution 28 containing 21.2 g and KI 2.21 g
Double jet while keeping 2mL and silver potential -10mV.
Method for 25 minutes. Then AgNO₃  
650 mL of an aqueous solution containing 200 g and KBr 134.
900 mL of an aqueous solution containing 1 g and KI 13.9 g
With the double jet method, the final flow rate is 1.5 times the initial flow rate.
The flow rate was accelerated so that it was added over 150 minutes. this
At this time, keep the silver potential at +5 mV with respect to the saturated calomel electrode.
It was After washing with water, add gelatin and pH 5.7, pAg
8.8, mass of silver equivalent 139.0 per kg of emulsion
g and gelatin mass 56 g were adjusted to obtain a seed emulsion.

Lime-treated Zera with a calcium concentration of 1 ppm
Aqueous solution 1200m containing 33g of Chin and 3.4g of KBr
L was kept at 75 ° C. and vigorously stirred. 8 seed emulsions
After adding 9g, modified silicone oil (Nippon Unica-stock
Company product; "L7602") 0.3 g was added. H₂
SO_FourWas added to adjust the pH to 5.8 and benzenethiol was added.
Sodium sulfonate 3 mg and thiourea dioxide 3 mg
After adding AgNO ₃  Aqueous solution 6 containing 51.0 g
00 mL with KBr 36.2 g and KI 3.49
600 ml of an aqueous solution containing g is finalized by the double jet method.
Accelerate the flow rate so that the flow rate is 1.1 times the initial flow rate,
Added over 85 minutes. At this time, set the silver potential to saturated calome.
-35 mV to the electrode. Furthermore, AgNO
₃  300 mL of an aqueous solution containing 44.7 g and KBr 3
300 m of an aqueous solution containing 0.6 g and KI 3.06 g
L and L are 1.
Accelerate the flow rate so that it becomes 1 time, and add over 56 minutes.
It was At this time, the silver potential was set to -25 with respect to the saturated calomel electrode.
kept at mV. Next, AgNO₃  Water containing 36.9 g
Double jet method with 180 mL of solution and KBr aqueous solution
For 40 minutes. At this time, the silver potential is saturated with
It was kept at +10 mV against the mel electrode. Add KBr
After adjusting the silver potential to -70 mV,
Grain size AgI fine grain emulsion is 1.3 in terms of KI mass.
8 g was added. AgNO immediately after addition₃  17.
100 mL of an aqueous solution containing 4 g was added over 15 minutes
It was After washing with water, gelatin was added and the pH was adjusted to 5.
8, pAg 8.7 was adjusted. After heating to 60 ℃,
Compound 2 and sensitizing dyes ExS-10 and ExS-13 are added.
Potassium thiocyanate, chloroauric acid, sodium thiosulfate
Lithium, hexafluorophenyldiphenylphosphine
Optimizing by adding selenide, compound F-11 and compound 3
Chemically sensitized. Compound F-3 was added at the end of chemical sensitization.
It was

This emulsion had an average equivalent spherical diameter of 1.90 μm.
m, average circle equivalent diameter 3.58 μm, variation coefficient of circle equivalent diameter 20%, average thickness 0.36 μm, average aspect ratio 1
It was a tabular grain of 0.0.

As a result of observing the obtained particles with a transmission electron microscope while cooling with liquid nitrogen, it was found that about 97% of the total number of particles in which dislocation lines did not exist within 80% of the projected area from the center of the particle were observed.
%, And 10 or more dislocation lines per grain were observed in the grain peripheral portion where the projected area was 20% from the grain outer peripheral portion.

(Production Method of Emulsion Em-N) 1250 mL of an aqueous solution containing 48 g of deionized gelatin and 0.75 g of KBr.
Was maintained at 70 ° C. and vigorously stirred.

To this solution, 276 mL of an aqueous solution containing 12.0 g of AgNO ₃ and an aqueous KBr solution having an equimolar concentration were added by the double jet method for 7 minutes while keeping the pAg at 7.5. Next, 600 mL of an aqueous solution containing 108.0 g of AgNO ₃ and equimolar concentrations of KBr and K
A mixed aqueous solution of I (2.2 mol% KI) was added by the double jet method over 28 minutes and 30 seconds while maintaining pAg at 7.30. At this time, 0.5 minutes before the addition was completed.
24.0 mL of 1 mass% thiosulfonic acid aqueous solution was added. After desalting and washing with a usual flocculation method to re-disperse it, pH 6.2 at 40 ° C. and pAg7.
Adjusted to 6. After controlling the temperature at 40 ° C., compound 2 and sensitizing dyes ExS-10 and ExS-12 were added, and potassium thiocyanate, chloroauric acid, sodium thiosulfate,
After adding hexafluorophenyldiphenylphosphine selenide, compound F-11, and compound 3, the temperature was 65 ° C.
The temperature was raised to, and optimal chemical sensitization was performed. At the end of the chemical sensitization, compound F-2 was added.

This emulsion was cubic grains having a sphere-equivalent diameter of 0.19 μm and a variation coefficient of 16% of the sphere-equivalent diameter.

Emulsions Em-B1, Em-C to J, L, M,
O is the emulsion Em-A1 of the above Example 1 and the above emulsion Em-A1.
Temperature, pH, silver potential, amount of silver nitrate, KI in the preparation of K
It was prepared by appropriately changing the amount, the amount of compound, the sensitizing dye species, the amount of seed emulsion, and the like. The details of the emulsion thus prepared are shown in Table 2.

[0133]

[Table 2]

(Preparation of Coating Sample) Onto an undercoated cellulose triacetate film support, each layer having the composition shown below was multilayer-coated to prepare a multilayer color light-sensitive material Sample 1
01 was produced.

(Composition of Photosensitive Layer) The main materials used for each layer are classified as follows: ExC: Cyan coupler ExS: Spectral sensitizing dye UV: Ultraviolet absorber ExM: Magenta coupler HBS: High Boiling point organic solvent ExY: Yellow coupler H: Gelatin hardening agent (specific compounds are described below, numerical values are given after the symbols, and chemical formulas are listed after them).

The numbers corresponding to the respective components indicate the coating amount expressed in g / m ² , and for silver halide, the coating amount in terms of silver. Further, with respect to the spectral sensitizing dye, the coating amount per mol of silver halide in the same layer is shown in mol unit.

[0137]   First layer (first antihalation layer)     Black colloidal silver 0.077     Gelatin 0.560     ExM-1 0.048     Cpd-2 0.001     F-8 0.001     HBS-1 0.120     HBS-2 0.015

[0138]   Second layer (second antihalation layer)     Black colloidal silver 0.088     Gelatin 0.830     ExM-1 0.057     ExF-1 0.002     F-8 0.001     HBS-1 0.090     HBS-2 0.010

[0139]   Third layer (middle layer)     ExC-2 0.010     Cpd-1 0.086     UV-2 0.029     UV-3 0.052     UV-4 0.011     HBS-1 0.100     Gelatin 0.580

Fourth Layer (Low Sensitivity Red Sensitive Emulsion Layer) Em-D Silver 0.67 Em-C Silver 0.37 ExC-1 0.282 ExC-2 0.012 ExC-3 0.102 ExC-40 .148 ExC-5 0.005 ExC-6 0.008 ExC-8 0.071 ExC-9 0.010 ExS-1 1.6 × 10 ⁻³ ExS-2 5.0 × 10 ⁻⁴ ExS-3 2 .6 * 10 < ^-5 > UV-2 0.036 UV-3 0.067 UV-4 0.014 Cpd-2 0.010 Cpd-4 0.012 HBS-1 0.240 HBS-5 0.010 Gelatin 1 .630

Fifth Layer (Medium Sensitivity Red Sensitive Emulsion Layer) Em-B1 Silver 0.73 ExC-1 0.111 ExC-2 0.039 ExC-3 0.018 ExC-4 0.074 ExC-5 0. 019 ExC-6 0.024 ExC-8 0.010 ExC-9 0.005 ExS-1 6.9 × 10 ⁻⁴ ExS-2 2.5 × 10 ⁻⁴ ExS-3 9.4 × 10 ⁻⁶ Cpd -2 0.020 Cpd-4 0.021 HBS-1 0.129 gelatin 0.900

Sixth Layer (High Sensitivity Red Sensitive Emulsion Layer) Em-A1 Silver 1.37 ExC-1 0.122 ExC-6 0.032 ExC-8 0.110 ExC-9 0.005 ExC-10 0. 159 ExS-1 4.7 × 10 ⁻⁴ ExS-2 2.5 × 10 ⁻⁴ ExS-3 9.9 × 10 ⁻⁶ Cpd-2 0.068 Cpd-4 0.015 HBS-1 0.440 Gelatin 1.610

[0143]   7th layer (middle layer)     Cpd-1 0.081     Cpd-6 0.002     Solid Disperse Dye ExF-4 0.015     HBS-1 0.049     Polyethyl acrylate latex 0.088     Gelatin 0.759

Eighth Layer (Layer that gives a layering effect to the red-sensitive layer) Em-J Silver 0.46 Cpd-4 0.010 ExM-2 0.082 ExM-3 0.006 ExM-4 0.026 ExY- 1 0.010 ExY-4 0.040 ExC-7 0.007 ExS-4 7.8 × 10 ^-4 ExS-5 3.5 × 10 ^-4 HBS-1 0.203 HBS-3 0.003 HBS- 5 0.010 Gelatin 0.570

Ninth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Em-H silver 0.20 Em-G silver 0.17 Em-I silver 0.30 ExM-2 0.388 ExM-3 0.040 ExY-1 0.003 ExY-3 0.002 ExC-7 0.009 ExS-5 3.4 × 10 ⁻⁴ ExS-6 7.4 × 10 ⁻⁵ ExS-7 1.1 × 10 ⁻⁴ ExS-8 3. 5 × 10 ⁻⁴ ExS-9 1.0 × 10 ⁻⁴ HBS-1 0.337 HBS-3 0.018 HBS-4 0.260 HBS-5 0.110 Cpd-5 0.010 Gelatin 1.470

10th layer (medium-speed green sensitive emulsion layer) Em-F silver 0.40 ExM-2 0.084 ExM-3 0.012 ExM-4 0.005 ExY-3 0.002 ExC-6 0. 003 ExC-7 0.007 ExC-8 0.008 ExS-7 1.0 × 10 ^-4 ExS-8 6.1 × 10 ^-4 ExS-9 1.3 × 10 ^-4 HBS-1 0.096 HBS -3 0.002 HBS-5 0.002 Cpd-5 0.004 Gelatin 0.382

11th layer (high-sensitivity green-sensitive emulsion layer) Em-E silver 0.90 ExC-6 0.002 ExC-8 0.010 ExM-1 0.014 ExM-2 0.023 ExM-3 0. 023 ExM-4 0.005 ExM-5 0.040 ExY-3 0.003 ExS-7 7.4x10 ^-4 ExS-8 6.9x10 ^-4 ExS-9 1.9x10 ^-4 Cpd -3 0.004 Cpd-4 0.007 Cpd-5 0.010 HBS-1 0.259 HBS-5 0.020 Polyethyl acrylate latex 0.099 Gelatin 0.781

[0148]   12th layer (yellow filter layer)     Cpd-1 0.088     Solid disperse dye ExF-2 0.051     Solid disperse dye ExF-8 0.010     HBS-1 0.049     Gelatin 0.593

Thirteenth Layer (Low Sensitivity Blue Sensitive Emulsion Layer) Em-N silver 0.18 Em-M silver 0.04 Em-L silver 0.60 ExC-1 0.024 ExC-7 0.011 ExY-1 0.002 ExY-2 0.956 ExY-4 0.091 ExS-10 8.5x10 ^-5 ExS-11 7.4x10 ^-4 ExS-12 9.5x10 ^-5 ExS-13 3. 0 × 10 ⁻⁴ Cpd-2 0.037 Cpd-3 0.004 HBS-1 0.372 HBS-5 0.047 Gelatin 2.201

14th layer (high-sensitivity blue-sensitive emulsion layer) Em-K silver 1.32 ExY-2 0.235 ExY-4 0.018 ExS-10 1.0 × 10 ⁻⁴ ExS-13 1.5 × 10 ^-4 Cpd-2 0.075 Cpd-3 0.001 HBS-1 0.087 gelatin 1.156

[0151]   Fifteenth layer (first protective layer)     0.07 μm silver iodobromide emulsion silver 0.28     UV-1 0.358     UV-2 0.179     UV-3 0.254     UV-4 0.025     F-11 0.0081     S-1 0.078     ExF-5 0.0024     ExF-6 0.0012     ExF-7 0.0010     HBS-1 0.175     HBS-4 0.050     Gelatin 2.231

[0152]   16th layer (2nd protective layer)     H-1 0.400     B-1 (diameter 1.7 μm) 0.050     B-2 (diameter 1.7 μm) 0.150     B-3 0.050     S-1 0.200     Gelatin 0.711

Further, in order to improve the storability, processability, pressure resistance, antifungal / antibacterial property, antistatic property and coating property of each layer, W-1 to W-6, B-4 to B are appropriately added. −
6, F-1 to F-17, and a lead salt, a platinum salt, an iridium salt, and a rhodium salt.

(Preparation of Dispersion of Organic Solid Disperse Dye) Wet cake of ExF-2 (containing 17.6 mass% water) 2.800 kg sodium octylphenyldiethoxymethanesulfonate (31 mass% aqueous solution) 0 .376 kg F-15 (7% aqueous solution) 0.011 kg water 4.020 kg total 7.210 kg (adjusted to pH = 7.2 with NaOH) After roughly dispersing the slurry of the above composition by stirring with a dissolver , Agitator mill LMK-4, peripheral speed 10m /
s, discharge rate of 0.6 kg / min, filling rate of zirconia beads having a diameter of 0.3 mm is 80%, and the absorbance ratio of the dispersion is 0.29.
To obtain a solid fine particle dispersion. The average particle size of the dye fine particles was 0.29 μm.

Similarly, solid dispersions of ExF-4 and ExF-8 were obtained. The average particle size of the fine dye particles was 0.28 μm and 0.49 μm, respectively.

The compounds used in each layer are shown below.

[0157]

[Chemical 20]

[0158]

[Chemical 21]

[0159]

[Chemical formula 22]

[0160]

[Chemical formula 23]

[0161]

[Chemical formula 24]

[0162]

[Chemical 25]

[0163]

[Chemical formula 26]

[0164]

[Chemical 27]

[0165]

[Chemical 28]

[0166]

[Chemical 29]

[0167]

[Chemical 30]

[0168]

[Chemical 31]

[0169]

[Chemical 32]

[0170]

[Chemical 33]

[0171]

[Chemical 34]

[0172]

[Chemical 35]

(Preparation of Emulsion Em-A2 to A10) Emulsion E
In m-A1, before the addition of the compound F-2 at the end of the chemical sensitization, the water-soluble synthetic polymer was 20 m with respect to 1 mol of silver.
g, an emulsion Em- except that it is added as shown in Table 3 below.
Emulsions Em-A2 to A10 were prepared in the same manner as A1.

(Production Method of Emulsion Em-B2 to B10) Emulsion E
In the m-B1, before the addition of the compound F-2 at the end of the chemical sensitization, the water-soluble synthetic polymer was 20 m per 1 mol of silver.
g, an emulsion Em- except that it is added as shown in Table 3 below.
Emulsions Em-B2 to B10 were prepared in the same manner as B1.

(Production of Samples 102 to 110) Sample 101
Except that the emulsion Em-A1 of the sixth layer was replaced with Em-A2 to A10, and the emulsion Em-B1 of the fifth layer was replaced with Em-B2 to B10 so as to have the same silver amount, respectively, as shown in Table 3 below. Is the same as the sample 101 and is a multilayer color light-sensitive material 102.
~ 110 were produced.

(Measurement of Specific Photographic Sensitivity) The sensitivity of a photographic light-sensitive material is generally ISO sensitivity, which is an international standard. With ISO sensitivity, the light-sensitive material is developed on the fifth day after exposure, and its development treatment is carried out. Is prescribed by each company, the present invention shortens the time until the development processing after exposure and carries out a constant development processing.

The method for determining the specific photographic sensitivity is JIS
According to K 7614-1981, the difference is that the development process is completed within 30 minutes or more and 6 hours after exposure for sensitometry, and the development process is based on Fuji Color Processing Formula CN-16 described below. . Others are substantially the same as the measuring method described in JIS.

Other than the development processing shown below, JP-A-63-63
The method was the same as the test conditions, exposure, density measurement, and determination of specific photographic sensitivity described in JP-A-226650.

[0179] Development is performed by Fuji Photo Film Co., Ltd. automatic developing machine F.
The following was performed using P-360B. The overflow solution of the bleaching bath was modified so that it was entirely discharged into the waste liquid tank without flowing into the post bath. This FP-360B is equipped with the evaporation correction means described in Published Technique No. 94-4992 (issued by the Institute of Invention and Innovation). The treatment process and the treatment liquid composition are shown below. (Treatment process) Process Treatment time Treatment temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C. 20 mL 11.5 L Bleach 50 seconds 38.0 ° C. 5 mL 5 L Fixing (1) 50 seconds 38.0 ° C. -5 L Fixing (2) 50 seconds 38.0 ° C 8mL 5L water washing 30 seconds 38.0 ° C 17mL 3L stable (1) 20 seconds 38.0 ° C -3L stable (2) 20 seconds 38.0 ° C 15mL 3L dry 1 minute 30 seconds 60.0 ° C * Replenishment amount: Replenishment amount per 1.1 m of 35 mm width of photosensitive material (equivalent to one shot for every 24 shots)

The stabilizing solution and the fixing solution were of the countercurrent system from (2) to (1), and the overflow solution of washing water was all introduced into the fixing bath (2). The amount of the developing solution brought into the bleaching process, the amount of the bleaching solution brought into the fixing process, and the amount of the fixing solution brought into the washing process were 1.
2.5mL, 2.0mL, 2.0m per 1m
It was L. The crossover time is 6
Seconds, and this time is included in the processing time of the previous step.
Open area 100 cm ² in the color developing solution in the processing machine, 120 cm ² in the bleaching solution, the other processing solutions was about 100 cm ^2.

The composition of the processing liquid is shown below.   (Color developer) Tank liquid (g) Replenisher (g)   Diethylenetriamine pentaacetic acid 3.0 3.0   Catechol-3,5-disulfonic acid     Disodium 0.3 0.3   Sodium sulfite 3.9 5.3   Potassium carbonate 39.0 39.0   Disodium-N, N-bis (2-sulfur     Honatoethyl) hydroxylamine 1.5 2.0   Potassium bromide 1.3 0.3   Potassium iodide 1.3 mg-   4-hydroxy-6-methyl-1,3     3a, 7-tetrazaindene 0.05-   Hydroxylamine sulfate 2.4 3.3   2-methyl-4- [N-ethyl-N-     (Β-hydroxyethyl) amino]     Aniline sulfate 4.5 6.5   Add water 1.0L 1.0L   pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18

[0182]   (Bleaching solution) Tank solution (g) Replenisher solution (g)   1,3-Diaminopropanetetraacetic acid secondary     Ammonium iron monohydrate 113 170   Ammonium bromide 70 105   Ammonium nitrate 14 21   Succinic acid 34 51   Maleic acid 28 42   Add water 1.0L 1.0L   pH [adjusted with ammonia water] 4.6 4.0

[0183]   (Fixing (1) Tank liquid)   5:95 (volume ratio) mixture of the above bleaching tank solution and the following fixing tank solution   (PH 6.8)   (Fixing (2)) Tank liquid (g) Replenisher (g)   Ammonium thiosulfate aqueous solution 240mL 720mL   (750g / L)   Imidazole 7 21   Ammonium methanethiosulfonate 5 15   Ammonium methanesulfinate 10 30   Ethylenediaminetetraacetic acid 13 39   Add water 1.0L 1.0L   pH [adjusted with aqueous ammonia and acetic acid] 7.4 7.45

(Washing water) The tap water was washed with H-type strongly acidic cation exchange resin (Amberlite IR-1 manufactured by Rohm and Haas).
20B) and an OH-type strongly basic anion exchange resin (Amberlite IR-400) are passed through a mixed bed column to adjust the concentration of calcium and magnesium ions to 3 m.
g / L or less, followed by 20 mg / L sodium diisocyanurate dichloride and 150 mg / L sodium sulfate
Was added. The pH of this liquid was in the range of 6.5 to 7.5. (Stabilizer) Common to tank liquid and replenisher (unit g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization 10) 1,2-Benzisothiazoline-3 -On sodium 0.10 ethylenediaminetetraacetic acid disodium salt 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0.75 water In addition 1.0 L pH 8.5

Further, the relative sensitivity of each color-sensitive layer is obtained from the measuring method of the specific photographic sensitivity. Fog is the minimum value of yellow density, magenta density, and cyan density (DYm
in, DMmin, DCmin), and the sensitivity of each color-sensitive layer was defined as the logarithm of the reciprocal of the exposure dose giving a density 0.15 higher than DYmin, DMmin, DCmin. The sensitivity value of the red color-sensitive layer of each sample was expressed as a relative value with respect to Sample 101.

Regarding the granularity, the same processing as in the measurement of the specific photographic sensitivity was performed, and the conventional RMS (Root Mean) was used.
It was measured by the Square method. At this time, the exposure is 0.0
The measurement was carried out by RMS measurement using an aperture having a diameter of 48 μm.

(Evaluation of Pressure Resistance) In order to evaluate the pressure resistance of the sample, the following test was conducted. Sample temperature 25 ℃
After controlling the humidity to 55% with a 0.05 mm fine needle applied with a load of 4 g, the emulsion surface was scratched in a certain direction, and then exposure, development and concentration were carried out by the method described above. D obtained by the above exposure, development and density measurement of a sample without scratching
The density difference (ΔD) between the scratched portion and the non-scratched portion was determined in the exposure amount that gives a density higher by 0.25 than Ymin, DMmin, and DCmin. It is shown that the smaller ΔD is, the better the pressure resistance is. The sum of ΔD of these color-sensitive layers was used as the evaluation value showing the pressure resistance.

(Evaluation of Deterioration of Photographic Performance Due to Aggregation of Particles during Coating) In Samples 101 to 110, the emulsion of the sixth layer was melted at 40 ° C. and aged for 8 hours.
Samples 111 to 120 were produced under the same coating conditions as those of 1-110. These samples were allowed to stand under conditions of 40 ° C. and 70% relative humidity for 14 hours, and then exposed through a continuous wedge in the same manner as above for 1/100 seconds for color development processing. The density of the processed sample was measured with a red filter, and the sensitivity was expressed as the relative value of the logarithm of the reciprocal of the exposure amount displayed in lux · second which gives a cyan density of 0.15. And). Further, the RMS granularity of each of Samples 101 to 110 and Samples 111 to 120 was measured at a fog density plus a density of 0.15. The relative value when the RMS granularity of Sample 101 was 100 was taken as the evaluation value showing the granularity. The smaller the value, the better the graininess.

Samples 101 to 11 thus obtained
The respective performances of 0 and 111 to 120 are shown in Table 3.

[0190]

[Table 3]

Sample 102 to which the polymer of the present invention is added
It can be seen that in 109, the pressure resistance is improved without lowering the sensitivity. In particular, it can be seen that in Samples 102 to 109 of the present invention, deterioration in photographic performance such as a decrease in sensitivity and deterioration in graininess in coating after the emulsion was dissolved and aged was improved, and production suitability was also excellent. It is presumed that the polymer of the present invention is difficult to be desorbed from silver halide grains even in the presence of other adsorptive additives, and the pressure resistance is improved by improving the protective colloid property. Further, the effect of improving the deterioration of photographic performance such as the decrease of sensitivity and the deterioration of graininess in the coating after the dissolution of emulsion of the emulsion is more effective as the number average molecular weight of the water-soluble synthetic polymer of the present invention is larger. Recognize. Further, the comparative sample 120 and the present invention samples 111 to 11
As can be seen from the comparison of No. 9, the effect of improving deterioration of photographic performance such as deterioration of sensitivity and deterioration of graininess in coating after dissolution of emulsion is improved by introducing a nitrogen-containing hetero ring containing a mercapto group as a partial structure of polymer. You can see that it was done.

Example 3 Emulsion E in Sample 101
After washing m-A1 and Em-B1 with water, after adding the compound 2 and before adding the sensitizing dye, the polymer WP-3a of the present invention.
Was added in an amount of 20 mg per mol of silver to prepare a multilayer color light-sensitive material in the same manner. As in Example 2, good results were obtained in terms of pressure resistance and prevention of deterioration of photographic performance during coating.

Example 4 Emulsion E in Sample 101
Prior to the addition of yellow blood salt in the grain forming process of m-A1 and Em-B1, 20 mg of the polymer WP-3a of the present invention was added per 1 mol of silver to prepare a multilayer color light-sensitive material in the same manner. As in Example 2, good results were obtained in terms of pressure resistance and prevention of deterioration of photographic performance during coating.

(Example 5) In the sample 101, the polymer WP of the present invention was prepared when the coating solutions for the fifth and sixth layers were prepared.
-3a was added in an amount of 20 mg per mol of silver to prepare a multilayer color light-sensitive material in the same manner. As in Example 2, good results were obtained in terms of pressure resistance and prevention of deterioration of photographic performance during coating.

[0195]

The silver halide photographic light-sensitive material containing the polymer of the present invention is excellent in pressure resistance without lowering the sensitivity. Further, the polymer of the present invention can prevent the aggregation of silver halide grains after the emulsion is dissolved, improve the deterioration of photographic performance during coating, and enable the preparation of a silver halide emulsion having excellent production suitability. Become. That is, according to the present invention, it is possible to suppress aggregation of silver halide grains having high aspect ratio and high sensitivity and excellent in flatness, and a novel novel useful for preparing a highly sensitive silver halide emulsion. A different polymer can be provided. Further, according to the present invention, it is possible to provide a high-sensitivity silver halide emulsion which stably contains silver halide grains having a high aspect ratio without causing aggregation. Further, according to the present invention, it is possible to provide a silver halide photographic light-sensitive material which has high sensitivity, excellent flatness, excellent pressure resistance and can be stably manufactured.

Continued front page    (72) Inventor Mamoru Sakurazawa             Fuji Photo, 210 Nakanuma, Minamiashigara City, Kanagawa Prefecture             Within Film Co., Ltd. F-term (reference) 2H023 BA01 CD00

Claims (3)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one synthetic polymer having a nitrogen-containing aromatic ring having a mercapto group represented by the following general formula (1) as a partial structure. General formula (1) Z-SH (In formula, Z represents a nitrogen-containing aromatic ring.) 2. A silver halide emulsion composition containing a silver halide grain and a synthetic polymer having a nitrogen-containing aromatic ring having a mercapto group represented by the general formula (1) as a partial structure. 3. A mercapto group-containing polymer compound represented by the following general formula (2). [Chemical 1] (In the formula, X represents a group of a homopolymer or a copolymer of a monomer having an ethylenically unsaturated bond. Y ¹ and Y ² are terminal groups of X, and at least one of them is SH-Z-L ^1-.
Represents Z represents a nitrogen-containing aromatic ring, and L ¹ represents a divalent linking group or a single bond. )