JPH0954377A - Manufacture of monodispersed silver halide flat grains and photographic sensitive material using this emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To form the hexagonal and monodispersed emulsion of the flat silver halide grains and to manufacture the photographic sensitive material high in sensitivity. SOLUTION: The manufacturing method of this silver halide emulsion composed of a dispersion medium and the silver halide grains comprises a process of preparing the flat silver halide grains in the presence of at least one kind of a polymer having repeating units represented by the formula -(R-O)n - in which R is a 2-10C alkylene group, and (n) is an average number of the repeating units of 4-200, and the following process of removing the polymer by water rinsing, and a process of further growing silver halide grains by using the emulsion of the obtained silver halide grains as seed crystals.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a tabular silver halide photographic emulsion and a photographic light-sensitive material using the emulsion, and more particularly to a method for producing a monodispersed and highly sensitive tabular silver halide emulsion.

[0002]

2. Description of the Related Art Silver halide grains containing two or more twin planes in parallel have a tabular form. (Hereinafter "tabular grain")
Call. ) These tabular grains have the following photographic properties: 1) Ratio of surface area to volume (hereinafter referred to as specific surface area)
And a large amount of sensitizing dye can be adsorbed on the surface. As a result, the color sensitization sensitivity is relatively high. 2) When an emulsion containing tabular grains is coated and dried, the grains are arranged parallel to the surface of the support, so that light scattering by the grains can be reduced and sharpness and resolution can be improved. In addition, the thickness of the coating layer can be reduced by this arrangement, and the sharpness can be improved. 3) Since the specific surface area is large, development can be accelerated. 4) The covering power is high and the silver can be saved. Because of these many advantages, they have been used in high-sensitivity commercial photosensitive materials. JP-A-58-113926
No. 58-113927 and No. 58-113928 disclose emulsion grains having an aspect ratio of 8 or more. The aspect ratio mentioned here is represented by the ratio of the diameter to the thickness of tabular grains. Further, the diameter of a particle refers to the diameter of a circle having an area equal to the projected area of the particle. The thickness is indicated by the distance between two parallel main surfaces constituting the tabular grains.

However, as seen in the examples of the above-mentioned patents, tabular grains prepared by known methods have poor monodispersity. This means that in addition to tabular grains having a wide distribution of projected area diameters of tabular grains, rod-shaped grains, tetrapot-shaped grains, single twin grains and grains having non-parallel twin planes are mixed. Therefore, 1) the characteristic curve cannot be expected to be hardened. 2) When chemical sensitization is performed on an emulsion in which large grains and small grains coexist, the optimum conditions for chemical sensitization differ between large grains and small grains. It is difficult to perform optimal chemical sensitization for 3) compared with the emulsion coating layer in which large grains and small grains are mixed, the multilayer system in which the monodisperse large grains are coated on the upper layer and the monodisperse small grains are coated on the lower layer Although it is highly sensitive in terms of light use efficiency, it has the drawback of not being able to fully utilize this layering effect.

Therefore, various attempts have hitherto been made to monodisperse tabular grains, and some patents have been disclosed. The monodisperse tabular grain grains described in JP-A No. 52-153428 have a limitation that AgI crystals are used as nuclei, and the grain shape obtained has a small tabular grain ratio. JP-A-55-142329 discloses growth conditions for monodispersion of tabular grains, but the grains produced have a low tabular grain ratio. JP-A-51-
The monodispersed twin grains of No. 39027 is a method in which after the nucleation, a silver halide solvent is added and ripened, and then grown.
The resulting grains have a low tabular grain ratio and a low aspect ratio. As a grain forming process, a monodisperse twin grain patent similar to this patent is disclosed in JP-A-61-112142.
There is an issue. In this patent, since spherical grains are used as seed crystals, only tabular grains having an aspect ratio of 2.2 or less and a low tabular grain ratio were obtained. The monodisperse tabular grains described in French Patent No. 2534036 are formed by a method of ripening after nucleation without using a silver halide solvent, and the coefficient of variation of equivalent circle diameter of the obtained tabular grains (equivalent circle diameter) The standard deviation of is divided by the average value of equivalent circle diameters
It is described that the value multiplied by 00) is 15%. The projection area diameter of the triangular tabular grains is 50% or more as calculated by the grain photographs shown in the examples of this patent. This triangular tabular grain is produced by JE Maskasky, J. Imaging Sci., 31,1.
According to p15-26, 987, it is a grain having three twin planes parallel to the principal plane.

Japanese Patent Laid-Open Nos. 63-11928 and 63-15
No. 1618 and JP-A-2-838 disclose monodisperse tabular grains containing hexagonal tabular grains. This hexagonal tabular grain differs from the above-mentioned triangular tabular grain in that the ratio of tabular grains having two parallel twin planes to the total projected area is 9%.
There is a description of monodisperse tabular grains having a variation coefficient of equivalent circle diameter of 9.7% and 10.1%. US Patent No. 514777
No. 1, No. 5171659, No. 5147772, No. 5
No. 145553 discloses a method for producing monodisperse tabular grains by allowing a polyalkylene oxide block copolymer to be present at the time of nucleation. Further, European Patent No. 514742A discloses a monodisperse tabular grain emulsion having a coefficient of variation of 10% or less. Also in this patent, the above polyalkylene oxide block copolymers are all used in the examples. Also,
Japanese Patent Application No. 5-191814 has filed an application for a method for producing monodisperse tabular grains using a compound that has achieved the drawback of the polyalkylene oxide block copolymer.
However, all of the compounds have a great effect on pure silver bromide tabular grains, that is, very high aspect ratios and monodisperse grains are obtained, but for silver iodobromide tabular grains, the tabular grain thickness increases and the aspect ratio There is a drawback that high tabular grains cannot be obtained.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to form a monodisperse tabular grain emulsion having a hexagonal shape and produce a high-sensitivity photographic light-sensitive material.

[0007]

The above object of the present invention is to halogenate a water-soluble polymer compound having a repeating unit represented by the general formula (1) which can achieve monodispersion of tabular silver halide grains. It was achieved by a method for producing a photographic emulsion characterized in that the compound was used during the formation of silver tabular grains, the grains were formed, and then unnecessary compounds were washed with water and then the tabular grains were grown. This makes it possible to obtain monodisperse tabular grains having a large aspect ratio, and particularly in the formation of silver iodobromide tabular grains in which it was difficult to obtain tabular grains having a small thickness when this compound was conventionally used.
Monodisperse tabular grains having a small thickness can be obtained.

The polymer used in the silver halide emulsion of the present invention will be described in detail below. The polymer used in forming the tabular grain emulsion of the present invention is a polymer having a repeating unit represented by the following general formula (1). Formula (1)-(RO) _n -wherein R represents an alkylene group having 2 to 10 carbon atoms.
n represents the average number of repeating units, and represents 4 or more and 200 or less. In forming the emulsion of the present invention, it is preferable to use a repeating unit of the general formula (1) as long as it contains at least one monomer represented by the following general formula (2). A vinyl polymer as a component or a polyurethane represented by the following general formula (3) is preferably used, and a vinyl polymer having a repeating unit represented by the general formula (2) is particularly preferable. General formula (2)

[0009]

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In the formula, R and n have the same meanings as described above and R ¹
Represents a hydrogen atom, a lower alkyl group, R ² represents a monovalent substituent, and L represents a divalent linking group.

More specifically, R ¹ is a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms (methyl, ethyl,
n-propyl, n-butyl), and a hydrogen atom and a methyl group are particularly preferred.

R ² represents a monovalent substituent having 20 or less carbon atoms, specifically, a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms (eg, methyl group, ethyl group, isopropyl group, n- hexyl, n- dodecyl group, a benzyl group, 2-cyanoethyl group, 2-chloroethyl group, 3-methoxypropyl group, 4-phenoxy-butyl group, 2-carboxyethyl _{group, -CH 2 CH 2 SO 3 Na} , −CH ₂ CH ₂ NHSO ₂ CH
₃ etc.), a substituted or unsubstituted aryl group (eg, phenyl group, p-methylphenyl group, p-methoxyphenyl group,
o- chlorophenyl group, p- octylphenyl group, a naphthyl group, etc.), an acyl group (e.g. acetyl group, a propionyl group, a benzoyl group, octanoyl group, etc.), a carbamoyl group (e.g. _{-CONHCH 3, -CON (CH 3)} 2, −CONHC ₆ H
₁₃ ) are preferable, and a hydrogen atom, a methyl group, an ethyl group, a phenyl group, and an acetyl group are particularly preferable.

L represents a divalent linking group, preferably a group represented by the following general formula (6) or general formula (7). Formula _{(6) -CO-X 1 -L} 1 -X 2 -

In the formula, X ₁ represents an oxygen atom or --NR ^6- (R ⁶ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted acyl group or --L. _{1 -X 2 - (R-O} ) a group represented by _n -R ^2, preferably a hydrogen atom, a substituted or C 1 -C unsubstituted to 10 alkyl group (e.g. methyl group, ethyl group, n- butyl Group, n-octyl group, etc.),
_{L 1 -X 2 - (R-} O) n -R 2, an acyl group (e.g. acetyl group,
Benzoyl group). Particularly preferred as X ₁ is
It is an oxygen atom or -NH-.

L ₁ is a single bond, a substituted or unsubstituted alkylene group (eg, dimethylene, trimethylene, tetramethylene, decamethylene, methyldimethylene, phenyldimethylene, --CH ₂ (C ₆ H ₄ ) CH _2- , −CH ₂ CH ₂ NHCOOCH ₂ −
Etc.), a substituted or unsubstituted arylene group (for example, o-
Phenylene, m-phenylene, p-phenylene, methylphenylene, etc.), and a single bond, — (CH ₂ ) ₁ — (l is 3 or more and 12 or less) is particularly preferable.

X₂Is a single bond, an oxygen atom, -COO-,-
OCO-, -CONR⁶-, -NR ⁶CO-, -OCO
O-, -NR⁶COO-, -OCONR⁶-, -NR⁶
− (R⁶Represents the same as above), etc., of which a single bond, an acid
An element atom, -COO-, -CONH-, -NHCOO-,
-NHCONH- is particularly preferred. General formula (7)

[0017]

[Chemical 6]

In the formula, R ⁷ represents a hydrogen atom, a halogen atom or a substituted or unsubstituted alkyl group or an acyl group, preferably a hydrogen atom, a chlorine atom, a lower alkyl group having 6 or less carbon atoms, a lower acyl group, A hydrogen atom and a methyl group are particularly preferable. L ₂ is a single bond, -L _1- , -X _2- , -L
_{1 -X 2 -, - X 1} -L 1 -X 2 -, - CO-X 1 -L
_{1 -X 2 - (X 1,} X 2, L 1 is as defined above) _{represents, -L 1 -, - X 2} -, - L 1 -X 2 - are preferred,
_{-CH 2 O -, - COO -} , - CONH -, - O- it is particularly preferred. Further, the repeating unit represented by R—O may be only one type for one monomer, or may be a copolymerization type of two or more types.

N represents the average number of moles of repeating units and is 4 to 200, preferably 4 to 50, and particularly preferably 6 to 40. Preferred examples of the monomer represented by the general formula (2) are shown below, but the invention is not limited thereto.

[0020]

[Chemical 7]

[0021]

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[0022]

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[0023]

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[0024]

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[0025]

[Chemical 12]

[0026]

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The vinyl polymer is preferably a copolymer with a monomer other than the monomer represented by the above general formula (2).

Examples of such copolymerizable monomers include acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, vinyl esters, vinyl ketones, allyl compounds, olefins, vinyl ethers, Examples thereof include N-vinyl amides, vinyl heterocyclic compounds, maleic acid esters, itaconic acid esters, fumaric acid esters, and crotonic acid esters. More specific examples include the following. Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, sec-butyl acrylate, octyl acrylate, diethylene glycol monoacrylate, trimethylolethane monoacrylate, 1-bromo-2-methoxyethyl acrylate, p-chlorophenyl acrylate, Methyl methacrylate, ethyl methacrylate,

N-tert-butylacrylamide, hexylacrylamide, octylacrylamide, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylbutyl vinyl ether, vinyl acetate, vinyl propionate, ethylene, propylene, 1-butene, 1-octene. , Dioctyl itaconate, dihexyl maleate, styrene, methylstyrene, dimethylstyrene, benzylstyrene, chloromethylstyrene, chlorostyrene, methyl vinylbenzoate,
Hydrophobic monomers whose homopolymers are insoluble in water, such as vinyl chlorobenzoate, acrylonitrile, methacrylonitrile, vinyl chloride, etc.

Acrylamide, N-methylacrylamide, N-ethylacrylamide, Nn-propylacrylamide, N-isopropylacrylamide, N, N
-Dimethylacrylamide, N-acryloylmorpholine, N-acryloylpiperidine, methacrylamide,
N-methylmethacrylamide, N-methacryloylmorpholine, N-vinylpyrrolidone, N-vinylacetamide, a -COOH monomer such as acrylic acid, methacrylic acid, itaconic acid, maleic anhydride, or
Homopolymers such as monomers having other anionic dissociative groups such as 2-acrylamido-2-methylpropanesulfonic acid (and its salts), sodium p-styrenesulfonate, phosphonoxyethylmethacrylate, etc. Are water-soluble monomers.

A monomer represented by the above general formula (2),
Two or more kinds of other ethylenically unsaturated monomers may be used.

The polymer having a repeating unit represented by the general formula (1) of the present invention is preferably soluble in a medium for forming tabular grains, and therefore preferably soluble in an aqueous medium. That is, it is only necessary to satisfy one of solubility in water or a mixed solvent of water and an organic solvent miscible with water. A measure of water solubility of the polymer in the present invention is that it dissolves at 1% by weight or more in either distilled water or a mixed solvent of distilled water and methanol (weight ratio of 9: 1) at room temperature (25 ° C.). .

The proportion of the monomer unit represented by the general formula (2) in the vinyl polymer of the present invention is 1 to 90% by weight, preferably 3 to 85% by weight, particularly preferably 5 to 70% by weight. . Further, as the type of the other ethylenically unsaturated monomer, it is preferable to use a monomer whose homopolymer is water-soluble in consideration of the solubility of the polymer in an aqueous medium. However, it goes without saying that a monomer in which the homopolymer is water-insoluble can also be used as long as the solubility of the polymer is not impaired.

The molecular weight of the polymer may be variously changed depending on the polarity of the polymer, the kind of the monomer used and the like, but a preferable range is 2 × 10 ³ to 1 × 1 in terms of weight average molecular weight.
0 ⁶ , particularly preferably 3 × 10 ³ to 5 × 10 ⁵ .

Next, the polyurethane will be described. The preferred polyurethane of the present invention can be represented by the general formula (3). General formula (3)

[0036]

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In the formula, R has the same meaning as in the general formula (2).

R ³ represents a divalent linking group, preferably an alkylene group having 1 to 20 carbon atoms (including a substituted alkylene group), an aralkylene group having 7 to 20 carbon atoms (including a substituted aralkylene group), and a carbon number. It represents a phenylene group of 6 to 20 (including a substituted phenylene group).

The substituent of the alkylene group, aralkylene group, or phenylene group of R ³ is not particularly limited, but preferably a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), cyano group, alkoxy group (eg, methoxy group, Ethoxy group, benzyloxy group etc.), aryloxy group (eg phenoxy group), nitro group, amino group, carboxyl group, alkyloxycarbonyl group (eg methoxycarbonyl group, propoxycarbonyl group etc.), acyl group (eg acetyl group, Examples thereof include a benzoyl group), an alkylcarbamoyl group (eg, dimethylcarbamoyl group), an acylamino group (eg, acetylamino group), a sulfonyl group and the like.

R ⁴ represents a divalent linking group, preferably an alkylene group having 1 to 20 carbon atoms (including a substituted alkylene group), an aralkylene group having 7 to 20 carbon atoms (including a substituted aralkylene group), and a carbon number. It represents a phenylene group of 6 to 20 (including a substituted phenylene group).

The substituent for the alkylene group or aralkylene group of R ⁴ is not particularly limited, but is preferably a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a cyano group, an alkoxy group (eg, a methoxy group, an ethoxy group, Benzyloxy group etc.), aryloxy group (eg phenoxy group), nitro group, alkyloxycarbonyl group (eg methoxycarbonyl group, propoxycarbonyl group etc.),
Examples thereof include an acyl group (eg, acetyl group, benzoyl group, etc.), an alkylcarbamoyl group (eg, dimethylcarbamoyl group), an acylamino group (eg, acetylamino group), a sulfonyl group and the like.

N represents the average number of repeating units, and n is 4 to 200, preferably 4 to 80, particularly preferably 6 to 40. When n is less than 4, the monodispersity developing ability of the obtained emulsion is small, and when n is too large, the number of diols that react with isocyanate is small, so that an oxyalkylene residue is efficiently introduced into polyurethane. Becomes difficult to do.

Explaining in more detail, the polyurethane in the present invention is basically synthesized by addition of a diol compound, a diisocyanate compound and polyethylene glycol. As the diol compound, first, a diol represented by the following general formula (8) is used. General formula (8)

[0044]

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In the formula, R and n have the same meanings as described above, and examples of the diol represented by the general formula (8) include the following compounds (n in the formula is the same as above). Represents the number of repeating units).

[0046]

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[0047]

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The diol may be a copolymer thereof (for example, a copolymer of MP-1 and MP-3).

In the polyurethane of the present invention,
In addition to the above general formula (6), other diols represented by the following general formula (9) are also used. Formula ^{(9) HO-R 3 -OH} (R 3 have the same meanings as defined above)

Specific examples of such organic diols include:
Ethylene glycol, 1,2-propanediol, 1,
3-propanediol, 1,2-butanediol, 1,
3-butanediol, 1,4-butanediol, 2,3
-Butanediol, 2,2-dimethyl-1,3-propanediol, 1,2-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2,4-pentanediol, 3,3-dimethyl -1,2-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,2-hexanediol, 1,5-hexanediol, 1,6-hexanediol, 2,5-hexanediol , 2-methyl-2,4-pentanediol,
2,2-diethyl-1,3-propanediol, 2,4
-Dimethyl-2,4-pentanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 2-ethyl-1 , 3-hexanediol,
1,2-octanediol, 1,8-octanediol, 2,2,4-trimethyl-1,3-pentanediol, 1,4-cyclohexanedimethanol, hydroquinone

Diethylene glycol, triethylene glycol, dipropylene glycol, tripropylene glycol and the like can be mentioned.

Since the polyurethane of the present invention is used for preparing an emulsion in an aqueous medium, it is preferable to introduce a dissociative group into the polymer to enhance the solubility of the polymer in the aqueous medium. Suitable dissociable groups include a carboxyl group,
Sulfonic acid group, sulfuric acid monoester group, -OPO (OH)
₂ , a sulfinic acid group, or a salt thereof (for example, N 2
Examples thereof include an anionic group such as an alkali metal salt of a, K or the like, or an ammonium salt such as trimethylamine, or a cationic group such as a quaternary ammonium salt, but an anionic group is preferable, and a carboxyl group is particularly preferable. Alternatively, its salt is preferred.

As the diol having a carboxyl group, 2,2-bis (hydroxymethyl) propionic acid,
2,2-bis (hydroxymethyl) butanoic acid, 2,5
6-trimethoxy-3,4-dihydroxyhexanoic acid,
Examples include 2,3-dihydroxy-4,5-dimethoxypentanoic acid, but are not particularly limited thereto.

The diisocyanate constituting the polyurethane compound of the present invention is represented by the following general formula (10). Formula (10) O = C = N -R 4 -N = C = O (R 4 have the same meanings as defined above)

Preferred specific examples of such a diisocyanate include methylene diisocyanate, ethylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1,4-cyclohexyl diisocyanate, 2,4-toluene diisocyanate, 2,
6-toluene diisocyanate, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, 1,5-naphthalene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, 3,3'-dimethyl-4,4'- Examples thereof include diphenylmethane diisocyanate, 3,3′-dimethylbiphenylene diisocyanate, 4,4′-biphenylene diisocyanate, dicyclohexylmethane diisocyanate, and methylenebis (4-cyclohexyl isocyanate).

The diols represented by the general formulas (8) and (9) and the diisocyanates represented by the general formula (10) of the present invention may be used alone or in combination of two or more. It doesn't matter.

Like the vinyl polymer, the polyurethane of the present invention is preferably soluble in the medium for forming the silver halide emulsion grains, and is therefore preferably soluble in the aqueous medium. It is the same.

In the polyurethane of the general formula (3) of the present invention, x, y and z represent the weight percentage ratio of each component, and x is 1
1 to 70, preferably 3 to 50, particularly preferably 5 to 40% by weight, y depends on x, but is 1 to 70, preferably 2 to 60, particularly preferably 3 to 50% by weight, z is 20 to 70, preferably 25 to 65, particularly preferably 30 to 60% by weight.

Further, considering the solubility of the polymer in the aqueous medium, among the diols represented by the general formula (9),
It is preferable to copolymerize a diol having an anionic group (particularly a carboxyl group) in the polymer in an amount of about 1 to 30% by weight, particularly preferably 2 to 25% by weight.

The molecular weight of polyurethane depends on the polarity of the polymer,
Although it may vary depending on the type of monomer used, etc., a preferred range is 2 × 10 ³ to 5 × 10 ⁵ , particularly preferably 3 × 10 ³ to 2 × 10 5 in terms of weight average molecular weight.
The range is ⁵ .

Specific examples of the polymer containing the repeating unit represented by the general formula (1) of the present invention will be listed below.
The present invention is not limited to these. In the parentheses, vinyl polymers (PP-1 to 13, P-1 to 28, P
In the case of E-1 to 13), the weight percentage ratio of each monomer in the polymer is shown, and the polyurethane (PP-14 to 1
8, PE-24 to 29), the first is the weight percentage ratio of each monomer, and the second is the mole percentage ratio. In addition, PPG in an exemplary compound represents polypropylene oxide.

PP-1 MP-3 / acrylamide copolymer (10/90) PP-2 MP-3 / acrylamide copolymer (25/75) PP-3 MP-3 / acrylamide copolymer (50/50 ) PP-4 MP-3 / acrylic acid / acrylamide copolymer (50/30/20) PP-5 MP-3 / acrylic acid copolymer (70/30)

PP-6 MP-2 / methacrylamide copolymer (30/70) PP-7 MP-4 / acrylamide copolymer (20/80) PP-8 MP-7 / acrylamide copolymer (30/70) 70) PP-9 MP-5 / acrylamide / methacrylic acid copolymer (25/50/25) PP-10 MP-12 / N, N-dimethylacrylamide / acrylic acid copolymer (30/35/35)

PP-11 MP-7 / diacetone acrylamide copolymer (30/70) PP-12 MP-13 / acrylamide / 2-acrylamido-2-methylpropane sulfonic acid sodium copolymer (30/60/10) PP-13 MP-3 / MP-18 / acrylamide / acrylic acid copolymer (20/20/40/20) PP-14 isophorone diisocyanate / 2,2-bis (hydroxymethyl) sodium propionate / PPG (Mw = 400) / PPG (Mw = 1000) (43.1 / 21.5 / 15.7 / 19.7; 50/35/10/5) PP-15 Toluene diisocyanate / 2,2-bis (hydroxymethyl) butanoic acid sodium / PPG ( (Mw = 1000) (29.3 / 20.1 / 50.6; 50/35/15)

PP-16 1,5-naphthylene diisocyanate / 2,2-bis (hydroxymethyl) potassium propionate / PPG (Mw = 400) (47.2 / 24.8 / 18.0; 50/40/10) PP-17 4 , 4'-Diphenylmethane diisocyanate / hexamethylene diisocyanate / 2,2-bis (hydroxymethyl) propionic acid soda / PPG (Mw = 700) (40.1 / 6.7 / 25.0 / 28.1; 40/10/40/10) PP- 18 1,5-naphthylene diisocyanate / hexamethylene diisocyanate / 2,2-bis (hydroxymethyl) butanoic acid soda / PPG (Mw = 400) / polybutylene oxide (Mw = 500) (36.2 / 12.4 / 29.3) /9.8/12.3; 35/15/40/5/5)

P-1 MP-3 / ME-4 / acrylamide copolymer (5/5/90) P-2 MP-3 / ME-4 / acrylamide copolymer (10/10/80) P-3 MP-3 / ME-4 / acrylamide copolymer (25/25/50) P-4 MP-3 / ME-4 / acrylamide copolymer (35/35/30) P-5 MP-3 / ME- 4 copolymer (50/50)

P-6 MP-2 / ME-3 / acrylamide copolymer (25/15/60) P-7 MP-5 / ME-7 / acrylamide / acrylic acid copolymer (20/20/50 / 10) P-8 MP-1 / MP-4 / ME-4 / acrylamide copolymer (15/10 0/25/50) P-9 MP-5 / ME-5 / methacrylamide / acrylic acid copolymer (25/25/30/20) P-10 MP-4 / ME-9 / acryloylmorpholine / methacrylic acid copolymer (20/10/50/20)

P-11 MP-16 / ME-4 / acrylamide / 2-acrylamido-2-methylpropanesulfonic acid sodium carbonate copolymer (25/15/45/15) P-12 MP-9 / ME-15 / 2-Hydroxyethyl Methacrylate / Styrene Sulfonic Acid Sodium Acid Copolymer (10/10/40/40) P-13 MP-3 / ME-2 / ME-4 / Acrylamide Copolymer (25/1 5/15) / 45) P-14 MP-3 / ME-13 / acrylamide copolymer (25/25/50) P-15 MP-8 / ME-9 / methyl methacrylate / acrylamide copolymer (20/20/10 / 50)

P-16 MP-2 / ME-2 / acrylamide copolymer (7.5 / 42.5 / 50) P-17 MP-2 / ME-1 / acrylamide copolymer (7.5 / 42 .5 / 50) P-18 MP-1 / ME-4 / acrylamide copolymer (7.5 / 42.5 / 50) P-19 MP-1 / ME-2 / acrylamide copolymer (7.5 /42.5/50) P-20 MP-2 / ME-4 / acrylamide copolymer (7.5 / 42.5 / 50)

P-21 MP-2 / ME-2 / acrylamide copolymer (6/34/60) P-22 MP-2 / ME-2 / acrylamide copolymer (4.5 / 23.5 / 70) ) P-23 MP-2 / ME-4 / acrylamide copolymer (25/25/50) P-24 MP-1 / ME-2 / acrylamide copolymer (25/25/50) P-25 MP- 1 / ME-4 / acrylamide copolymer (25/25/50)

P-26 MP-3 / ME-2 / acrylamide copolymer (25/25/50) P-27 MP-3 / ME-1 / acrylamide copolymer (25/25/50) P-28 MP-3 / ME-5 / acrylamide copolymer (25/25/50) P-29 MP-4 / ME-5 / acrylamide copolymer (25/25/50)

PE-1 ME-4 / acrylamide copolymer (10/90) PE-2 ME-4 / acrylamide copolymer (25/75) PE-3 ME-4 / acrylamide copolymer (50/50 ) PE-4 ME-4 / acrylamide / acrylic acid copolymer (50/25/25) PE-5 ME-4 homopolymer

PE-6 ME-2 / acrylamide copolymer (30/70) PE-7 ME-1 / ME-4 / methacrylamide copolymer (15/15/70) PE-8 ME-7 / Acrylamide / methacrylic acid copolymer (35/60/5) PE-9 ME-13 / N, N-dimethylacrylamide / 2-acrylamido-2-methylpropanesulfonic acid sodium copolymer (40/45/15) ) PE-10 ME-16 / sodium styrene sulfonate copolymer (50/50)

PE-11 ME-10 / acrylamide / 2-acrylamido-2-methylpropanoic acid sodium copolymer (25/65/10) PE-12 ME-3 / 2-hydroxyethyl methacrylate / methacrylic acid copolymer (30/30/40) PE-13 ME-9 / methyl acrylate / acrylamide / acrylic acid copolymer (25/15/50/10)

PE-14 polyethylene glycol (molecular weight 200-5000)

[0076]

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[0077]

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PE-24 Toluene diisocyanate / 2,2-bis (hydroxymethyl) butanoic acid soda / Polyethylene glycol (Mw = 1000) (29.3 / 20.1 / 50.6; 50/35/15) PE-25 4,4 ′ -Diphenylmethane diisocyanate / 2,2-bis (hydroxymethyl) sodium propionate / polyethylene glycol (Mw = 400) (45.3 / 11.3 / 43.4; 50/20/30) PE-26 4,4'-diphenylmethane diisocyanate / hexamethylene Diisocyanate / ethylene glycol / 2,2-bis (hydroxymethyl) propionate potassium / polyethylene glycol (Mw = 600) (39.1 / 6.6 / 2.4 / 16.8 / 35.1; 40/10/10/25/15)

PE-27 Isophorone diisocyanate / diethylene glycol / 2,2-bis (hydroxymethyl) sodium propionate / polyethylene glycol (Mw = 400) (48.2 / 6.9 / 10.2 / 34.7; 50/15/15/20 ) PE-28 4,4′-diphenylmethane diisocyanate / hexamethylene diisocyanate / ethylene glycol / 2,2-bis (hydroxymethyl) butanoic acid sodium salt / polyethylene glycol (Mw = 1000) / polyethylene glycol (Mw = 400) ( 35.0 / 5.9 / 2.2 / 14.9 / 35.0 / 7.0; 40/10/10/25/10/5) PE-29 4,4'-diphenylmethane diisocyanate / 2,2-bis (hydroxymethyl) sodium propionate / polyethylene glycol (Mw = 300) / Polyethylene glycol (Mw = 400) (4 7.9 / 11.9 / 17.2 / 23.0; 50/20/15/20)

Among the polymers of the present invention, a method for producing a vinyl polymer and polyurethane will be described below.

The vinyl polymer can be produced by various polymerization methods such as solution polymerization, precipitation polymerization, suspension polymerization, bulk polymerization and emulsion polymerization. Examples of the method for initiating polymerization include a method using a radical initiator, a method of irradiating light or radiation, and thermal polymerization. These polymerization methods and the method of initiating the polymerization are described in, for example, Teiji Tsuruta, “Polymer Synthesis Reaction” revised edition (published by Nikkan Kogyo Shimbun, 1971), Takatsu Otsu and Masayoshi Kinoshita, “Experimental Method for Polymer Synthesis”, Kagaku Doujin, 47 years, 12
Pp. 4-154.

Among the above-mentioned polymerization methods, the solution polymerization method using a radical initiator is particularly preferable. The solvent used in the solution polymerization method is water or, for example, ethyl acetate, methanol, ethanol, 1-propanol, 2-propanol, acetone, dioxane, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, n-
Various organic solvents such as hexane and acetonitrile may be used alone or as a mixture of two or more thereof, or may be used as a mixed solvent with water. Among them, in the polymer of the present invention, water or a mixture of water and an organic solvent miscible with water is particularly preferred.

The polymerization temperature must be set in relation to the molecular weight of the polymer to be produced, the kind of the initiator, etc., and can be from 0 ° C. or lower to 100 ° C. or higher, but usually 30 ° C. to 1 ° C.
Polymerizes in the range of 00 ° C.

The radical initiator used for the polymerization is, for example, 2,2'-azobisisobutyronitrile,
Such as 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanopentanoic acid) Azo initiators and peroxide initiators such as benzoyl peroxide, t-butyl hydroperoxide, potassium persulfate (which may be used as a redox initiator in combination with sodium bisulfite) are preferred.

The amount of the polymerization initiator to be used can be adjusted according to the polymerizability of the monomer and the required molecular weight of the polymer, but 0.01 to 10 mol% based on the monomer. The range is preferable, and the range of 0.01 to 2.0 mol% is particularly preferable.

When the polymer of the present invention is synthesized in the form of copolymerization, all the monomers to be used may be initially charged in a reaction vessel and an initiator may be added to carry out the polymerization. It is preferable to synthesize the monomer through a process of dropping the monomer into the polymerization medium.

As the ethylenically unsaturated monomer to be dropped, two or more kinds of monomers to be used may be mixed and added dropwise, or may be added separately. In addition, the ethylenically unsaturated monomer may be dissolved in a suitable auxiliary solvent when dropping. The auxiliary solvent may be water, an organic solvent (for example, those described above), or a mixed solvent of water and the organic solvent.

The time required for dropping may vary depending on the polymerization reaction activity of the ethylenically unsaturated monomer, the polymerization temperature, etc., but it is preferably 5 minutes to 8 hours, particularly preferably 30 minutes to 4 hours. The dropping speed may be constant throughout the dropping, or may be appropriately changed within the dropping time. When the ethylenically unsaturated monomers are separately dropped, the total dropping time and dropping rate of each can be freely changed as necessary. In particular, when the difference in polymerization reactivity between the ethylenically unsaturated monomers is large, a method of dropping a highly reactive monomer more slowly is preferred.

The polymerization initiator may be added to the polymerization solvent in advance, or may be added simultaneously with the ethylenically unsaturated monomer. Alternatively, it may be dissolved in a solvent and dropped separately from the ethylenically unsaturated monomer. Further, two or more of such addition methods may be combined.

The method for producing the polyurethane compound is not particularly limited, and a method in which a diisocyanate is reacted with a diol containing the repeating unit represented by the general formula (1) and a mixture of other diols is preferably used.

The temperature of the above synthetic reaction is 30 ° C to 15 ° C.
The reaction is preferably performed at 0 ° C., particularly preferably at 50 ° C. to 80 ° C. A tertiary amine (eg, tetramethylethylenediamine, 4-dimethylaminopyridine, etc.) or an organic tin compound (dibutyltin laurate, dioctyltin laurate, etc.) is added as a catalyst to promote the reaction between isocyanate groups and hydroxyl groups. Is also preferred.

Further, in order to prevent the reaction product from solidifying or having a high viscosity, an appropriate organic solvent may be used during the reaction. A solvent that is inert to the isocyanate group and dissolves the reaction product is preferably used. Examples of such preferred solvents include ketones (acetone,
Methyl ether, etc.), ethers (tetrahydrofuran, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dioxane, etc.), alkyl halides (chloroform, dichloroethane, etc.),
Aromatic hydrocarbons (benzene, toluene, chlorobenzene, etc., amides (N, N-dimethylformamide, N,
N-dimethylacetamide, etc.).
The solvent can be removed by a usual method if necessary.

Regarding the method of synthesizing polyurethane, the method of polymer chemistry (Yoshio Iwakura, Eiichi Masuhara, Shigeyuki Suzuki, Naotake Okada, Asakura Shoten, 1965), pages 186-187 and 19
Pages 7-204, Gunter Oertel: Polyurethane Handboo
k) p. 21 (1985), Shunsuke Murahashi et al., "Synthetic Polymer" Vp. 309 to 359, polyurethane, Bridgestone Tire Co., Ltd., Nippon Trading Co., Ltd. (Maki Shoten, 1960), etc., and it is convenient to carry out by referring to the method. It goes without saying that the polyaddition initiator, concentration, polyaddition temperature, reaction time and the like can be widely and easily changed according to the purpose.

The synthesis examples of the polymer of the present invention are shown below. Synthesis Example 1 (Synthesis of Exemplified Compound PP-2) 2.5 g of MP-3 and 7.5 g of acrylamide were placed in a 1-liter three-necked flask equipped with a stirrer and a reflux condenser.
g, sodium bisulfite 0.39 g, ethanol 28
0 ml and 140 g of distilled water were added, and the mixture was heated and stirred at 70 ° C. under a nitrogen stream.

20 ml of an aqueous solution of 0.20 g of potassium persulfate
After heating and stirring for 1 hour, potassium persulfate 0.60
g, 50 ml of ethanol, 50 ml of distilled water, and a mixed solution of 22.5 g of MP-3, 67.5 g of acrylamide, 100 ml of ethanol, and 100 g of distilled water were simultaneously dropped at a constant rate over 1.5 hours.

After the completion of dropping, 20 ml of an aqueous solution of 0.20 g of potassium persulfate was added, and the mixture was heated and stirred at 70 ° C. for 3 hours. Ethanol was distilled off from the obtained polymer solution under reduced pressure, and acetone / ethyl acetate (1/1 vol.
The mixture was subjected to reprecipitation for 7 liters of the mixed solvent (ratio). The resulting powder was collected by filtration and dried under reduced pressure to give the title polymer 87.
0 g was obtained (weight average molecular weight 49,700, by gel permeation chromatography).

Synthesis Example 2 (Synthesis of Exemplified Compound PE-2) In a 1 liter three-necked flask equipped with a stirrer and a reflux condenser, 2.5 g of ME-4 and 7.5 of acrylamide.
g, sodium bisulfite 0.39 g, ethanol 28
0 ml and 140 g of distilled water were added, and the mixture was heated and stirred at 70 ° C. under a nitrogen stream.

20 ml of an aqueous solution of 0.20 g of potassium persulfate
After heating and stirring for 1 hour, potassium persulfate 0.60
g, 50 ml of ethanol and 50 ml of distilled water, and a mixed solution of 22.5 g of ME-4, 67.5 g of acrylamide, 100 ml of ethanol and 100 g of distilled water were simultaneously added dropwise at a constant rate over 1.5 hours.

After the completion of dropping, 20 ml of an aqueous solution of 0.20 g of potassium persulfate was added, and the mixture was heated and stirred at 70 ° C. for 3 hours. Ethanol was distilled off from the obtained polymer solution under reduced pressure, and acetone / ethyl acetate (1/1 vol.
The mixture was subjected to reprecipitation for 7 liters of the mixed solvent (ratio).
The resulting powder was collected by filtration and dried under reduced pressure to give the title polymer 9
0.5 g was obtained (weight average molecular weight 47,500, by gel permeation chromatography).

Synthesis Example 3 (Synthesis of Exemplified Compound PE-26) In a 300 ml three-necked flask equipped with a stirrer and a reflux condenser, 19.6 g of 4,4'-diphenylmethane diisocyanate, 3.3 g of hexamethylene diisocyanate and ethylene glycol were added. 1.2 g, 2,2-bis (hydroxymethyl) propionic acid 6.5 g, polyethylene glycol (Mw = 600) 17.6 g and dimethylacetamide 70 ml were added and dissolved at room temperature with stirring.

Di-n-butyltin dilaurate 0.10
After adding g, the mixture was heated to 90 ° C. and stirred under heating for 6 hours, diluted with 30 ml of dimethylformamide, further cooled to room temperature, and then 2.7 g of potassium hydroxide dissolved in 100 ml of methanol was added. Was added. The obtained polymer solution was poured into 5 liters of ethyl acetate to cause precipitation, which was filtered and dried to obtain the title polyurethane PE-26 in a yield of 47.3 g. Synthesis Example 4 (Synthesis of Exemplified Compound P-2) MP-1 (1.0 g), ME-4 (1.0 g), acrylamide (8.0 g), and sodium bisulfite (0) were placed in a 1-liter three-necked flask equipped with a stirrer and a reflux condenser. .39
g, 280 ml of ethanol and 140 g of distilled water were added, and the mixture was heated and stirred at 70 ° C. under a nitrogen stream.

20 ml of an aqueous solution of 0.20 g of potassium persulfate
After heating and stirring for 1 hour, potassium persulfate 0.60
g, 50 ml of ethanol, 50 ml of distilled water, and a mixed solution of 9.0 g of MP-3, 9.0 g of ME-4, 72 g of acrylamide, 100 ml of ethanol, and 100 g of distilled water at a constant speed over 1.5 hours. It was dropped simultaneously.

After completion of the dropping, 20 ml of an aqueous solution of 0.20 g of potassium persulfate was added, and the mixture was heated and stirred at 70 ° C. for 3 hours. From the obtained polymer solution, ethanol was distilled off under reduced pressure, and further atocene / ethyl acetate (1/1 vol
The mixture was subjected to reprecipitation for 7 liters of the mixed solvent (ratio). The resulting powder was collected by filtration and dried under reduced pressure to give the title polymer 85.
5 g was obtained. (Weight average molecular weight is 53,500, by gel permeation chromatography).

Preferred examples of the polymer having the repeating unit represented by the general formula (1) of the present invention further include block polymers of polyalkylene oxide represented by the following general formulas (4) and (5). To be The polyalkylene oxide block polymer will be described. The polyalkylene oxide compound particularly useful in the present invention includes a block copolymer component of a hydrophobic polyalkylene oxide represented by the general formula (4) and a hydrophilic polyalkylene oxide represented by the general formula (5). It is a polymer having in the molecule. General formula (4)

[0105]

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General formula (5)

[0107]

[Chemical 21]

In the formula, R ⁵ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms (eg, methyl group, chloromethyl group, ethyl group, n-butyl group), an aryl group having 6 to 10 carbon atoms (eg, phenyl). Group, naphthyl group), and n is 1 to 1
Represents an integer of 0. Here, when n = 1, R ¹⁴ does not become a hydrogen atom.

R ⁶ is a hydrogen atom or has 4 carbon atoms substituted with a hydrophilic group (eg, hydroxy group, carboxyl group).
The following lower alkyl groups (for example, a hydroxymethyl group and a carboxymethyl group) are represented.

X and y represent the number of repeating units (number average degree of polymerization). Regarding x and y, depending on the structure of the polymer,
Although the preferred range is different, x is 2 to 1000,
It is preferably 3 to 500, and y is 1 to 100
0, preferably 2 to 400.

General formula (4) in the block polymer
And the proportion of the component of the general formula (5)
It may vary depending on the hydrophobicity and the type of emulsion to be prepared, but roughly speaking, the weight ratio is 4:96 to 96: 4.
Is within the range.

Among the hydrophobic polyalkylene oxides represented by the general formula (4), polypropylene oxide (R ⁵ = methyl group, n = 1) is particularly preferable, and among the hydrophilic polyalkylene oxides represented by the general formula (5). Polyethylene oxide (R ⁶ = hydrogen atom) and polyglycerol (R ⁶ = CH ₂ OH) are preferable, and polyethylene oxide is particularly preferable.

With respect to the polymer having the above block copolymer component in its molecule, a compound having polypropylene oxide-polyethylene oxide as a typical component as a block copolymer component will be described in more detail below.

Representative examples of polymers used in the present invention are:
It can be represented by the following general formulas (11) to (18). General formula (11)

[0115]

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General formula (12)

[0117]

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General formula (13)

[0119]

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General formula (14)

[0121]

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General formula (15)

[0123]

[Chemical formula 26]

General formula (16)

[0125]

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General formula (17)

[0127]

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General formula (18)

[0129]

[Chemical 29]

Of the above general formulas (11) to (18),
x, x ', x ", x"', y, y ', y ", y"'"
Represents the number of repetitions of each unit, and the preferred range is the same as x and y in the general formulas (4) and (5). R ⁸ represents a monovalent group, specifically a hydrogen atom, a substituted or unsubstituted alkyl group or an aryl group, and preferably a substituted or unsubstituted lower alkyl group (having 6 or less carbon atoms). R
Specific examples of ⁸ include methyl group, ethyl group, n-propyl group, isopropyl group, t-butyl group, chloromethyl group, methoxycarbonylmethyl group, N-methyl-N-ethylaminoethyl group, N, N- Examples thereof include a diethylaminoethyl group.

L represents a trivalent or tetravalent linking group.
Specific examples of L are shown below, but are not limited thereto.

[0132]

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[0133]

[Chemical 31]

Specific examples of polymers used in the present invention having a block polymer component in the molecule are shown in Table 1 below.
As shown in Table 2, the present invention is not limited to these.

[0135]

[Table 1]

[0136]

[Table 2]

For specific examples and general description of the above-mentioned polymers used in the present invention, as well as specific examples of preparation of silver halide emulsions using this type of polymer, European Patent Publication No. 513722, ibid. 513723, same 5
13724, 513725, 513742, 51
3743 and 51806 can be mentioned.

Next, the method for producing the silver halide emulsion of the present invention will be described. (A) First, a method for producing a silver halide tabular grain emulsion will be described. The silver halide emulsion of the present invention can be manufactured in the process of nucleation → ripening → growth. The water-soluble polymer represented by the general formula (1) may be present anywhere during grain formation, but it is desirable that it exists at least before growth, preferably before ripening, and more preferably before nucleation. Further, the amount thereof is 0.1 times or more and 50 times or less by weight, preferably 0.
It can be used at 1 to 30 times.

The respective steps of nucleation, ripening, and growth, which are the basic steps of the production of silver halide tabular grains, will be described below. (I) Nucleation The nucleation of tabular grains is generally carried out by adding a silver salt aqueous solution and an alkali halide aqueous solution to a reaction vessel holding a gelatin aqueous solution, or a gelatin solution containing an alkali halide. A single jet method in which a silver salt aqueous solution is added to is used. Further, a method of adding an aqueous solution of an alkali halide to a gelatin solution containing a silver salt, if necessary, can also be used. Further, if necessary, a gelatin solution, a silver salt solution, and an alkali halide aqueous solution are added to the mixer disclosed in JP-A-2-44335, and the mixture is immediately transferred to a reaction vessel to form tabular grain nuclei. You can also do Further, as disclosed in US Pat. No. 5,104,786, nucleation can be performed by passing an aqueous solution containing an alkali halide and a protective colloid solution through a pipe and adding an aqueous silver salt solution thereto. For the nucleation, it is preferable that the protective colloid is used as the dispersion medium and the dispersion medium is formed under the condition of pBr of 1 to 4, and the range of 1 to 3.5 is particularly preferable. Protective colloids include gelatin and protective colloid polymers. Alkali-treated gelatin is usually used as the type of gelatin, but phthalated gelatin may be used, and low-molecular weight gelatin (molecular weight: 3000 to 40,000) and oxidation-treated gelatin are preferred. As a protective colloid polymer,
The following are suitable.

(1) Polyvinylpyrrolidone A homopolymer of vinylpyrrolidone, French Patent 203
1396, a copolymer of acrolein and pyrrolidone. (2) Polyvinyl alcohol Homopolymer of vinyl alcohol, US Pat. No. 3,0007
Organic acid monoesters of polyvinyl alcohol shown in No. 41, maleic acid esters shown in US Pat. No. 3,236,653, and copolymers of polyvinyl alcohol and polyvinyl pyrrolidone shown in US Pat. No. 3,479,189. (3) Polymer Having Thioether Group US Pat. Nos. 3,615,624, 3,860,428 and 3,
A polymer having a thioether group shown in 706564. (4) Polyvinylimidazole Homopolymer of polyvinylimidazole, copolymer of polyvinylimidazole and polyvinylamide, JP-B-4
3-7561, German Patent 2012095, 20
12970 No. acrylamide, acrylic acid,
Vinyl imidazole terpolymer. (5) Polyethyleneimine (6) Acetal polymer Water-soluble polyvinyl acetal shown in US-2358836, Polyvinyl acetal having a carboxyl group shown in US-3003879, Brit 771155
The polymer shown in. (7) Amino Polymer US Pat. Nos. 3,345,346, 3,706,504 and 4,
No. 350759, Amino Polymers shown in West German Patent 2138872, British Patent 1413125, Polymers having quaternary amines shown in US Patent 3425836, Polymers having amino groups and carboxyl groups shown in US Patent 3511818, US Patents 3832
The polymer shown in No. 185. (8) Polyacrylic amide polymer A homopolymer of acrylic amide, US Pat. No. 25414
No. 74, a copolymer of polyacrylic amide and imidized polyacrylic amide, West German Patent 120
No. 2132, a copolymer of acrylic amide and methacrylic amide, a partially aminated acrylic amide polymer shown in US Pat. No. 3,284,207,
JP-B-45-14031, US Pat. No. 3,713,834
Substituted acrylic amide polymers shown in U.S. Pat. No. 3,746,548 and British Patent 788,343. (9) Polymers having hydroxyquinoline Polymers having hydroxyquinoline shown in US Pat. Nos. 4,030,929 and 4,152,161. (10) Others A vinyl polymer having an azaindene group described in JP-A-59-8604, a polyalkylene oxide derivative described in US Pat. No. 2976150, and US Pat.
No. 623, a polyvinylamine imide polymer,
Polymers shown in US Pat. Nos. 4,294,920 and 4,089,688, polyvinyl pyridines shown in US Pat. No. 2,484,456, vinyl polymers having an imidazole group shown in US Pat. No. 3,520,857, JP-B-60.
No. 658, a vinyl polymer having a triazole group, and a water-soluble polyalkyleneaminotriazoles described in Ziet Schrift Bisenschlich Photography 45:43 (1950).

The concentration of the dispersion medium is preferably 10% by weight or less, more preferably 1% by weight or less. The temperature during nucleation is preferably 5 to 60 ° C., but the average particle size is 0.5 μm.
When making the following fine tabular grains, 5 to 48 ° C. is more preferable. The pH of the dispersion medium is 8 or less, preferably 6 or less. With respect to the composition of the alkali halide solution to be added, the I ⁻ content with respect to Br ⁻ is not more than the solid solubility limit of AgBrI produced, preferably not more than 10 mol%.

(II) Aging 1. In the nucleation in (1), fine particles other than tabular grains (particularly, octahedral and single twin grains) are formed. Prior to the growth process described below, it is necessary to eliminate grains other than tabular grains to obtain nuclei having a shape to be tabular grains and good monodispersity. To make this possible, it is well known to carry out Ostwald ripening following nucleation. Immediately after the nucleation, pBr is adjusted, and the temperature is increased to ripen until the hexagonal tabular grain ratio becomes maximum. At this time, the gelatin concentration may be adjusted in some cases. The gelatin concentration is preferably 1 to 10% by weight based on the dispersion medium solution.
The gelatin used at this time is usually alkali-processed gelatin, but it is also preferable to use oxidation-processed gelatin or phthalated gelatin. The gelatin may be added at any time during the ripening process. Further, the above-mentioned protective colloid polymer may be used instead of gelatin. The aging temperature is 40 to 80 ° C, preferably 50 to 80 ° C, and p
Br is 1.2 to 3.0. At this time, a silver halide solvent may be added in order to quickly eliminate grains other than tabular grains. In this case, the concentration of the silver halide solvent is preferably 0.3 mol / liter or less,
It is more preferably 0.2 mol / liter or less. When used as a direct reversal emulsion, as a silver halide solvent,
A silver halide solvent such as a thioether compound used on the neutral or acidic side is more preferable than NH ₃ used on the alkaline side. By aging in this manner, only tabular grains of approximately 100% are obtained. After ripening, if the silver halide solvent is unnecessary in the next growth process, the silver halide solvent is removed as follows. In the case of an alkaline silver halide solvent such as NH ₃ , an acid having a large solubility product with Ag ⁺ such as HNO ₃ is added to nullify the solvent. In the case of a thioether-based silver halide solvent, Japanese Patent Laid-Open No.
It is made ineffective by adding an oxidizing agent such as H ₂ O ₂ as described in 0-136736.

(III) Growth After completion of the ripening process, gelatin may be added before starting the growth process. The gelatin concentration at this time is preferably 1 to 10% by weight based on the dispersion medium solution. The gelatin used at this time is usually alkali-processed gelatin, but it is also preferable to use oxidation-processed gelatin or phthalated gelatin.
Further, the above-mentioned protective colloid polymer may be used instead of gelatin. The pBr during the crystal growth period is 1.4 to 3.
It is preferable to keep it at 5. A during the crystal growth period
It is preferable that the addition rate of g ⁺ and the halogen ion is set to 20 to 100%, preferably 30 to 100% of the crystal critical growth rate. in this case,
The rate of addition of silver ions and halogen ions is increased along with the crystal growth.
As described in No. 890 and No. 52-16364, the addition rate of the silver salt and halogen salt aqueous solution may be increased,
The concentration of the aqueous solution may be increased. In addition, JP-A-46-
For example, a method of adding AgX fine particles prepared in advance to a reaction vessel such as JP-A No. 23932 and JP-B-63-30615, and growing the AgX fine particles in a mixer outside the reaction vessel as in JP-A-1-183417. Alternatively, a method of immediately forming fine particles and adding the fine particles to a reaction vessel for growth can be used.
During the growing period, the iodine content of AgX deposited on the nucleus is preferably from 0 mol% to the solid solution limit concentration.

(B) Next, the step of washing the water-soluble polymer used in (A) with water will be described. Washing the water-soluble polymer with water
This can be achieved by using the conventionally used flocculation method. At this time, as a method for quantifying the water-soluble polymer removed by washing with water, "New Edition Surfactant Analysis Method (Surfactant Analysis Study Group, Koshobo, 197
5) ”in P323 to P328. That is, the cobalt thiocyanate method, the bismuth iodide method, and the HPLC analysis method. Also, an analysis method by NMR can be performed. By this step, most of the water-soluble polymer added at the time of forming tabular grains is removed. (C) Finally, a step of further growing the emulsion obtained in (A) and (B) will be described. The growth process is based on the growth process described in (III) of (A). Also,
The water-soluble polymer described in (1) may be allowed to exist during the growth step. The amount thereof is preferably 0.001 times or more and 0.1 times or less by weight of the total amount of silver added during growth.

The silver halide in the present invention is, for example, silver bromide, silver iodobromide, silver chlorobromide having a silver chloride content of 30 mol% or less, silver chloroiodobromide and the like. The other constitution of the emulsion layer of the silver halide photographic light-sensitive material of the present invention is not particularly limited, and various additives can be used if necessary. Chemical sensitizers, spectral sensitizers, antifoggants, metal ion dopants, silver halide solvents, stabilizers, dyes, color couplers, DIR couplers, binders, hardeners, coating aids, which can be added. Thickeners, emulsion precipitation agents, plasticizers, dimensional stability improvers, antistatic agents, fluorescent whitening agents, lubricants, surfactants, UV absorbers, scattering or absorbing materials, curing agents, adhesion prevention, photographic property improvement Agents (eg development accelerator, contrast enhancer, etc.), developer, etc. Photographically advantageous fragments (development inhibitor or accelerator, bleaching accelerator, developer, silver halide solvent, toner, hardener, antifoggant) Agents, competitive couplers, chemical or spectral sensitizers and desensitizers)
Releasing coupler, image dye stabilizer, self-inhibiting developer,
And its use, also supersensitization in spectral sensitization, halogen acceptor effect and electron acceptor effect of spectral sensitizing dye, antifoggant, stabilizer, action of development accelerator or inhibitor,
In addition, a production apparatus, a reaction apparatus, a stirring apparatus, a coating method, a drying method, an exposure method (a light source, an exposure atmosphere, an exposure method) used for producing the emulsion of the present invention, a photographic support, a microporous support, an undercoat layer, For the surface protective layer, matting agent, intermediate layer, antihalation layer, layer structure of AgX emulsion and photographic processing agent, and photographic processing method, see Research Journal, 1
Volume 76, December 1978 issue (Item 1764
3), volume 184, August 1979 issue (item 1843
1), vol. 134, June 1975 (item 1345
2), Product Licensing Index Magazine 9
Volume 107-110 (December 1971), JP-A-58
-113926-113928, ibid. 61-3134
No. 62-6251, JCIA Monthly Report December 1984, P18-27, JP-A No. 62-219982, TH
James, The Theory of The Photographic Process, Fou
rth Edission, Macmillan, New York, 1977,
Making and Coating Photogra by VL Zelikman et al.
The description in phic Emulsion (published by The Focal Press, 1964) can be referred to. One or more silver halide emulsions of the present invention can be provided on a support together with other emulsions, if necessary. Further, it can be provided on both sides of the support, not limited to one side. Further, they can be overlaid as emulsions having different color sensitivity. The silver halide emulsion of the present invention is a black and white silver halide photographic light-sensitive material (for example,
It can be used as an X-ray sensitive material, a squirrel-type sensitive material, a black and white photographing negative film) and a color photographic light-sensitive material (for example, a color negative film, a color reversal film, a color paper, etc.). Further, a photosensitive material for diffusion transfer (for example,
It can also be used for a color diffusion transfer element, a silver salt diffusion transfer element), a photothermographic material (black and white, color) and the like.

[0146]

The tabular silver halide emulsion of the present invention thus obtained has a monodisperse grain shape. The projected area diameter is monodisperse. The particle thickness is uniform. The chemical sensitization can be optimally set for each particle, and large particles, medium particles, and small particles are coated in multiple layers such as high-sensitivity layer, middle-sensitivity layer, and low-sensitivity layer. When used, a photosensitive halogen that can fully exhibit its multi-layer effect and has excellent characteristics in sensitivity, gradation, graininess, sharpness, resolution, covering power, image quality, storage stability, latent image stability and pressure resistance. A silver halide emulsion can be provided. Hereinafter, the present invention will be further described with reference to examples.

[0147]

EXAMPLES The present invention will be described below in more detail with reference to examples, but embodiments of the present invention are not limited thereto. (Comparative Example 1) 1) Preparation of seed crystal To a dispersion medium solution (1.6 liter) containing 0.6 g of KBr and 0.8 g of low-molecular-weight gelatin kept at 40 ° C. was added by a double jet method while stirring it. 2.35
M silver nitrate solution and 2.35M KBr solution
120 cc was added for each minute. At this time, KBr
4.8 g of low molecular weight gelatin dissolved in the solution was added. In addition, pBr was kept at 2.7 during this period. After the addition, the dispersion medium solution was heated to 75 ° C. 10 immediately after the temperature rise
350 cc of% gelatin solution was newly added. 1 at 75 ° C
After stirring for 5 minutes, 164 g of silver nitrate was added at an accelerated flow rate. During this period, pBr was kept at 2.42.
This emulsion was washed with water and then dispersed. 2) Growth step 1 liter of a dispersion medium solution containing 30 g of the emulsion obtained in 1) was kept at 75 ° C., and 145 g of silver nitrate and potassium bromide were added at a accelerated flow rate by the double jet method while stirring. At this time, pBr was kept at 2.42.

Example 1 1) Preparation of seed crystal (emulsion A) 1.6 g of KBr and 0.8 g of low-molecular-weight gelatin kept at 40 ° C. were added to 1.6 liter of a dispersion medium solution. 2.35 with double jet method with stirring
M silver nitrate solution and 2.35M KBr solution
120 cc was added for each minute. At this time, KBr
4.8 g of low molecular weight gelatin dissolved in the solution was added. In addition, pBr was kept at 2.7 during this period. After the addition, the dispersion medium solution was heated to 75 ° C. Immediately after the temperature was raised, 2 g of the synthetic polymer (P-3) was added to adjust the pH to 7. After stirring at 75 ° C. for 20 minutes, 350 cc of 10% gelatin solution was added to adjust the pH to 5. 1 minute later 16
4 g of silver nitrate was added at an accelerated flow rate. During this time,
pBr was kept at 2.42.

2) Washing of Synthetic Polymer with Water The emulsion of 1) was washed with water three times by the usual flocculation method. At this time, when each supernatant liquid at the time of washing with water was collected and the synthetic polymer was quantified by the cobalt thiocyanate method described in the text, 91.5% of the polymer was removed by the aqueous solution. After washing with water, this emulsion was dispersed.

3) Growth Step 1 liter of a dispersion medium solution containing 30 g of the emulsion obtained in 1) was kept at 75 ° C., and 145 g of silver nitrate and potassium bromide were accelerated by a double jet method while stirring the solution. Was added. At this time, pBr was kept at 2.42.

(Example 2) 1) Preparation of seed crystal (emulsion B) 1.6 g of KBr kept at 40 ° C. and 1.6 g of a dispersion medium solution containing 0.8 g of low-molecular-weight gelatin were added to it. 2.35 with double jet method with stirring
M silver nitrate solution and 2.35M KBr solution
120 cc was added for each minute. At this time, KBr
4.8 g of low molecular weight gelatin dissolved in the solution was added. In addition, pBr was kept at 2.7 during this period. After the addition, the dispersion medium solution was heated to 75 ° C. Immediately after the temperature was raised, a synthetic polymer (2 g of PP-2 and 2 g of PE-3) was added to adjust the pH to 7. After stirring at 75 ° C. for 20 minutes, 350 cc of 10% gelatin solution was added to adjust the pH to 5. After 1 minute, 164 g of silver nitrate was added at an accelerated flow rate. During this period, pBr was kept at 2.42. 2) Washing of synthetic polymer with water The emulsion of 1) was washed with water three times by the usual flocculation method. At this time, when each supernatant in the aqueous state was collected and the synthetic polymer was quantified by the cobalt thiocyanate method described in the text, 92.2% of the polymer (PP-2 and PE-3 combined) was removed by washing with water. Was there. After washing with water, this emulsion was dispersed. 3) Growth step 1 liter of a dispersion medium solution containing 30 g of the emulsion obtained in 1) was kept at 75 ° C., and 145 g of silver nitrate and potassium bromide were added at a accelerated flow rate by the double jet method while stirring. At this time, pBr was kept at 2.42. The sizes of the particles obtained in (Comparative Example 1) and (Examples 1 and 2) above are shown in (Table 3).

[0152]

[Table 3]

It can be seen that monodispersed particles having a projected area diameter can be obtained by growing using a seed crystal in which the projected area diameter of particles is monodispersed using a synthetic polymer.

(Example 3) Using the seed crystal emulsion (emulsion A) obtained in Example 1, the synthetic polymer (P-3) of the present invention was used.
Was present and the pH was maintained at 6.3, and the same step as the growth step of 3) of Example 1 was performed. The size of the grown emulsion at this time is shown in (Table 4).

[0155]

[Table 4]

A more monodisperse emulsion was obtained by the presence of the polymer of the present invention in the growth step.

Comparative Example 2 AgBrI Tabular Grain Formation A dispersion medium solution containing 0.6 g of KBr and 0.8 g of low-molecular weight gelatin kept at 40 ° C. was added to 1.6 liter of a dispersion medium solution, and a double jet was made while stirring the mixture. By law 2.35
M silver nitrate solution and 2.35M KBr solution
120 cc was added for each minute. At this time, KBr
4.8 g of low molecular weight gelatin dissolved in the solution was added. In addition, pBr was kept at 2.7 during this period. After the addition, the dispersion medium solution was heated to 75 ° C. Immediately after the temperature was raised, 2 g of the synthetic polymer (P-3) was added to adjust the pH to 7. After stirring at 75 ° C. for 20 minutes, 350 cc of 10% gelatin solution was added to adjust the pH to 5. 1 minute later 16
4 g of silver nitrate was added at an accelerated flow rate. During this time,
pBr was kept at 2.42. After completion of the addition, 80 cc of this emulsion solution was sampled and added to a gelatin solution kept at 75 ° C. in another reaction vessel. While stirring, 145 g of silver nitrate was added at a accelerated flow rate by the double jet method. The halogen solution added at the same time was potassium bromide containing 4 mol% of potassium iodide. At this time, pBr was kept at 2.42. (Example 4) 1) Preparation of seed crystal (Emulsion C) To 1.6 liter of a dispersion medium solution containing 0.6 g of KBr and 0.8 g of low molecular weight gelatin kept at 40 ° C., while stirring it Double jet method 2.35
M silver nitrate solution and 2.35M KBr solution
120 cc was added for each minute. At this time, KBr
4.8 g of low molecular weight gelatin dissolved in the solution was added. In addition, pBr was kept at 2.7 during this period. After the addition, the dispersion medium solution was heated to 75 ° C. Immediately after the temperature was raised, 2 g of the synthetic polymer (P-3) was added to adjust the pH to 7. After stirring at 75 ° C. for 30 minutes, a gelatin solution was newly added to adjust the pH to 5. After 1 minute, 164 g of silver nitrate was added at an accelerated flow rate. During this period, pBr was kept at 2.42. 2) Washing of synthetic polymer with water The emulsion of 1) was washed with water three times by the usual flocculation method. At this time, when each supernatant liquid at the time of washing with water was collected and the synthetic polymer was quantified by the cobalt thiocyanate method described in the text, 91.3% of the polymer was removed by washing with water. After washing with water, this emulsion was dispersed. 3) Growth step 1 liter of a dispersion medium solution containing 30 g of the emulsion obtained in 1) was kept at 75 ° C., and 145 g of silver nitrate was added at a accelerated flow rate by a double jet method while stirring the solution. The halogen solution added at the same time was potassium bromide containing 4 mol% of potassium iodide. At this time, p
Br was kept at 2.42. The sizes of the particles obtained in the above (Comparative Example 2) and (Example 4) are shown in (Table 5).

[0158]

[Table 5]

As can be seen from the results of (Table 5), when AgBrI was grown without removing the used synthetic polymer, the thickness of tabular grains was increased and the aspect ratio was decreased, whereas the washed with water was washed. When most of the synthetic polymer was removed by the method, tabular grain thickness was small and monodisperse grains with high aspect ratio were obtained.

Example 5 Using the seed crystal emulsion (Emulsion C) obtained in Example 4, the synthetic polymer (P-1) of the present invention was used.
Example 4 except that 8) was present and the pH was maintained at 5.0.
The same process as the growth process of 3) was performed. The size of the grown emulsion at this time is shown in (Table 6).

[0161]

[Table 6]

As in this example, after the polymer used for monodispersion of AgBr seed crystals was removed by washing with water, a polymer suitable for AgBrI was newly added in the AgBrI growth step to obtain a high aspect ratio and further Monodisperse AgBrI
Tabular grains can also be obtained.

Comparative Example 3 Reference was made to Example 5 of US Pat. No. 5210013. 1.3g K kept at 45 ° C
Br, 0.83 g of oxidized gelatin, 15.2 cc of 1
N nitric acid, and 0.11 g of PLURONIC TM31R1 (BASF
1L of a silver nitrate solution and 8.5N of a 1N KBr solution are added to 1 liter of a dispersion medium solution containing a product (corresponding to the compound B-1 in the present invention) produced by the company by a double jet method while stirring the solution.
8.53 cc was added at each addition rate of cc / min. 1 minute later, 16.9 cc of 0.84N KBr solution was added, and then 6
The temperature was raised to 0 ° C. After heating, 16.8 cc of aqueous solution containing 3.36 g of ammonium sulfate and 27 cc of 2.5N NaOH
Was added at the same time. After stirring for 9 minutes, 167cc of 10
% Gelatin solution and 43cc of 1N nitric acid, and 0.11g
PLURONIC TM31R1 (same as above) was added. After stirring for 2 minutes, 0.8N silver nitrate and 0.8N KBr solution was added to 2.
7.5 cc of each was added at an addition rate of 5 cc / min. Furthermore,
79.6 cc of 1.6N silver nitrate solution and 1.6N KBr solution were added over 22 minutes. After the addition was completed, 1050 cc of this emulsion solution was sampled and added to the gelatin solution kept at 75 ° C. in another reaction vessel. While stirring, 132.6 g of silver nitrate was added at a accelerated flow rate by the double jet method. The halogen solution added at the same time was potassium bromide containing 4 mol% of potassium iodide. At this time, pBr was kept at 2.42.

Example 6 1) Preparation of seed crystal (emulsion D) 1.3 g of KBr kept at 45 ° C., 0.93 g of oxidized gelatin, 15.2 cc of 1N nitric acid, and 0.11 g
PLURONIC TM31R1 (manufactured by BASF, corresponding to the compound B-1 in the present invention) in 1 liter of a dispersion medium solution, while stirring the solution, a 1N silver nitrate solution and a 1N KBr solution are added in an amount of 8.53 cc. 8.53 cc was added at each addition rate of 1 / min. After 1 minute, 16.9 cc of 0.84N KBr solution was added and the temperature was raised to 60 ° C. After heating 3.
An aqueous solution of 16.8 cc containing 36 g of ammonium sulfate and 27 cc of 2.5 N NaOH were added simultaneously. After stirring for 9 minutes, 167 cc of 10% gelatin solution and 43 cc of 1
N nitric acid, and 0.11 g of PLURONIC TM31R1 (same as above)
Was added. After stirring for 2 minutes, 0.8N silver nitrate and 0.8N KBr solution were added at a rate of 2.5cc / min and 7.5cc each. Further, a 1.6N silver nitrate solution and a 1.6N KBr solution were added over 22 minutes in an amount of 79.6cc each. 2) Washing of polymer (PLURONIC) with water 1) The emulsion of 1) was washed with water three times by the usual flocculation method. At this time, when each supernatant liquid at the time of washing with water was collected and the amount of the polymer was determined by the cobalt thiocyanate method described in the text, 89.5% of the polymer was removed by washing with water. After washing with water, this emulsion was dispersed. 3) Growth step 1 liter of a dispersion medium solution containing 360 g of the emulsion obtained in 1) was kept at 75 ° C., and 132.6 g of silver nitrate was added by the double jet method at an accelerated flow rate while stirring. The halogen solution added at the same time was potassium bromide containing 4 mol% of potassium iodide. At this time, pBr was kept at 2.42. The sizes of the particles obtained in the above (Comparative Example 3) and (Example 6) are shown in (Table 7).

[0165]

[Table 7]

As can be seen from the results of (Table 7), when AgBrI was grown without removing the used polymer, the thickness of tabular grains increased and the aspect ratio decreased, whereas washing with water caused When the polymer was removed, the thickness of the tabular grains was small and monodisperse grains with a high aspect ratio were obtained.

Example 7 The emulsion obtained in Example 2 was washed with water by a conventional flocculation method and redispersed. The emulsion (emulsion E) thus prepared was used in Japanese Patent Laid-Open No. 6-258788.
Sample No. 101 (sample No. 101) of Example 3 of No. 3 of the above publication was used as the fifth layer, and the same treatment as that of the same example was performed to obtain good performance.

Example 8 The emulsion E obtained in Example 5 was used as the emulsion of the light-sensitive material-X of Example 1 of JP-A-6-273860 and combined with the screen B and processed as in the same example. And good performance was obtained.

(Example 9) The emulsion E obtained in Example 5 was used as the sixth layer of the light-sensitive material of Example 1 (Sample No. 101) of JP-A-2-854, and the same treatment as in the same example was carried out. And obtained good results.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] July 29, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0168

[Correction method] Change

[Correction contents]

Example 8 The emulsion E obtained in Example 5 was used as the emulsion of the light-sensitive material-X of Example 1 of JP-A-6-273866, combined with the screen B and processed as in the same example. And good performance was obtained. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] September 18, 1996

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0167

[Correction method] Change

[Correction contents]

Example 7 The emulsion obtained in Example 2 was washed with water by a conventional flocculation method and redispersed. The emulsion (Emulsion E) thus obtained was subjected to chemical sensitization and spectral sensitization to obtain Sample 6 of Example 3 of JP-A-6-258788.
Using the same as the fifth layer of the light-sensitive material of (Sample No. 101), the same processing as in the same example was carried out to obtain good performance.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0168

[Correction method] Change

[Correction contents]

Example 8 The emulsion E obtained in Example 5 was chemically and spectrally sensitized and used as the emulsion of the photosensitive material-X of Example 1 of JP-A-6-273866, and the screen B was used.
In combination with the above, the same processing was performed as in the example, and good performance was obtained.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name]

[Correction method] Change

[Correction contents]

Example 9 Emulsion E obtained in Example 5 was chemically and spectrally sensitized to give a sixth light-sensitive material of Example 1 (Sample No. 101) of JP-A-2-854. It was used as a layer and the same treatment as in the example was carried out with good results.

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Claims (8)

[Claims] 1. A method for producing a silver halide emulsion comprising a dispersion medium and silver halide grains, which comprises (1) a tabular silver halide grain having a repeating unit represented by the following general formula (1). A step of preparing in the presence of at least one of the combination, a step of removing the compound by washing with (2) and (1), and (3) a tabular grain of silver halide obtained in (1) and (2) And a step of further growing the emulsion as a seed crystal. Formula (1)-(RO) _n -wherein R represents an alkylene group having 2 to 10 carbon atoms.
n represents the average number of repeating units, and represents 4 or more and 200 or less. 2. A polymer having a repeating unit represented by the general formula (1) is a vinyl polymer having at least one monomer of the following general formula (2) as a constituent component and a vinyl polymer represented by the following general formula (3). The method according to claim 1, wherein the polymer is at least one polymer selected from polyurethane. General formula (2) General formula (3) In the formula, R and n have the same meanings as described above. R ¹ represents a hydrogen atom or a lower alkyl group, and R ² represents a monovalent substituent. L represents a divalent linking group. R ³ and R ⁴ represent an alkylene group having 1 to 20 carbon atoms, a phenylene group having 6 to 20 carbon atoms, or an aralkylene group having 7 to 20 carbon atoms. x, y, z, x ', y', z'represent the weight percentage of each component, x is 1 to 70, y is 1 to 70, z
Represents 20 to 70. Where x + y + z = 100
It is. 3. A polymer having a repeating unit represented by the general formula (1) has a block polymer component of polyalkylene oxide represented by the following general formulas (4) and (5). The manufacturing method according to claim 1. General formula (4) General formula (5) In the formula, R ⁵ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms,
Represents an aryl group having 6 to 10 carbon atoms, and n is 1 to 10
Represents the integer. Here, when n = 1, R ⁵ does not become a hydrogen atom. R ⁶ represents a hydrogen atom or a lower alkyl group having 4 or less carbon atoms and substituted by a hydrophilic group. x, y
Represents the number of repetitions of each unit (number average degree of polymerization). 4. The production according to claim 1, wherein at least one kind of polymer having a repeating unit represented by the general formula (1) is present during the grain growth of (3) of claim 1. Method. 5. pBr during nucleation during tabular grain formation process
The method according to claim 1, wherein the heat treatment is performed at 1.0 or more and 3.5 or less. 6. The silver halide grain is a tabular grain having an aspect ratio of 2 or more, and the coefficient of variation of equivalent circle diameter is 20%.
The manufacturing method according to claim 1, wherein: 7. The bromine content is 80 mol% relative to the total silver amount.
It is above, The manufacturing method of Claim 1 characterized by the above-mentioned. 8. A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support, wherein the silver halide emulsion layer contains the silver halide emulsion according to claim 1. A characteristic silver halide photographic light-sensitive material.