JPH09197591A - Manufacture of silver halide photographic emulsion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the manufacturing method for the silver halide emulsion superior in a sensitivity to graininess ratio and less in occurrence of fog due to pressure and superior in the reprocity law characteristics. SOLUTION: The host flat silver halide grains having principal (111) faces and an aspect ratio of >=3 and comprising silver iodobromide or bromide occupy >=50% of the projection areas of the total silver halide grains and compose the silver halide emulsion together with a water and a dispersion medium, and another emulsion containing less hardly soluble silver halide grains than these host silver halide grains are added in this process of forming the silver halide grains and the -NH2 groups of a gelatin in 30-100weight% of the dispersion medium are chemically modified by >=30% immediately after the end of the addition step of the above hardly soluble silver halide grains.

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 silver halide photographic emulsion. The present invention particularly relates to a method for producing a silver halide tabular grain photographic emulsion.

[0002]

2. Description of the Related Art US Pat. No. 4,9,947 discloses the introduction of dislocation lines into tabular grain emulsions to increase the sensitivity of silver halide photographic emulsions.
No. 56,269 and the like are known. Regarding the method of introducing the dislocation lines, it is also known to add a silver iodide fine grain emulsion during the growth of a tabular grain emulsion in US Pat. No. 5,061,616 and JP-A-3-213845. However, when the silver iodide fine grain emulsion is added during the growth of the tabular grain emulsion, the effect of the dispersion medium of the silver halide grains on the characteristics has not been known at all.

The tabular grain emulsion in which the above dislocation lines are introduced has the following problems in pressure characteristics and reciprocity law characteristics.

Regarding the pressure characteristics, when an external force such as a scratch is applied to the light-sensitive material coated with the above emulsion, the fog is easily increased. US 5,06
No. 1,616, a silver iodide fine grain emulsion was added during the growth of a tabular grain emulsion, and grain formation was performed while controlling the temperature and silver potential in the subsequent grain growth to appropriate values, resulting in good pressure characteristics. A method of obtaining a tabular emulsion is disclosed. However, the achievement level of the pressure characteristic was insufficient.

Japanese Patent Laid-Open No. 147324/1975 uses a silver halide emulsion containing chemically modified gelatin in a silver halide light-sensitive layer and uses formalin and glyoxal as a hardener together to obtain pressure characteristics of a light-sensitive material. A technique for improving the above is disclosed. The patent describes that the chemically modified gelatin may be added to the silver halide emulsion at any time during the emulsion manufacturing process. Further, the method for forming emulsion grains is not particularly limited. Therefore, the present inventor
No. 56,269, a tabular grain emulsion having dislocation lines was applied with the technique of Japanese Patent Laid-Open No. 50-147324 to make a light-sensitive material as a prototype and the pressure characteristics were evaluated, but its effect was very slight. there were. Also, JP-A-50-14732
No. 4 is an essential technique for using formalin as a hardening agent, but today, the use of formalin is not acceptable from the viewpoint of environmental protection.

Regarding the reciprocity law characteristic, there is a large so-called low illuminance reciprocity law failure in which the sensitivity decreases when the exposure time becomes long. To improve the reciprocity law failure, it is known to dope silver halide grains with a metal such as Ir or a compound thereof such as JP-A-61-133,941 and JP-A-3-15,04.
Although it is publicly known as No. 0 and the like, there are side effects such as a decrease in sensitivity due to doping, the amount of doping is limited, and the improvement of reciprocity law characteristics is also limited.

On the other hand, there is a demand for higher sensitivity of silver halide photographic light-sensitive materials. Reduction sensitization is known as one of the techniques for increasing the sensitivity, and US Pat. No. 2,487,850
No., US2,512,925, GB789,823
A number of patents such as Japanese Patent Laid-Open No. Hei 2-136,852 disclose specific methods of reduction sensitization and are widely used, but they are a factor for deteriorating the pressure characteristics of photosensitive materials. . That is, a light-sensitive material containing a reduction-sensitized silver halide emulsion has a drawback in that a large increase in fog occurs when an external force such as scratching is applied.

[0008]

The present invention provides a method for producing a silver halide photographic emulsion having excellent sensitivity / granularity ratio, pressure characteristics and reciprocity law characteristics.

[0009]

The object of the present invention can be achieved by the following method for producing a silver halide photographic emulsion or a light-sensitive material.

(1) In a dispersion medium solution containing water and a dispersion medium, host parallel tabular grains made of silver iodobromide or silver bromide having an aspect ratio of 3 or more and having parallel (111) planes. In a silver halide grain forming step, which comprises a step of adding an emulsion containing a slightly soluble silver halide grain which is more insoluble than the host tabular grain to an emulsion occupying 50% or more of a projected area, the above insoluble silver halide grain Immediately after the completion of the grain addition step, 30 to 100% by weight of the dispersion medium has a ratio of the number of chemically modified --NH ₂ groups in gelatin to 30
% Of the modified gelatin is a modified gelatin, and a method for producing a silver halide photographic emulsion. (2) The production of the silver halide photographic emulsion according to (1), wherein the host tabular grains have a structure inside the grains, and the outermost layer of the host tabular grains consists essentially of silver bromide. Method. (3) The hardly soluble silver halide grains have a sphere-equivalent diameter of 0.1 μm.
The method for producing a silver halide photographic emulsion according to (1) or (2), characterized in that the silver iodide fine particles have a size of m or less. (4) The method for producing a silver halide photographic emulsion as described in any one of (1) to (3), wherein the host tabular grain is subjected to reduction sensitization. (5) In any one of the steps for producing the silver halide emulsion, there is a step of adding at least one kind of radical scavenger, (1), (2),
The method for producing a silver halide photographic emulsion according to (3) or (4). (6) The radical scavenger is represented by the general formula [A],
The method for producing a silver halide photographic emulsion according to (5), which is a compound represented by [B] or [C].

[0011]

Embedded image

In the general formula [A], R and R'may be the same or different and each is an alkyl group (for example, methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, hexyl, cyclohexyl, t-octyl, Decyl, dodecyl, hexadecyl, benzyl) or aryl groups (eg phenyl, naphthyl). In the general formula [B], R ₁ and R ₂ may be the same or different and each represents a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group (for example, methylamino, ethylamino, diethylamino, methylethylamino, propyl). Amino, dibutylamino, cyclohexylamino, t-octylamino, dodecylamino, hexadecylamino, benzylamino, benzylbutylamino), arylamino groups (eg, phenylamino, phenylmethylamino, diphenylamino, naphthylamino), alkoxy groups ( For example, methoxy, ethoxy, butoxy, t-butoxy, cyclohexyloxy, benzyloxy, octyloxy, tridecyloxy, hexadecyloxy), an aryloxy group (for example, phenoxy,
Naphthoxy), alkylthio groups (eg methylthio, ethylthio, i-propylthio, butylthio, cyclohexylthio, benzylthio, t-octylthio, dodecylthio), arylthio groups (eg phenylthio, naphthylthio), alkyl groups (eg methyl, ethyl, propyl, butyl, Cyclohexyl, i-amyl, sec-hexyl, t-octyl, dodecyl, hexadecyl) and aryl groups (eg phenyl, naphthyl). In the general formula [C], R _{a1 to} R _a5 may be the same or different,
A hydrogen atom, an alkyl group (eg, methyl, t-butyl, t-octyl, cyclohexyl, 2′-hydroxybenzyl, 4′-hydroxybenzyl, carboxyethyl), an alkenyl group (eg, allyl, vinyl), an aryl group (eg, phenyl). , 2-hydroxyphenyl, 4
-Hydroxyphenyl), a heterocyclic group (for example, 4-morpholinyl, 1-piperidyl, 1-pyrrolidinyl), an alkyloxycarbonyl group (for example, ethoxycarbonyl,
Hexadecyloxycarbonyl), aryloxycarbonyl groups (eg phenoxycarbonyl, 2,4-di-
t-butylphenoxycarbonyl), acyl group (eg acetyl, benzoyl, myristoyl), sulfonyl group (eg alkylsulfonyl, methanesulfonyl, arylsulfonyl, benzenesulfonyl, 2-hydroxybenzenesulfonyl), carboxyl group, carbamoyl group (eg dimethyl). It represents carbamoyl, methylphenylcarbamoyl, dodecylcarbamoyl), a sulfamoyl group (eg dimethylsulfamoyl, dodecylsulfamoyl), a halogen atom (eg chlorine, bromine, fluorine) or —X—R _a0 . X- is -O-,-
Represents S- or -N (R _a6 )-. R _a0 is an alkyl group (eg, methyl, isopropyl, octyl, benzyl,
Hexadecyl, methoxyethyl, cyclohexyl), alkenyl groups (eg allyl, vinyl), aryl groups (eg phenyl, 4-methoxyphenyl, naphthyl), heterocyclic groups (eg 2-tetrahydropyranyl, pyridyl), acyl groups (eg acetyl). , Benzoyl, tetradecanoyl) or a sulfonyl group (for example, alkylsulfonyl, methanesulfonyl, octanesulfonyl,
Arylsulfonyl, benzenesulfonyl),
R _a6 represents a hydrogen atom or a group defined by R _a0 . R
Of the groups _{a1 to} R _a5 , the substituents in the ortho positions may be bonded to each other to form a 5- to 7-membered ring (eg, chroman ring, indane ring), which forms a spiro ring or a bicyclo ring. It may be. However, each group of R _{a1 to} R _a5 is not a hydrogen atom at the same time, and R _a3 is a halogen atom or —O.
In the case of -R _a0 or -S-R _a0 , at least one of R _a1 and R _a5 is an alkyl group. (7) In the production method according to any one of (1) to (6), a silver bromide or iodide is further added following the step of adding an emulsion containing hardly soluble silver halide grains or silver iodide fine grains. A method for producing a silver halide photographic emulsion in which a region made of silver bromide is grown. (8) A silver halide color photographic light-sensitive material comprising a silver halide photographic emulsion manufactured by the manufacturing method according to any one of (1) to (7) in a photosensitive silver halide emulsion layer. material.

Hereinafter, the present invention will be described in detail. In the present invention, a sparingly soluble silver halide emulsion is added to a silver iodobromide or silver bromide host tabular grain emulsion, and thereafter, an aqueous silver nitrate solution and / or an aqueous halide solution is added, preferably a dislocation line is added to the tabular grain emulsion. Is about how to introduce.

Host tabular grain emulsions face (111)
It is composed of a main surface and side surfaces connecting the main surface. The host tabular grain emulsion comprises silver iodobromide or silver bromide. Although it may contain silver chloride, the silver chloride content is preferably 8 mol% or less, more preferably 3 mol% or less, or 0 mol%. In the case of silver iodobromide, the variation coefficient of the grain size distribution of the tabular grain emulsion is preferably 25% or less, and therefore the silver iodide content is preferably 20 mol% or less. By reducing the silver iodide content, the coefficient of variation of the grain size distribution of the tabular grain emulsion can be easily reduced. In particular, the coefficient of variation of the grain size distribution of the host tabular grain emulsion is preferably 20% or less, and the silver iodide content is preferably 10 mol% or less. The variation coefficient of the distribution of silver iodide content between grains is 2
It is preferably 0% or less, particularly preferably 10% or less.

When the host tabular grain emulsion is silver iodobromide, the tabular grain emulsion preferably has a structure within the grain with respect to silver iodide distribution. In this case, with respect to the silver iodide distribution, the grain structure may have a double structure, a triple structure, a quadruple structure or more. In any case, it is particularly preferable that the outermost layer of the structure is silver bromide which does not substantially contain silver iodide. Silver bromide containing substantially no silver iodide means that the silver iodide content of the outermost layer is 3 mol% or less, most preferably 1 mol% or less. The effect of the present invention on the silver iodide content of the outermost layer will be described in detail in Examples. A preferred structure of the host tabular grain emulsion is, for example, a triple structure grain composed of silver bromide / silver iodobromide / silver bromide. Other higher order structures are also preferred as long as the outermost layer is substantially silver bromide. 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 having 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 inner layer than the outermost layer is preferably higher than the silver iodide content of the outermost layer, and the silver iodide content of the inner layer is preferably 3 or more. Mol%
that's all. More preferably, when it is at least 5 mol%, the effect of the invention becomes remarkable.

Host tabular grain emulsion comprises 50% of total projected area
The above is occupied by particles having an aspect ratio of 3 or more. Here, the projected area and the aspect ratio of the tabular grains can be measured from an electron micrograph by a carbon replica method shadowed with a latex sphere for reference. When viewed from above, tabular grains are usually hexagonal, triangular or circular in shape, and the aspect ratio is the value obtained by dividing the equivalent diameter of a circle having an area equal to the projected area by the thickness.
The shape of the tabular grains is preferably as high as the ratio of hexagons, and the ratio of the lengths of adjacent sides of the hexagons is preferably 1: 2 or less. The higher the aspect ratio, the more remarkable the effect of the present invention is. Therefore, 50% or more of the total projected area of the host tabular grain emulsion is preferably occupied by grains having an aspect ratio of 5 or more. More preferably, the aspect ratio is 8 or more. However, if the aspect ratio is too large, the variation coefficient of the particle size distribution described above tends to increase, so that the aspect ratio is usually preferably 20 or less.

In the present invention, the host tabular grain emulsion comprises (111) major surfaces facing each other and side faces connecting the major surfaces. At least one twin plane is included between the main surfaces. Two twin planes are usually observed in the host tabular grain emulsion of the present invention. The interval between the two twin planes is US5
It can be less than 0.012μ as described in 219,720. Furthermore, JP-A-5-249585
As described in (1), the value obtained by dividing the distance between the (111) main surfaces by the twin plane spacing may be 15 or more.

In the present invention, the side faces connecting the opposite (111) main surfaces of the host tabular grain emulsion account for 75% of all the side faces.
The following is preferably composed of the (111) plane. Here, 75% or less of all side surfaces are composed of (111) planes, which is higher than 25% of all side surfaces (11
1) There is a crystallographic plane other than the plane. 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, it is more preferable that 70% or less of all side surfaces be composed of (111) planes.

Whether 70% or less of all the side faces are composed of (111) faces can be easily judged from an electron micrograph by a carbon replica method in which the host tabular grain is shadowed. 75% or more of the normal side surface is (11
In the case of the hexagonal tabular grains in the case of 1) planes, the six side faces directly connected to the (111) main surface are alternately connected to the (111) main surface at an acute angle and an obtuse angle. On the other hand, when 70% or less of all side faces are composed of (111) faces, in hexagonal tabular grains, (1
11) All six sides directly connected to the main surface are connected to the (111) main surface at an obtuse angle. By applying shadowing at an angle of 50 ° C. or less, the obtuse angle and the acute angle of the side surface with respect to the main back surface can be determined. Preferably, shadowing at an angle of 30 ° or less and 10 ° or more makes it easy to determine an obtuse angle and an acute angle.

Further, a method using adsorption of a sensitizing dye is effective as a method for obtaining the ratio of the (111) plane to the (100) plane. Journal of the Chemical Society of Japan, 1984, Volume 6, Page 94
The ratio of the (111) plane to the (100) plane can be quantitatively obtained by using the method described in Nos. 2-947.
It is possible to calculate the ratio of (111) planes on all side faces by using the ratio and the equivalent circle diameter and thickness of the tabular grains described above. In this case, tabular grains are assumed to be cylindrical using the equivalent circle diameter and thickness. By this assumption, the ratio of the side surface to the total surface area can be obtained. The value obtained by dividing the ratio of the (100) plane obtained by adsorption of the above-mentioned sensitizing dye by the ratio of the above-mentioned side faces and multiplying by 100 is the ratio of the (100) face on all side faces. If the value is subtracted from 100, the ratio of (111) planes on all side surfaces can be obtained.

EP 515,894A1 and the like can be referred to as a method for changing the plane index of the side surface of the host tabular grain emulsion. Further, the polyalkylene oxide compounds described in US Pat. No. 5,252,453 can also be used. US 4,680,254 as an effective method,
The surface index modifiers described in US Pat. No. 4,680,255, US Pat. No. 4,680,256 and US Pat. No. 4,684,607 can be used. Ordinary photographic spectral sensitizing dyes can also be used as a modifier having the same surface index as above.

The effect of the present invention is most remarkably obtained. The host tabular grain emulsion is silver iodobromide, and in the silver iodide distribution structure of the tabular grains, the outermost layer is substantially free of silver iodide. It is silver bromide, and 75% or less of the side faces are composed of (111) faces. Therefore, pBr may be selected so that the ratio of the (100) faces on the side faces increases when the substantially outermost silver iodide-free silver bromide layer of the host tabular grain emulsion is formed. Alternatively, by adding a silver halide solvent and / or a surface index modifier,
It suffices to increase the ratio of the 0) plane.

The pBr for increasing the ratio of the (100) plane on the side surface is the value depending on the temperature of the system, pH, the type and concentration of the dispersion medium such as gelatin, the presence or absence of the silver halide solvent, the type and the concentration. Can vary widely. Usually, preferably p
Br is 2.0 or more and 5.0 or less. More preferably pB
It is r2.4 or more and 4.5 or less. However, as described above, this pBr value can be easily changed by the presence of a silver halide solvent or the like. In the present invention, it is preferable not to use a silver halide solvent.

As the silver halide solvent which can be used in the present invention, US Pat. Nos. 3,271,157, 3,531,289, 3,574,628 and JP-A-54-1019 are known. (A) Organic thioethers described in JP-A No. 54-158917 and JP-A No. 53-824.
No. 08, No. 55-77737, No. 55-2982 and the like, (b) thiourea derivative, JP-A-53-14.
4319 (c) a silver halide solvent having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom, (d) imidazoles described in JP-A-54-100717, Examples include e) sulfite, (f) ammonia, (g) thiocyanate and the like.

Particularly preferred solvents are thiocyanate, ammonia and tetramethylthiourea. The amount of solvent used varies depending on the type, but in the case of thiocyanate, the preferred amount is silver halide 1.
It is 1 × 10 ⁻⁴ mol or more and 1 × 10 ⁻² mol or less per mol.

In the present invention, the silver iodobromide or silver bromide host tabular grain emulsion can be prepared by various methods as long as the above requirements are satisfied. The preparation of a host tabular grain emulsion usually comprises basically three steps of nucleation, ripening and growth. In the step of nucleation, use of gelatin having a low methionine content described in US4713320 and US4942120, U
It is extremely effective in the nucleation step of the host tabular grain emulsion of the present invention to perform nucleation with a high pBr described in S4914014 and to perform nucleation in a short time described in JP-A-2-222940. US in the aging process
It may be effective in the ripening step of the host tabular grain emulsion of the present invention to carry out in the presence of a low-concentration base as described in US Pat. No. 5,254,453 and at a high pH as described in US5013361. US in the growth process
Grow at low temperature described in No. 5248587, U
The use of silver iodide fine particles described in S4672027 and US Pat. No. 4,693,964 is particularly effective in the step of growing the host tabular grain emulsion of the present invention.

In the present invention, it is particularly preferable to use gelatin having a --NH ₂ group chemically modified as the dispersion medium used for the host tabular grain emulsion. In particular, the sparingly soluble silver halide emulsion added after the formation of host tabular grains is
When the NH ₂ group does not contain any chemically modified gelatin as the dispersion medium, it is essential that the host tabular grain emulsion contains the -NH ₂ group chemically modified gelatin as the dispersion medium. In the dispersion medium used for the host tabular grain emulsion, the proportion of gelatin having the —NH ₂ group chemically modified is preferably 30% by weight or more, more preferably 60% by weight or more, and most preferably 90% by weight. That is all.

Here, the gelatin whose -NH ₂ group is chemically modified will be described. As the -NH ₂ group in gelatin, the amino group of gelatin molecule terminal group, lysine group, hydroxylysine group, histidine group, amino group of arginine group and, if the arginine group is converted to an ortinine group, the amino group Can be mentioned. Furthermore, impurity groups such as adenine and guanine groups can also be mentioned. −
What is the chemical modification of NH ₂ group?
Reacting with the amino group to form or deaminate a covalent bond. That is, primary amino group (-NH ₂₎
Is converted to a secondary amino group (-NH-), a tertiary amino group, or a deaminated form.

Specifically, for example, acid anhydride (maleic anhydride, o-phthalic anhydride, succinic anhydride, isatoic
anhydride, benzoic anhydride, etc., acid halide (R
_{-COX, R-SO 2 X,} R-O-COX, Phenyl-C
OCl), compounds having an aldehyde group (R-CHO
Etc.), compounds having an epoxy group, deamination base (HN
O ₂ , deaminase, etc.), active ester compounds (sulfonic acid ester, p-nitrophenyl acetate, isopropenyl acetate, methyl-o-chlorobenzoate,
p-nitrophenyl benzoate etc.), isocyanate compounds (Aryl isocyanate etc.), active halogen compounds,
For example, [Aryl halide (benzyl bromide, biphenyl-halom
ethanes, benzoyl halomethane, phenyl benzoylhalo-m
ethane, 1-Fluoro-2,4-dinitro-benzene), β-Ketohalid
e, α-haloaliphatic acid, β-halonitrile, (s-tria
zine, pyrimidine, pyridazine, pyrazine, pyridazone, qu
inoxaline, quinazoline, phthalazine, benzoxazole, benz
chloro derivatives of othiazole, benzoimidazole), carbamoylating agents (cyanate, nitrourea, etc.), compounds having an acrylic type active double bond group (maleimide, acryamine, acry)
lamide, acrylonitrile, methylmetha acrylate, vinyl su
lphone, vinylsulphonate ester, sulphonamide, styrene
and vinylpyridine, allylamine, butadiene, isoprene, c
hloroprene, etc.), sultones (butane sultone, propane
sultone), Guanidine agent (o-methylisourea, etc.), ca
It can be achieved by adding rboxylazide etc. and reacting.

In this case, the --OH group of gelatin and --COO
A reagent that reacts mainly with the -NH ₂ group of gelatin is more preferable than a reagent that also reacts with an H group and forms a covalent bond. Mainly 60% or more, preferably 80-100
%, More preferably 95 to 100%. Furthermore, it is more preferable that the reaction product does not substantially contain a group in which oxygen of a ether group or a ketone group replaces a chalcogen atom, (eg, —S—, thione group). Here, "not substantially containing" means preferably 10% or less, and more preferably 0 to 3% of the number of chemically modified groups. Therefore, of the above,
Acid anhydrides, sultones, compounds having an active double bond group, carbamoylating agents, active halogen compounds, isocyanate compounds, active ester compounds, compounds having an aldehyde, and deamination bases are more preferred. It is more preferable that the chemical modification does not substantially allow crosslinking between gelatin molecules. The term "substantially impossible" means preferably 10% or less, more preferably 0 to 3% of the chemically modified group.

Other details of the chemical modifying agent and the method for chemically modifying gelatin are described in the following references, JP-A-4-4-2.
No. 26449, JP-A-50-3329, U.S. Pat. Nos. 2,525,753, 2,614,928, 2,614,929, 2,763,639, and 2,594. No. 293, No. 3,132,945, edited by Yoshihiro Abiko, Nikawa and Gelatin, Chapter II, Japan Nikawa Gelatin Industry Union (1987), Ward et al., The Scienc.
e and Technology of Gelatin, Chapter 7, Academic Pre
The description of ss (1977) can be referred to. The ratio of the number of chemically modified --NH ₂ groups of the modified gelatin can be determined as follows. The unmodified gelatin and the modified gelatin are prepared, and the -NH _{2 group} numbers of both are determined as e ₁ and e ₂ . The ratio (%) of the chemically modified number can be obtained from 100 × (e ₁ −e ₂ ) / e ₁ . The method for obtaining e ₁ and e ₂ is -NH ₂
The infrared absorption intensity based on a group, the NMR signal intensity of the proton, and a method utilizing a color reaction and a fluorescence reaction can be mentioned. For details, see Analytical Chemistry Handbook, Organic Edition-2, Maruzen (19).
The description in 91) can be referred to. Other examples include changes in the titration curve of gelatin and quantitative methods such as the formol titration method. For details, see The Science and Technology of Ge.
You can refer to the description of latin, Chapter 15, Academic Press (1977).

In addition, glutaraldehyde and Britton-Ro
binson A method in which a mixture of high pH buffer solution is added to a gelatin solution of a specified concentration to cause color development, and the spectral absorption intensity near 450 nm is measured and colorimetrically determined [Photogrnap
hic Gelatin II, p.297 ~ 315, Academic Press (1976)
Can be referred to].

[0033] Gelatin -NH ₂ group has been chemically modified for use in the present invention, the proportion of the number of -NH ₂ group has been chemically modified is 30% or more, preferably 50% or more,
More preferably, 80% or more, and most preferably 90% or more of the —NH ₂ groups are chemically modified.

In the present invention, a sparingly soluble silver halide emulsion is added to the silver iodobromide or silver bromide host tabular grain emulsion described above. Here, the slightly soluble silver halide emulsion means that the halogen composition is less soluble than the host tabular grain emulsion.

In the present invention, dislocation lines are preferably introduced by rapidly adding a silver iodide fine grain emulsion to the above-described silver iodobromide or silver bromide host tabular grain emulsion. This step consists essentially of two steps: a step of rapidly adding a silver iodide fine grain emulsion to the host tabular grain emulsion, and a step of growing silver bromide or silver iodobromide to introduce dislocation lines. It is. These two steps may be carried out completely separately, or they may be duplicated and carried out at the same time. It is preferably performed separately. The step of rapidly adding a silver iodide fine grain emulsion to the first host tabular grain emulsion will be described.

Rapid addition of a silver iodide fine grain emulsion means that
Preferably, the silver iodide fine grain emulsion is added within 10 minutes. More preferably, it means addition within 5 minutes. These conditions can vary depending on the temperature of the system to be added, pBr, pH, the type and concentration of the protective colloid agent such as gelatin, the presence or absence of the silver halide solvent, the type and the concentration, etc., but the shorter is preferable as described above. It is preferable that the addition of an aqueous solution of silver salt such as silver nitrate is not substantially performed during the addition.
The temperature of the system at the time of addition is preferably from 40 ° C to 90 ° C,
A temperature of 50 ° C or higher and 80 ° C or lower is particularly preferred. PBr when added
The optimum value of depends on the temperature of the system. For example, when the system temperature is 75 ° C., pBr is preferably 0.8 or more and 2.0 or less.

The silver iodide fine grain emulsion may be substantially silver iodide and may contain silver bromide and / or silver chloride as long as it can form a mixed crystal. Preferably 100%
It is silver iodide. In its crystal structure, silver iodide has β-form and γ-form.
Body and α-form or α-form-analogous structure as described in US 4,672,026. In the present invention, the crystal structure is not particularly limited, but a mixture of β-form and γ-form, more preferably β-form, is used. The silver iodide fine grain emulsion may be formed immediately before addition as described in US Pat. No. 5,004,679 or may be subjected to a usual washing step. Is used. The silver iodide fine grain emulsion can be easily formed by the method described in US Pat. No. 4,672,026 mentioned above. PI during particle formation
A double jet addition method of a silver salt aqueous solution and an iodide salt aqueous solution, which performs grain formation with a constant value, is preferable. Where pI
Is the logarithm of the reciprocal of the I ^- ion concentration of the system. Temperature, p
I, pH, presence or absence of silver halide solvent, type, concentration, etc.
Although not particularly limited, the particle size of 0.1 μm or less, more preferably 0.07 μm or less is convenient for the present invention.
Although the particle shape cannot be completely specified because of the fine particles, the variation coefficient of the particle size distribution is preferably 25% or less.
In particular, when the content is 20% or less, the effect of the present invention is remarkable. Here, the size and size distribution of the silver iodide fine grain emulsion are determined by placing silver iodide fine grains on a mesh for observation with an electron microscope and observing them directly by a transmission method instead of a carbon replica method. This is because the observation error by the carbon replica method becomes large due to the small particle size. Particle size is defined as the diameter of a circle having a projected area equal to the observed particle. The particle size distribution is also determined using the same projected area circle diameter. The most effective silver iodide fine grains in the present invention have a grain size of 0.0
It is 6 μm or less and 0.02 μm or more, and the variation coefficient of the particle size distribution is 18% or less.

After forming the above-mentioned grains, the silver iodide fine grain emulsion is preferably washed with water as described in US Pat. No. 2,614,929, and the pH, pI, the concentration of the dispersion medium such as gelatin, and the concentration of the silver iodide contained are preferably adjusted. Adjustments are made. The pH is preferably 5 or more and 7 or less. The pI value is preferably set near the pI value at which the solubility of silver iodide is the lowest. Usual gelatin may be used as the dispersion medium, but it is preferable to use gelatin in which the --NH ₂ group is chemically modified. In the dispersion medium used for the silver iodide fine grain emulsion, the proportion of gelatin whose -NH ₂ group is chemically modified is preferably 30% by weight or more, more preferably 60% by weight or more, and most preferably 90% by weight. % Or more. Regarding the molecular weight of gelatin, those having an average molecular weight of about 100,000 or low molecular weight gelatin having an average molecular weight of 20,000 or less are preferably used. It is sometimes convenient to use a mixture of gelatins having different molecular weights. The amount of gelatin per kg of emulsion is preferably 10 g or more and 100 g or less. More preferably, it is 20 g or more and 80 g or less. The amount of silver in terms of silver atoms per kg of the emulsion is preferably from 10 g to 100 g. More preferably 20 g or more and 80 g
It is as follows. The amount of gelatin and / or silver is preferably selected to a value suitable for rapidly adding a silver iodide fine grain emulsion.

The addition amount of the silver iodide fine grain emulsion is preferably 1 mol% or more and 1 in terms of silver amount with respect to the host tabular grain emulsion.
It is 0 mol% or less. Most preferably, it is 3 mol% or more and 7 mol% or less. By selecting this addition amount, a dislocation line described later is preferably introduced, and the effect of the invention becomes remarkable. The silver iodide fine grain emulsion is usually dissolved and added beforehand, but at the time of addition, it is necessary to sufficiently increase the stirring efficiency of the system. Preferably, the stirring rotation speed is set higher than usual. The addition of an antifoaming agent is effective to prevent the generation of foam during stirring. Specifically, US 5,275,929
The antifoaming agents described in the examples of the above item are used.

Immediately after the silver iodide fine grain emulsion was rapidly added to the host tabular grain emulsion, -N was used as a dispersion medium for the emulsion.
It is a feature of the present invention that gelatin containing chemically modified H ₂ group is contained. Immediately after the step of adding the silver iodide fine grain emulsion, the proportion of gelatin having the --NH ₂ group chemically modified in all the dispersion medium in the emulsion must be 30% by weight or more, preferably 60% by weight. % Or more, more preferably 90% by weight or more. It has been found by the present inventor that the pressure characteristic and the reciprocity law characteristic are improved and the photographic sensitivity is increased by satisfying the above conditions. The present invention is a tabular grain emulsion in which a sparingly soluble silver halide emulsion typified by a silver iodide fine grain emulsion is added in the grain forming step, and a chemically modified gelatin is allowed to exist in the emulsion having a dislocation. It is a technology that is clearly different from Japanese Patent Application Laid-Open No. 50-147324 in that it clearly shows that it is an important requirement for improving the pressure characteristics of the above. The mechanism by which the effects of the present invention are expressed is unknown and is currently under analysis. There is no description in the publicly known patents and documents that suggests that the above effects are exhibited by the constituent features of the present invention, and therefore, there is currently no knowledge that teaches the mechanism by which the effects of the present invention are exhibited.

After the silver iodide fine grain emulsion is rapidly added to the host tabular grain emulsion, silver bromide or silver iodobromide is grown to preferably introduce dislocation lines. The growth of silver bromide or silver iodobromide may be started before or simultaneously with the addition of the silver iodide fine grain emulsion. Start growing. The time from the addition of the silver iodide fine grain emulsion to the start of the growth of silver bromide or silver iodobromide is preferably within 10 minutes and 1 second or more. More preferably, it is 3 seconds or more within 5 minutes. More preferably, it is within 3 minutes and 10 seconds or more. This time interval is basically preferably as short as possible, but depending on conditions such as temperature immediately after addition of silver iodide fine particles and pBr,
If the time interval is short, the reproducibility of photographic performance may deteriorate. Therefore, it is preferable to appropriately set the above time interval depending on the conditions immediately after the addition of the silver iodide fine particles. It is preferable that the addition of fine silver iodide grains is completely completed before the start of growth of silver bromide or silver iodobromide.

Growth after addition of the silver iodide fine grain emulsion is preferably silver bromide. In the case of silver iodobromide, the silver iodide content is preferably within 5 mol% with respect to the layer. More preferably, it is within 3 mol%. The silver content of the layer grown after the addition of the silver iodide fine grain emulsion is preferably 20 or more and 70 or less, when the silver content of the host tabular grain emulsion is 100. Most preferably, it is 25 or more and 65 or less. The temperature, pH and pBr for forming this layer are not particularly limited, but the temperature is usually 40 ° C. or more and 90 ° C. or less, and the pH is usually 2 or more and 9 or less. More preferably, a temperature of 50 ° C. or more and 80 ° C. or less, and a pH of 3 or more and 7 or less are used. With respect to pBr, in the present invention, it is preferable that pBr at the end of the formation of the layer be higher than pBr at the beginning of the formation of the layer.
Preferably, the pBr at the beginning of formation of the layer is 2.9 or less and the pBr at the end of formation of the layer is 1.0 or more. More preferably, the pBr at the beginning of formation of the layer is 2.5 or less, and the pBr at the end of formation of the layer is 1.4 or more. Most preferably, the pBr at the beginning of formation of the layer is 2.1 or less and the pBr at the end of formation of the layer is 1.6 or more. The dislocation lines in the present invention are preferably introduced by the above method.

In the present invention, the tabular grains preferably have dislocation lines. Dislocation lines of tabular grains are described, for example, in J. Am. F. H
amilton, Photo. Sci. Eng. , 11,
57, (1967); Shiozawa, J .; So
c. Photo. Sci. Japan, 35, 213,
(1972) can be observed by a direct method using a transmission electron microscope at a low temperature. In other words, the silver halide grains taken out carefully so as not to apply pressure enough to generate dislocation lines from the emulsion, place them on a mesh for electron microscope observation, and 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. Therefore, it is possible to more clearly observe using a high-voltage electron microscope (200 kV or more for particles having a thickness of 0.25 μm). . From the photograph of the particles obtained by such a method, the position and the number of dislocation lines for each particle 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, an average of 20 per particle
More than a book. When dislocation lines are densely present or when dislocation lines are observed to intersect each other, the number of dislocation lines per grain may not be clearly counted. However, even in these cases, it is possible to count to about 10, 20, or 30 pieces, and it can be clearly distinguished from the case where there are only a few pieces. The average number of dislocation lines per particle is determined as a number average by counting the number of dislocation lines for 100 particles or more.

The dislocation lines can be introduced, for example, near the outer periphery of the tabular grains. In this case, the dislocation is almost perpendicular to the outer periphery, and a dislocation line is generated from the position of x% of the distance from the center of the tabular grain to the side (outer periphery) to the outer periphery. The value of x is preferably 10 or more and less than 100, more preferably 30 or more and less than 99, and most preferably 50 or more and less than 98. At this time, the shape formed by connecting the start positions of the dislocation lines is similar to the particle shape, but it is not a perfect similar shape and may be distorted. This type of dislocation number is not found in the central region of the grain.
The direction of the dislocation lines is approximately (211) crystallographically, but often meanders, and may intersect each other.

The tabular grains may have dislocation lines almost uniformly over the entire area on the outer circumference, or may have dislocation lines at local positions on the outer circumference. That is, in the case of hexagonal tabular silver halide grains, dislocation lines may be limited only to the vicinity of six vertices, or dislocation lines may be limited to only one of the vertices. Conversely, it is also possible that the dislocation lines are limited only to the sides excluding the vicinity of the six vertices.

Further, dislocation lines may be formed over a region including the centers of two parallel main planes of tabular grains. When dislocation lines are formed over the entire area of the main plane, the direction of the dislocation lines may be approximately (211) crystallographically when viewed from a direction perpendicular to the main plane. In some cases, the dislocation lines are formed randomly, and the length of each dislocation line is also random. In some cases, the dislocation lines are observed as short lines on the main plane, and in other cases, they are observed as long lines reaching the side (outer circumference). is there. Dislocation lines are sometimes straight or meandering. They also often intersect with each other.

The position of the number of dislocations may be limited to the outer circumference, the main plane, or a local position as described above, or may be formed by combining these.
That is, they may be present simultaneously on the outer periphery and on the main plane.

The present invention is very effective as a means for reducing the deterioration of pressure characteristics that occurs when reduction sensitization is performed in the silver halide emulsion manufacturing process.

The reduction sensitization in the present invention will be described. The reduction sensitization may be carried out at any of the steps of grain formation, desalting, dispersion and chemical sensitization, which are the steps for producing a silver halide emulsion, but in the present invention, grain formation is carried out. It is preferable to carry out in a step, particularly preferably in the step of forming host tabular grains. Reduction sensitization may be carried out at the initial stage of host tabular grain formation, that is, during nucleation, during physical ripening, or during growth. The reduction sensitization during growth includes a method of performing reduction sensitization while growing, and a method of further performing reduction sensitization after growth is temporarily stopped during growth.

The reduction sensitization of the present invention means a method of adding a known reducing agent to a silver halide emulsion, pAg called silver ripening.
Either a method of growing or aging in a low pAg atmosphere of 1 to 7 or a method of growing or aging in a high pH atmosphere of pH 8 to 11 called high pH aging can be selected. Also, two or more methods can be used in combination.

The method of adding a reduction sensitizer is a preferable method because the level of reduction sensitization can be finely adjusted.

Known reduction sensitizers are stannous salts, amines and polyamic acids, hydrazine derivatives, formamidinesulfinic acid, silane compounds and borane compounds. In the present invention, these known compounds can be selected for use, and two or more compounds can be used in combination. Stannous chloride, thiourea dioxide, and dimethylamine borane are preferred compounds as reduction sensitizers. The addition amount of the reduction sensitizer depends on the emulsion production conditions, so it is necessary to select the addition amount, but 10 ^-7 to 10 ^-3 per mol of silver halide
A molar range is appropriate.

Ascorbic acid and its derivatives can also be used as the reduction sensitizer of the present invention.

Ascorbic acid and its derivatives (hereinafter referred to as
It is called "ascorbic acid compound". The following can be mentioned as specific examples of ()). (V-1) L-ascorbic acid (V-2) L-ascorbate sodium (V-3) L-ascorbate potassium (V-4) DL-ascorbic acid (V-5) D-ascorbate (V -6) L-ascorbic acid-6-acetate (V-7) L-ascorbic acid-6-palmitate (V-8) L-ascorbic acid-6-benzoate (V-9) L-ascorbic acid-5,6 -Diacetate (V-10) L-ascorbic acid-5,6-O-isopropylidene The ascorbic acid compound used in the present invention is used in a large amount as compared with the addition amount in which a reduction sensitizer is conventionally used preferably. Is desirable. For example, JP-B-57-33572
No. "The amount of reducing agent is usually 0.75 × g per silver ion.
Does not exceed 10 ^-2 meq (8 × 10 ^-4 mol / AgX mol). An amount of 0.1 to 10 mg per kg of silver nitrate (10 ^-7 to 10 ^-5 mol / AgX mol as ascorbic acid) is often effective. (The converted value is based on the inventors). U.S. Pat. No. 2,487,850 states that "the amount of tin compound which can be used as a reduction sensitizer is 1
× 10 ^{-7 to} 44 × 10 ^-6 mol ". JP-A-57-179835 states that it is appropriate to use about 0.01 mg to about 2 mg of thiourea dioxide per mole of silver halide and about 0.01 mg to about 3 mg of stannous chloride. It has been described. The preferred amount of the ascorbic acid compound used in the present invention depends on factors such as the grain size of the emulsion, the halogen composition, the temperature for preparing the emulsion, the pH and the pAg, but is preferably from 5 × 10 ^-5 to 1 × 10 ^-5 per mol of silver halide.
It is desirable to select from the range of × 10 ^-1 mol. More preferably, it is preferably selected from the range of 5 × 10 ⁻⁴ mol to 1 × 10 ⁻² mol. Particularly preferred is 1 × 10 ⁻³ mol or more.
It is to select from a range of 1 × 10 ^-2 mol.

The reduction sensitizer is water or alcohols,
It can be dissolved in a solvent such as glycols, ketones, esters and amides and added before or after the grain formation step or chemical sensitization. It may be added at any stage of the emulsion manufacturing process, but it is preferably added in the grain forming process, and particularly preferably added during the growth of host tabular grains. It may be added to the reaction vessel in advance, but it is more preferable to add it at an appropriate time during particle formation. Alternatively, a reduction sensitizer may be added to an aqueous solution of a water-soluble silver salt or a water-soluble alkali halide in advance, and particles may be formed using these aqueous solutions. It is also a preferred method to add the solution of the reduction sensitizer in several portions as the grains are formed, or to add the solution continuously for a long time.

It is preferable to use an oxidizing agent for silver during the process of producing the emulsion of the present invention. The oxidizing agent for silver is
A compound that acts on metallic silver to convert it into silver ions. In particular, a compound that converts extremely fine silver grains by-produced during the formation process of silver halide grains and the chemical sensitization process into silver ions is effective. The silver ion generated here may form a silver salt which is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt which is easily soluble in water such as silver nitrate. Is also good. The oxidizing agent for silver may be an inorganic substance or an organic substance. Examples of the inorganic oxidizing agent include ozone, hydrogen peroxide and adducts thereof (for example, NaBO ₂ .H ₂ O ₂ .3H ₂ O, 2Na
_{CO 3 · 3H 2 O 2,} Na 4 P 2 O 7 · 2H 2 O 2, 2
Na ₂ SO ₄ · H ₂ O ₂ · 2H ₂ O), peroxy acid salts (eg K ₂ S ₂ O ₈ , K ₂ C ₂ O ₆ , K ₂ P ₂ O ₈ ),
Peroxy complex compound (for example, K ₂ [Ti (O ₂ ) C ₂
O ₄ ] ・ 3H ₂ O, 4K ₂ SO ₄・ Ti (O ₂ ) OH ・ S
_{O 4 · 2H 2 O, Na} 3 _{[VO (O 2) (C 2} H 4) 2 · 6
H ₂ O), permanganates (eg KMnO ₄ ), chromates (eg K ₂ Cr ₂ O ₇ ) and other oxyacid salts, iodine and bromine and other halogen elements, perhalogenates (eg Potassium iodate) salts of high valent metals (eg potassium hexacyanoferrate) and thiosulfonates. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and compounds that release active halogen (eg, N-bromosuccinimide, chloramine T, chloramine B). ) Is given as an example.

Preferred oxidizing agents of the present invention are ozone, hydrogen peroxide and its adducts, halogen elements, thiosulfonate inorganic oxidizing agents and quinone-type organic oxidizing agents.
It is a preferable embodiment to use the reduction sensitization and the oxidizing agent for silver in combination. The method can be selected from a method of performing reduction sensitization after using an oxidizing agent, a method reverse thereto, or a method of coexisting the two simultaneously. These methods can be selectively used in both the grain formation step and the chemical sensitization step.

In the present invention, it was found that the preparation of the silver halide emulsion in the presence of the radical scavenger significantly promotes the improvement of the pressure characteristics and the reciprocity law characteristics, which are the effects of the present invention. .

It is known that a silver halide photographic light-sensitive material contains a radical scavenger according to the present invention as defined below. JP-B-43-413
3, 49-10692, JP-A-57-17603.
No. 2, No. 56-52734, No. 58-28714,
61-91651, 59-971134, 5
9-162546, British Patent No. 2,054,187
U.S. Pat. Nos. 3,582,333 and 3,671,
248, 3,902,905, 3,522,0
In each specification of No. 53, development of a light-sensitive material (not silver halide photographic emulsion), prevention of fogging, improvement of gradation,
It is known to contain various compounds within the scope of the radical scavenger defined in the present invention for the purpose of improving the raw storage stability and the latent image storage stability.

However, these inventions are only those which are contained by mixing with a silver halide photographic emulsion immediately before coating, or are added to an intermediate layer or the like, or the timing of addition is clearly indicated. Radical scavengers, especially the general formula [A], during the production process of silver emulsion,
It is not known at all that the addition of the compound represented by [B] or [C] has the effect of improving the pressure characteristic and the reciprocity law characteristic, and it is novel.

Although the mechanism of the present invention is not always clear, at present, it has a radical scavenging ability to substantially prevent the influence of oxygen or radical species derived from oxygen on silver halide, and at the same time, direct halogen A compound that does not affect silver halide and exerts no adverse effect is considered most preferable. In this sense, the general formula [A] containing certain hydroxylamines, phenols, tocopherols, etc.
The compound represented by [B] or [C] is most preferable.

Next, the radical scavenger used in the present invention will be described. The radical scavenger in the present invention refers to galvinoxyl of 0.
05 mmol / dm ³ ethanol solution and 2.5 of test compound
It refers to a compound which is mixed with a mmol / dm ³ ethanol solution by the stopped-flow method and the time change of the absorbance at 430 nm is measured to substantially decolorize galvinoxyl (decrease the absorbance at 430 nm). The decolorization rate constant of galvinoxyl determined by the above method is preferably 0.01 dm ³ / mmol · s or more, more preferably 0.1 dm ³ / mmol · s or more. The method for determining the radical scavenging rate using galvinoxyl is
Microchemical Journal 31, 18-21 (1985)
For the stopped-flow method, for example, spectroscopic studies
Vol. 19, No. 6, (1970), p. 321.

In the present invention, it is more preferable to use a compound represented by the general formula [A], [B] or [C] as the radical scavenger.

First, the compound represented by the following general formula [A] or [B] will be described in detail.

[0066]

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In the general formula [A], R and R'may be the same or different and each represents an alkyl group (for example, methyl, ethyl, i-propyl, cyclopropyl, butyl, isobutyl, hexyl, cyclohexyl, t-octyl, Decyl, dodecyl, hexadecyl, benzyl) or aryl groups (eg phenyl, naphthyl).

In the general formula [B], R ₁ and R ₂ may be the same or different and each represents a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group (for example, methylamino, ethylamino, diethylamino, methylethyl). Amino, propylamino, dibutylamino,
Cyclohexylamino, t-octylamino, dodecylamino, hexadecylamino, benzylamino, benzylbutylamino), arylamino groups (eg phenylamino, phenylmethylamino, diphenylamino, naphthylamino), alkoxy groups (eg methoxy, ethoxy, Butoxy, t-butoxy, cyclohexyloxy,
Benzyloxy, octyloxy, tridecyloxy,
Hexadecyloxy), aryloxy groups (eg phenoxy, naphthoxy), alkylthio groups (eg methylthio, ethylthio, i-propylthio, butylthio, cyclohexylthio, benzylthio, t-octylthio,
Dodecylthio), arylthio groups (eg phenylthio, naphthylthio), alkyl groups (eg methyl, ethyl, propyl, butyl, cyclohexyl, i-amyl,
sec-hexyl, t-octyl, dodecyl, hexadecyl) and aryl groups (eg phenyl, naphthyl).

The groups represented by R, R ', R ₁ and R ₂ represented by the general formula [A] or [B] may be further substituted with a substituent. Examples of these substituents include an alkyl group, an aryl group, a heterocyclic group, a hydroxy group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amino group, an acylamino group, a sulfonamide group, an alkylamino group and an arylamino group. ,
Examples thereof include a carbamoyl group, a sulfamoyl group, a sulfo group, a carboxyl group, a halogen atom, a cyano group, a nitro group, a sulfonyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group and an acyloxy group. In the general formula [A], it is preferred that R and R'are alkyl groups. On the other hand, in the general formula [B], R ₁
And R ₂ is a hydroxyamino group, an alkylamino group,
A group selected from alkoxy groups is preferred. Particularly preferred compounds of the present invention can be represented by the general formula [B '].

[0070]

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[0071] In the formula, R ₂ represents a same group as R ₂ in the general formula (B), the same as in the preferred group of the general formula (B). Specific examples of the compounds represented by formulas [A] and [B] of the present invention are shown below, but the present invention is not limited thereto.

[0072]

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[0073]

[Chemical 6]

[0074]

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[0075]

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[0076]

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[0077]

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[0078]

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These compounds of the present invention are described in J. Org. Chem.,
27, 4054 ('62), J. Amer. Chem. Soc., 73, 2981 ('51),
It can be easily synthesized by the method described in JP-B-49-10692 or the like.

Next, the compound represented by the general formula [C] will be described in detail.

[0081]

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The substituent described in the present invention may further have a substituent.

In the general formula [C], R _{a1 to} R _a5 may be the same or different and each is a hydrogen atom or an alkyl group (for example, methyl, t-butyl, t-octyl, cyclohexyl, 2'-hydroxybenzyl, 4 '). -Hydroxybenzyl, carboxyethyl, preferred carbon absorption is 1
To 30), an alkenyl group (for example, allyl or vinyl, preferably 2 to 30 carbon atoms), an aryl group (for example, phenyl, 2-hydroxyphenyl, 4-hydroxyphenyl, preferably phenyl having 6 to 30 carbon atoms and substituted). Phenyl), heterocyclic groups (eg 4-morpholinyl,
1-piperidyl and 1-pyrrolidinyl, preferably a saturated heterocycle having 4 to 15 carbon atoms), an alkyloxycarbonyl group (eg, ethoxycarbonyl, hexadecyloxycarbonyl), an aryloxycarbonyl group (eg, phenoxycarbonyl, 2,4) -Di-t-butylphenoxycarbonyl), an acyl group (eg acetyl, benzoyl, myristoyl), a sulfonyl group (preferably an alkylsulfonyl group such as methanesulfonyl, an arylsulfonyl group such as benzenesulfonyl, 2-hydroxybenzenesulfonyl), a carboxyl group. Groups, carbamoyl groups (eg dimethylcarbamoyl, methylphenylcarbamoyl, dodecylcarbamoyl), sulfamoyl groups (eg dimethylsulfamoyl, dodecylsulfamoyl), ha Gen atom (e.g., chlorine, bromine, fluorine) represent or -X-R _a0.

--X-- is --O--, --S-- or --N (R
_a6 ) represents-. R _a0 is an alkyl group (eg, methyl, isopropyl, octyl, benzyl, hexadecyl, methoxyethyl, cyclohexyl, and the preferred carbon absorption is 1
To 26), an alkenyl group (e.g., allyl and vinyl, preferably having 2 to 26 carbon atoms), and an aryl group (e.g., phenyl, 4-methoxyphenyl, and naphthyl, preferably phenyl having 6 to 30 carbon atoms or substituted phenyl) A heterocyclic group (eg, 2-tetrahydropyranyl,
Pyridyl), acyl groups (eg acetyl, benzoyl,
Tetradecanoyl) or a sulfonyl group (preferably an alkylsulfonyl group such as methanesulfonyl, octanesulfonyl, an arylsulfonyl group such as benzenesulfonyl), and R _a6 represents a hydrogen atom or a group defined by R _a0 . Of the groups R _{a1 to} R _a5 , substituents in the ortho positions may be bonded to each other to form a 5- to 7-membered ring (eg, chroman ring, indane ring), which forms a spiro ring or a bicyclo ring. You can do it.

However, if each group of R _{a1 to} R _a5 is not a hydrogen atom at the same time, and R _a3 is a halogen atom, —O—R _a0 or —S—R _a0 , then R _a1 and R _a5 At least one is an alkyl group.

Among the compounds represented by the general formula [C], preferred compounds from the viewpoint of the effects of the present invention are listed.

A compound having a substituent at any position of R _a1 , R _a3 or R _a5 and having a hydrogen atom at the α-position of at least one of the substituents.

Compounds in which R _a1 is substituted with an alkyl group.

Compounds in which R _a1 is substituted with an acylamino group.

A compound in which the substituents in the ortho positions among the groups R _{a1 to} R _a5 are bonded to each other to form a chroman ring, a Claman ring or an indane ring.

Among the compounds represented by the general formula [C], the particularly preferable compounds from the viewpoint of the effect of the present invention are the general formulas (C-I) and (C-II) shown below, and the most preferable compounds are the general formulas. (C-II).

[0092]

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In the general formula (CI), R _a10 represents an alkyl group, R _a11 represents an alkyl group, an alkoxy group,
Or an aryloxy group. R _a2 , R _a4 and R
_a5 represents a group defined by the general formula [C]. General formula (C
In -I), a compound in which R _a2 , R _a4 and R _a5 are a hydrogen atom, an alkyl group or an alkoxy group is preferable from the viewpoint of the effect of the present invention.

In the general formula (C-I), R _a2 and R _a11 , R _a2 and R _a10 or R _a4 and R _a11 are binders,
A compound forming a signet ring, a coumaran ring, a chroman ring or their spiro ring or bicyclo ring is also preferable.

In formula (C-II), R _{a12 to} R a
_a15 represents an alkyl group, and R _a15 represents a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, an acyl group or a sulfonyl group. X _a1 represents a single bond, —O—, —S— or —CH (R _a17 ) —. Here, _Ra17 represents a hydrogen atom, an alkyl group or an aryl group. In the general formula (C-II), in view of the effect of the present invention, a compound in which R _a16 is a hydrogen atom, or X _a1 is —CH (R _a17 ).
Is preferred, and in this case, it is particularly preferable that _Ra17 is a hydrogen atom or an alkyl group (preferably having 1 to 11 carbon atoms).

Specific examples of the compound represented by the formula [C] of the present invention are shown below, but the compounds used in the present invention are not limited thereto.

[0097]

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[0098]

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[0099]

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[0100]

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[0101]

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[0102]

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[0103]

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[0104]

[Chemical 21]

[0105]

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[0106]

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[0107]

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[0108]

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[0109]

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[0110]

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Other preferred compound examples and synthetic methods of the compound represented by the general formula [C] of the present invention are described in US Pat. Nos. 3,432,300, 3,573,050 and 3,574. , 627, 3,700, 455,
No. 3,764,337, No. 3,930,866
No. 4,113,495, No. 4,120,72
No. 3, No. 4,268,593, No. 4,430,4
25, 4,745,050, U.S. Pat. No. 2,0
No. 43,931, European Patent No. 176,845, Japanese Patent Publication Nos. 48-31256, 54-12055, and Japanese Patent Laid-Open Publication No.
No. 137258, No. 1-137254 and the like.

Table 1 shows the decolorization rate constants of some radical scavengers galvinoxyl.

[0113]

[Table 1]

In the method of the present invention, the radical scavenger compound may be added after being dissolved in water, alcohol, ester or ketone or a mixed solvent thereof. In the case of being dissolved in water, if the solubility is increased by increasing or decreasing the pH, the compound may be dissolved by increasing or decreasing the pH and then added. Soluble radical scavengers may also be added in dispersed form in aqueous gelatin solution.

In the method of the present invention, the addition amount of the radical scavenger compound is preferably in the range of 1 × 10 ⁻⁶ to 1 × 10 ⁻² mol per mol of silver halide to be added,
The amount is more preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻³ mol, and further preferably 5 × 10 ⁻⁵ to 1 × 10 ⁻³ mol.

In the method of the present invention, the radical scavenger may be added at any of the grain formation step (including physical ripening), the desalted water washing step, and the chemical sensitization step. It is preferably added during the beginning of the process. Further, it is particularly preferable to add it in the particle forming step.

As a dispersion medium used in combination with gelatin whose -NH ₂ group is chemically modified during the preparation of the emulsion of the present invention,
And as the binder of the other hydrophilic colloid layer,
It is advantageous to use gelatin, but other hydrophilic polymer compounds having protective colloid ability can also be used. For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein; cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose and cellulose sulfates; sugar derivatives such as sodium alginate and starch derivatives; polyvinyl alcohol Use of various kinds of synthetic hydrophilic high-molecular substances such as mono- or copolymers of polyvinyl alcohol, partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be.

As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin and Bull. Soc. Sci. Photo. Japan. No.
16, P30 (1966), and enzyme-treated gelatin may be used, and a hydrolyzate or an enzyme-decomposed product of gelatin may also be used.

The emulsion of the present invention is preferably washed with water for desalting and then dispersed using a newly prepared dispersion medium having a protective colloid ability. The temperature for washing with water can be selected according to the purpose, but it is preferably selected within the range of 5 ° C to 50 ° C. The pH at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 2 and 10. More preferably, it is in the range of 3 to 8. The pAg at the time of washing with water can also be selected according to the purpose, but it is preferably selected between 5 and 10. Noodle water washing method,
A dialysis method using a semipermeable membrane, a centrifugation method, a coagulation sedimentation method, or an ion exchange method can be selected and used. In the case of the coagulation sedimentation method, 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 can be selected.

During preparation of the emulsion of the present invention, for example, during grain formation,
In the desalting step, at the time of chemical sensitization, the presence of a metal ion salt before coating is preferable depending on the purpose. In the case of doping the grains, it is preferable to add them at the time of grain formation, when modifying the grain surface or when using as a chemical sensitizer, after grain formation and before the end of chemical sensitization. A method of doping the whole grain and a method of doping only the core part, only the shell part, only the epitaxial part, or only the base grain of the grain can be selected. Mg, Ca, Sr, Ba, Al, S
c, Y, LaCr, Mn, Fe, Co, Ni, Cu, Z
n, Ga, Ru, Rh, Pd, Re, Os, Ir, P
t, Au, Cd, Hg, Tl, In, Sn, Pb, Bi
Etc. 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, CdB
r ₂ , CdCl ₂ , Cd (NO ₃ ) ₂ , Pb (NO ₃ ) ₂ ,
Pb (CH ₃ COO) ₂ , K ₃ [Fe (CN) ₆ ], (NH
₄ ) ₄ [Fe (CN) ₆ ], K ₃ IrCl ₆ , (NH ₄ ) ₃ R
hCl ₆ , K ₄ Ru (CN) _{6 and the} like. The ligand of the coordination compound can be selected from halo, aquo, cyano, cyanate, thiocyanate, nitrosyl, thionitrosyl, oxo, and carbonyl. These may be used alone or in combination of two or more metal compounds.

The metal compound is preferably added by dissolving it in water or a suitable solvent such as methanol or acetone.
In order to stabilize the solution, an aqueous solution of hydrogen halide (eg, HC
1, HBr, etc.) or alkali halides (eg KC
1, NaCl, KBr, NaBr, etc.). If necessary, an acid or alkali may be added. The metal compound may be added to the reaction vessel before the formation of the particles or may be added during the formation of the particles. 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 alkali halide may be prepared and added continuously 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 preparation of an emulsion may be useful. In addition to S, Se, Te, cyanide, thiocyanate, selenocyanic acid, carbonate,
Phosphates and acetates may be present.

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

One of the chemical sensitizations which can be preferably carried out in the present invention is chalcogenide sensitization and noble metal sensitization, either alone or in combination, by TH James, The Photographic Process, 4th Edition, Macmillan Company. Published, 1977
Year, (THJames, The Theory of the Photographic Proc
ess, 4th ed, Macmillan, 1977) 67-76, using active gelatin, and Research Disclosure 120, 19
Research Disclosure, 34, June 1975, 13452, U.S. Pat. Nos. 2,642,361, 3,297,446, 3,772,031, and 3; 857,711, 3,901,714, 4,266,018, and 3,904,415, and British Patent 1,31.
PAg 5-10, pH as described in US Pat.
Sulfur, selenium at 5-8 and a temperature of 30-80 ° C.
It can be tellurium, gold, platinum, palladium, iridium or combinations of these sensitizers. In the noble metal sensitization, noble metal salts such as gold, platinum, palladium and iridium can be used, and among them, gold sensitization, palladium sensitization and a combination of both are preferable. In the case of gold sensitization, known compounds such as chloroauric acid, potassium chloroaurate, potassium aurithiocyanate, gold sulfide and gold selenide can be used. The palladium compound means a divalent palladium salt or a tetravalent salt. Preferred palladium compounds are represented by R ₂ PdX ₆ or R ₂ PdX ₄ . Here, R represents a hydrogen atom, an alkali metal atom or an ammonium group. X represents a halogen atom, and represents a chlorine, bromine or iodine atom.

Specifically, K ₂ PdCl ₄ , (NH ₄ ) ₂
PdCl ₆ , Na ₂ PdCl ₄ , (NH ₄ ) ₂ PdC
l ₄ , Li ₂ PdCl ₄ , Na ₂ PdCl ₆ or K ₂
PdBr ₄ is preferred. The gold compound and the palladium compound are preferably used in combination with a thiocyanate or a selenocyanate. As sulfur sensitizers, hypo, thiourea compounds, rhodanine compounds and US Pat.
57,711, 4,266,018 and 4,
The sulfur-containing compounds described in 054,457 can be used. Chemical sensitization can also be performed in the presence of a so-called chemical sensitization aid. Useful chemical sensitization aids include compounds known to suppress fog and increase sensitivity during chemical sensitization, such as azaindene, azapyridazine and azapyrimidine. Examples of chemical sensitization aid modifiers are described in US Pat. No. 2,131,038,
No. 3,411,914, No. 3,554,757, JP-A No. 58-126526, and Duffin, "Photographic Emulsion Chemistry", pages 138-143.

The emulsion of the present invention is preferably combined with gold sensitization. The preferred amount of the gold sensitizer is 1 × 10 ^-4 to 1 × 10 ^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 10 ^-7 mol, per mol of silver halide. The preferable range of the palladium compound is 1 × 10 ⁻³ to 5 × 10 ⁻⁷ . The preferred range of the thiocyan compound or selenocyan compound is from 5 × 10 ⁻² to 1 × 10 ⁻⁶ . The preferred amount of sulfur sensitizer used for the silver halide grains of the present invention is from 1 × 10 ⁻⁴ to 1 × 10 ⁴ per mol of silver halide.
^-7 mol, more preferably 1 × 10 ^{-5 to} 5 × 1
^0-7 mol.

Selenium sensitization is a preferable sensitizing method for the emulsion of the present invention. In selenium sensitization, a known unstable selenium compound is used, and specifically, colloidal metal selenium, selenoureas (eg, N, N-dimethylselenourea, N, N-diethylselenourea, etc.), selenoketone And selenium compounds such as selenoamides can be used. It may be preferable to use selenium sensitization in combination with sulfur sensitization and / or noble metal sensitization.

The photographic emulsion used in the present invention may contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the photographic material, 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 and the like can be added. For example, U.S. Pat. Nos. 3,954,474 and 3,982,9
No. 47 and JP-B No. 52-28660 can be used. Japanese Patent Application No. Sho 6
There is a compound described in 2-47225. Antifoggants and stabilizers are used at various times before, during and 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 according to the purpose. In addition to exhibiting the original antifogging and stabilizing effects by adding during emulsion preparation, it controls the crystal wall of the grains, reduces the grain size, reduces the solubility of the grains, controls the chemical sensitization, It can be used for various purposes such as controlling the arrangement of dyes.

The photographic emulsion used in the present invention is preferably spectrally sensitized with a methine dye or the like in order to exert the effects of the present invention. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Particularly useful dyes are those belonging to the cyanine dyes, merocyanine dyes, and complex merocyanine dyes. Any of the nuclei usually used for cyanine dyes as basic heterocyclic nuclei can be applied to these dyes. That is, a pyrroline nucleus, an oxazoline nucleus, a thiozoline nucleus, a pyrrole nucleus, an oxazole nucleus, a thiazole nucleus, a selenazole nucleus, an imidazole nucleus, a tetrazole nucleus, a pyridine nucleus, etc .; A nucleus in which an aromatic hydrocarbon ring is fused to the nucleus of
That is, an indolenine nucleus, a benzindolenin nucleus, an indole nucleus, a benzoxadol nucleus, a naphthoxazole nucleus, a benzothiazole nucleus, a naphthothiazole nucleus, a benzoselenazole nucleus, a benzimidazole nucleus, a quinoline nucleus, and the like can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, as a nucleus having a ketomethylene structure, a pyrazolin-5-one nucleus, a thiohydantoin nucleus, a 2-thiooxazolidine-2,4-dione nucleus, a thiazolidine-2,4-
A 5- to 6-membered heterocyclic nucleus such as a dione nucleus, a rhodanine nucleus, and a thiobarbituric acid nucleus can be applied. These sensitizing dyes may be used alone or in combination, and a combination of sensitizing dyes is often used particularly for supersensitization. A representative example is U.S. Pat.
8,545, 2,977,229, 3,39
7,060, 3,522,052, 3,52
No. 7,641, No. 3,617,293, No. 3,62
8,964, 3,666,480, 3,67
2,898, 3,679,428, 3,70
No. 3,377, No. 3,769,301, No. 3,81
4,609, 3,837,862, 4,02
6,707, British Patents 1,344,281, 1,507,803, and Japanese Patent Publication No. 43-4936, 5
3-12,375, JP-A-52-110,618,
52-109,925.

Along with the sensitizing dye, a dye having no spectral sensitizing effect itself or a substance which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion. The sensitizing dye may be added to the emulsion at any stage in the preparation of the emulsion which has been known to be useful. Most commonly, this is done after completion of chemical sensitization but before coating, but US Pat. No. 3,628,969.
As described in JP-A-58-113,928, spectral sensitization can be carried out simultaneously with chemical sensitization by adding a chemical sensitizer at the same time as described in JP-A-58-113,928. Can be carried out prior to chemical sensitization as described in (1), or can be added before the completion of silver halide grain precipitation to start spectral sensitization. It is also possible to add these said compounds separately, as taught in U.S. Pat. No. 4,225,666, i.e. to add some of these compounds prior to chemical sensitization and the rest to chemical sensitization. It is also possible to add it after the feeling, and it is possible to add it after the sensation.
It may be at any time during the formation of silver halide grains, including the method disclosed in US Pat. No. 3,756.

The addition amount is 4 × per mol of silver halide.
It can be used in an amount of 10 ⁻⁶ to 8 × 10 ⁻³ mol, but in the case of a more preferable silver halide grain size of 0.2 to 1.2 μm, about 5 × 10 ⁻⁵ to 2 × 10 ⁻³ mol is more effective. Is. The above-mentioned various additives are used in the photosensitive material according to the present technology, but other various additives can be used according to the purpose. These additives are described in more detail in Research Disclosure Item 17643 (1
December 1978), Item 18716 (December 1979, 1)
January) and Item 308119 (December 1989)
), And the relevant locations are summarized in the table below.

Additive type RD17643 RD18716 RD308119 1 Chemical sensitizer page 23 648 page right column 996 page 2 Sensitivity enhancer same as above 3 Spectral sensitizer, page 23 to page 648 right column to 996 right to 998 right strong color Sensitizer page 649 right column 4 whitening agent page 24 998 right 5 antifoggant page 24 to 25 page 649 right column 998 right to 1000 right and stabilizer 6 light absorber, page 25 to 26 page 649 right column to 1003 Left to 1003 Right Filter dye Page 650 Left column UV absorber 7 Anti-staining agent Page 25 Right column 650 Left to right column 1002 Right 8 Dye image stabilizer Page 25 1002 Right 9 Hardener 26 Page 651 Left column 1004 Right ~ 1005 left 10 binder 26 pages same as above 1003 right to 1004 right 11 plasticizers and lubricants page 27 650 right column 1006 left to 1006 right 12 coating aid, pages 26 to 27 same as above 1005 left to 1006 left surface active agent 13 Static Page 27 Same as above 1006 Right to 1007 Left Preventive agent 14 Matting agent 1008 Left to 1009 Left

Techniques such as layer arrangement that can be used for the emulsion of the present invention and photographic light-sensitive materials using the emulsion, silver halide emulsions, dye-forming couplers, functional couplers such as DIR couplers, and various additives. , And the development processing are described in European Patent No. 0565096A1 (published on October 13, 1993) and the patents cited therein. The following is a list of each item and the corresponding places.

[0135] 1. Layer structure: page 61, lines 23-35, page 61, line 41-page 62, line 14. 2. Intermediate layer: page 61, lines 36-40, 3. Multilayer effect imparting layer: page 62, lines 15-18, 4. Silver halide composition: page 62, lines 21-25, 5. Silver halide crystal habit: page 62, line 26-30, 6. Silver halide grain size: page 62, lines 31-34, 7. Emulsion manufacturing method: page 62, line 35-40, Silver halide grain size distribution: 62-page 41-42
Line, 9. 9. Tabular grains: page 62, lines 43-46, 10. Internal structure of particle: page 62, line 47 to line 53, Emulsion latent image forming type: page 62 line 54-page 63 5
Line, 12. 12. Physical ripening and chemical ripening of emulsion: page 63, line 6-9, 13. Mixed use of emulsion: page 63, lines 10-13, Fogging emulsion: p. 63, lines 14-31, 15. Non-photosensitive emulsion: page 63, lines 32-43, 16. 16. Silver coating amount: page 63, lines 49-50, Photographic additives: Research Disclosure (R
D) Item17643 (December 1978), Item18
716 (November 1979) and Item 307105.
(November, 1989), and each item and relevant description place are shown below.

Types of Additives RD17643 RD18716 RD307105 1 Chemical sensitizer page 23 648 page right column 866 page 2 Sensitivity enhancer page 648 right column 3 Spectral sensitizer, page 23-24 page 648 right column 866-868 page strong Color sensitizer: page 649, right column, 4 whitening agent, page 24, 647 page, right column, page 868, 5 antifoggant, page 24 to 25, page 649, right column, page 868 to 870, stabilizer 6, light absorber, page 25 to 26, 649 Page right column page 873 filter dye, ~ page 650 left column UV absorber 7 anti-stain agent page 25 right column 650 left column ~ right column 872 page 8 dye image stabilizer page 25 650 page left column page 872 9 hardener 26 Page 651 page left column 874 to 875 page 10 binder 26 page 651 page left column 873 to 874 page 11 plasticizer, lubricant page 27 650 page right column 876 page 12 coating aid, page 26 to page 650 right column 875 ... Page 876 Surfactant 13 Static 27 page 650 Page right column 876-877 page Anti-prevention agent 14 Matting agent 878-879 page 18. Formaldehyde scavenger: page 64, 54-5
7 lines, 19 Mercapto-based antifoggant: page 65, lines 1-2, 20. Release agents such as fogging agents: Page 65, lines 3-7, 21. Dye: page 65, line 7-10, 22. General color couplers: p. 65, lines 11-13, 23. Yellow, magenta and cyan couplers: p. 65 1
Lines 4-25, 24. Polymer coupler: page 65, lines 26-28, 25. Diffusible dye-forming coupler: p. 65, lines 29-31, 26. Colored coupler: page 65, lines 32-38, 27. General functional couplers: p. 65, lines 39-44, 28. Bleach accelerator releasing coupler: page 65, lines 45-48, 29. Development accelerator releasing coupler: page 65, lines 49-53, 30. Other DIR couplers: Page 65, Line 54-Page 66, 4
Line, 31. Coupler dispersion method: page 66, lines 5-28, 32. Preservatives / fungicides: page 66, lines 29-33, 33. Type of photosensitive material: page 66, lines 34 to 36, 34. Photosensitive layer thickness and swelling speed: page 66, line 40-page 67, 1
Row, 35. Back layer: page 67, line 3-8, 36. General 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 to 56, 40. Processing solution opening ratio: page 67, line 57-page 68, line 12, 41. Developing time: page 68, lines 13-15, 42. Bleaching-fixing, bleaching, fixing: page 68, 16 lines-page 69, 31
Row, 43. Automatic processor: Page 69, lines 32-40, 44. Rinsing, rinsing, stabilization: page 69, line 41-page 70, line 18
Line, 45. Processing solution replenishment, reuse: page 70, lines 19-23, 46. 47. Built-in developer sensitive material: page 70, lines 24-33, Developing temperature: 70, lines 34-38, 48. Use for a film with a lens: page 70, lines 39-41, and 2-ferriccarboxylic acid or 2,6-pyridinedicarboxylic acid and ferric salts such as ferric nitrate described in EP 602600. And a bleaching solution containing persulfate can also be preferably used. In the use of this bleaching solution, it is preferable to interpose a stopping step and a water washing step between the color developing step and the bleaching step. Use an organic acid such as acetic acid, succinic acid or maleic acid as the stopping solution. Is preferred. Further, this bleaching solution may contain an organic acid such as acetic acid, succinic acid, maleic acid, glutaric acid, adipic acid in the range of 0.1 to 2 mol / liter for the purpose of adjusting pH and bleaching fog. preferable.

[0137]

Examples of the present invention will be described below. However, it is not limited to this embodiment. (Example 1) In order to bring out the effect of the present invention in a tabular grain emulsion having dislocation lines, a sparingly soluble silver halide emulsion represented by a silver iodide fine grain emulsion is used in the step of forming silver halide grains. adding, and -NH ₂ groups are described that it is essential to use a chemically modified gelatin.

(Preparation of gelatin chemically modified with --NH ₂ group) Alkali-treated ossein gelatin made from beef bone as a raw material was subjected to cation exchange treatment and anion exchange treatment to give an average molecular weight of about 100,000. Gelatin 1, which is an inactive gelatin, was prepared. Then, to the gelatin aqueous solution containing 10% by weight of the above gelatin 1,
Gelatin 1 was obtained by adding phthalic anhydride and reacting with gelatin 1 under the conditions of 40 ° C. to 50 ° C. and pH 9.0.
Gelatins ₂ to 4, which are chemically modified gelatins obtained by phthalating the —NH ₂ group in the gelatin, were prepared. Gelatins 2 to 4 were prepared by adjusting the conditions such as the amount of phthalic anhydride added, the temperature, and the treatment time so that the proportion of phthalated -NH ₂ groups (phthalation rate) was as follows. Prepared. Gelatin 2: Phthalation rate 96% Gelatin 3: 〃 33% Gelatin 4: 〃 18%

(Preparation of seed emulsion a) 1600 ml of an aqueous solution containing 4.2 g of KBr and 7.9 g of low molecular weight gelatin (average molecular weight of about 15,000) was kept at 40 ° C. and stirred. AgNO
KBr containing ₃ (8.6 g) aqueous solution and 19.0 wt% KI
An aqueous solution (7.0 g) was added by the double jet method over 40 seconds. 58g after adding 38g of gelatin 1
The temperature rose. After adding an aqueous solution of AgNO ₃ (2.5 g), 0.1 mol of ammonia was added, and 15 minutes later, the mixture was neutralized with acetic acid to adjust the pH to 5.0. An AgNO ₃ (210 g) aqueous solution and a KBr aqueous solution were added over 40 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was kept at -30 mV with respect to the saturated calomel electrode. After desalination,
Seed emulsion a was prepared by adding 50 g of gelatin 1 and adjusting the pH to 5.8 at 40 ° C. This seed emulsion contains 1.2 mol of Ag and 65 g of gelatin 1 per 1 kg of emulsion, the average equivalent circle diameter is 0.40 μm, and the variation coefficient of equivalent circle diameter is 16
%, The average thickness was 0.09 μm, and the average aspect ratio was 4.4.

(Preparation of silver iodide fine grain emulsion i-1) KI
An aqueous solution 1700 containing 0.23 g and 23 g of gelatin 1.
The ml was kept at 40 ° C. and stirred. An AgNO ₃ (153 g) aqueous solution and a KI (149.5 g) aqueous solution were added by the double jet method over 13 minutes. After desalting, gelatin 1 to 7
8 g was added and the pH was adjusted to 5.8 at 40 ° C. to prepare a silver iodide fine grain emulsion i-1. This silver iodide fine grain emulsion is 1 kg of emulsion
In this case, 0.53 mol of Ag and 50 g of gelatin 1 were contained, the average equivalent circle diameter was 0.045 μm, and the variation coefficient of equivalent circle diameter was 18%.

(Preparation of silver iodide fine grain emulsion i-2) In the method for producing silver iodide fine grain emulsion i-1, gelatin 1 added after the desalting step is replaced with gelatin 2 of equal weight to obtain silver iodide fine grains. Emulsion i-2 was prepared. This silver iodide fine grain emulsion contained 0.53 mol of Ag, 4.0 g of gelatin 1 and 46 g of gelatin 2 per 1 kg of emulsion, and showed the same grain size and shape as emulsion i-1.

(Preparation of emulsion A) 35 g of seed emulsion a, KB
An aqueous solution 1200 containing 1.2 g of r and 35 g of gelatin 1.
The ml was kept at 75 ° C and stirred. An AgNO ₃ (120 g) aqueous solution and a KBr aqueous solution containing 5.7% by weight of KI were added over 40 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential was 0 mV against the saturated calomel electrode.
Kept. Then, AgNO ₃ (22.2 g) aqueous solution and K
The Br aqueous solution was added by the double jet method over 5 minutes. At this time, the silver potential was 0 mV against the saturated calomel electrode.
Kept. Sodium ethylthiosulfonate 10mg and K
The silver potential was adjusted to -90 mV by adding Br aqueous solution.
The silver iodide fine grain emulsion i-1 (102 g) was rapidly added within 5 seconds, and 90 seconds later, an aqueous AgNO ₃ (64.5 g) solution was quantitatively added over 12 minutes. The silver potential after the addition was -23 mV. After normal washing with water and addition of 75 g of gelatin 1, pH 5.8 at 40 ° C, pAg 8.8
Was adjusted. This emulsion was designated as Emulsion A. Emulsion A has an average equivalent circle diameter of 1.33 μm, a coefficient of variation of equivalent circle diameter of 22.5%,
The tabular grains had an average thickness of 0.26 μm, an average aspect ratio of 5.1, and an average equivalent spherical diameter of 0.85 μm. Further, particles having an aspect ratio of 5 or more occupied 60% or more of the total projected area.

(Production Method of Emulsion B) In the production method of Emulsion A,
Of gelatin 1 (35 g) added before starting the step of growing silver halide grains from seed emulsion a, 8.9
Emulsion B was prepared by replacing g with gelatin 2. Emulsion B had almost the same grain size and shape as Emulsion A.

(Production Method of Emulsion C) In the production method of Emulsion A,
Of gelatin 1 (35 g) added before starting the step of growing silver halide grains from seed emulsion a, 13.
Emulsion C was prepared by replacing 6 g with gelatin 2. Emulsion C had almost the same grain size and shape as Emulsion A.

(Production Method of Emulsion D) In the production method of Emulsion A,
Emulsion D was prepared by substituting gelatin 2 for the total amount of gelatin 1 (35 g) added before starting the step of growing silver halide grains from seed emulsion a. Emulsion D
Had almost the same grain size and shape as Emulsion A.

(Production Method of Emulsion E) In the production method of Emulsion A,
Emulsion E was prepared by replacing silver iodide fine grain emulsion i-1 to be added with an equal weight of i-2. Emulsion E is emulsion A
It showed almost the same particle size and shape.

(Production Method of Emulsion F) In the production method of Emulsion A,
Of gelatin 1 (35 g) added before starting the step of growing silver halide grains from seed emulsion a, 8.9
Emulsion F was prepared by substituting g for gelatin 2 and substituting silver iodide fine grain emulsion i-1 for addition with i-2 of equal weight. Emulsion F had almost the same grain size and shape as emulsion A.

(Production Method of Emulsion G) In the production method of Emulsion A,
The total amount of gelatin 1 (35 g) added before starting the step of growing silver halide grains from seed emulsion a is replaced with gelatin 2, and silver iodide fine grain emulsion i is added.
Emulsion F was prepared by replacing -1 with an equal weight of i-2. Emulsion F had almost the same grain size and shape as emulsion A.

(Production Method of Emulsion H) In the production method of Emulsion A,
Of gelatin 1 (35 g) added before starting the step of growing silver halide grains from seed emulsion a, 13.
Emulsion H was prepared by replacing 6 g with gelatin 3. Emulsion H had almost the same grain size and shape as Emulsion A.

(Production Method of Emulsion I) In the production method of Emulsion A,
Emulsion I was prepared by substituting gelatin 3 for the total amount of gelatin 1 (35 g) added before starting the step of growing silver halide grains from seed emulsion a. Emulsion I
Had almost the same grain size and shape as Emulsion A.

(Production Method of Emulsion J) In the production method of Emulsion A,
Emulsion J was prepared by substituting gelatin 4 for the total amount of gelatin 1 (35 g) added before starting the step of growing silver halide grains from seed emulsion a. Emulsion J
Had almost the same grain size and shape as Emulsion A.

(Production Method of Emulsion K) In the production method of Emulsion A,
The total amount of gelatin 1 (35 g) added before starting the step of growing silver halide grains from seed emulsion a was replaced with gelatin 4, and silver iodide fine grain emulsion i was added.
Emulsion K was prepared by replacing -1 with an equal weight of i-2. Emulsion K had almost the same grain size and shape as Emulsion A.

(Preparation of Emulsion L) In the process for preparing Emulsion A,
Instead of adding a silver iodide fine grain emulsion, an AgNO ₃ aqueous solution (AgNO ₃ 9.3 g) and a KI aqueous solution (KI 9.0) are used.
Emulsion L was prepared in the same manner except that g) was added by the double jet method over 5 minutes. Emulsion L had almost the same grain size and shape as Emulsion A.

(Preparation of Emulsion M) In the process for preparing Emulsion A,
The total amount of gelatin 1 (35 g) added before starting the step of growing silver halide grains from seed emulsion a was replaced with gelatin 2, and instead of adding silver iodide fine grain emulsion, an AgNO ₃ aqueous solution (AgNO ₃ 9.3g) and K
Emulsion M was prepared in the same manner except that the I aqueous solution (KI 9.0 g) was added by the double jet method over 5 minutes. Emulsion M showed almost the same grain size and shape as Emulsion A.

(Preparation of Emulsion N) In the process for preparing Emulsion A,
After adding a silver iodide fine grain emulsion and quantitatively adding an AgNO ₃ aqueous solution for 12 minutes, a step of adding a gelatin aqueous solution containing 42 g of gelatin 2 is provided before the water washing step, and gelatin 1 added after the water washing is completed. An emulsion N was prepared in the same manner except that the amount of was changed to 53 g. Emulsion N has the same grain size and shape as Emulsion A.

(Preparation of Emulsion O) In the production method of Emulsion A,
16 out of 1 (75 g) gelatin added after washing
Emulsion O was prepared in the same manner except that g was replaced with gelatin 2. Emulsion O has the same grain size and shape as emulsion A.

(Preparation of Emulsion P) In the process for preparing Emulsion A,
Emulsion O was prepared in the same manner except that gelatin 2 was substituted for the total amount of gelatin 1 (75 g) added after washing with water. Emulsion P has the same grain size and shape as emulsion A.

Table 2 shows a breakdown of the dispersion media present in the emulsions during the emulsion manufacturing process for the above emulsions A to P. Since the breakdown of the dispersion medium changes depending on the time of the emulsion manufacturing process, 1) when the host tabular emulsion is completed 2) when the silver iodide fine grain emulsion is completed 3) immediately after addition of the silver iodide fine grain emulsion to the host tabular emulsion or AgNO ₃ / KI Immediately after double jet addition 4) Immediately after washing step 5) Immediately after gelatin addition after washing
The values at 5 periods are shown.

[0159]

[Table 2]

[0160]

[Table 3]

[0161]

[Table 4]

Emulsions A to D were heated to 59 ° C., and dipotassium iridium hexachloride, the following sensitizing dyes I to III, potassium thiocyanate, chloroauric acid, sodium thiosulfate and N,
Optimal chemical sensitization was performed by adding N-dimethylselenourea.

[0163]

Embedded image

Emulsions A to P chemically sensitized as described above were coated on a cellulose triacetate film support having an undercoat layer under the coating conditions shown in Table 3 below with a protective layer,
Sample Nos. 1 to 16 were prepared.

[0165]

[Table 5]

These samples were hardened for 14 hours under the conditions of 40 ° C. and 70% relative humidity. Then, it was exposed through a gelatin filter SC-50 manufactured by FUJIFILM Corporation and a continuous wedge. To evaluate the reciprocity law property,
Adjust the exposure illuminance so that the exposure amount is the same,
The exposure was performed under two conditions of 0 second and 10 seconds.

Further, in order to evaluate the pressure characteristics, the load 4
A sample was also prepared in which the emulsion-coated surface was scratched with a fine needle having a diameter of 50 μm and was exposed under the same conditions as the above 1/100 second exposure.

[0168] Negative Processor FP-350 manufactured by Fuji Photo Film Co., Ltd. was used and processed in the following manner (until the cumulative replenishment amount of the solution became 3 times the capacity of the mother liquor tank). (Processing method) Process processing time Processing temperature Replenishment amount Color development 2 minutes 45 seconds 38 ° C. 45 ml Bleach 1 minute 00 seconds 38 ° C. 20 ml Bleaching solution overflows into bleach-fixing tank 3 minutes 15 seconds 38 ° C. 30 ml Washing with water (1) 40 seconds 35 ° C Countercurrent piping system from (2) to (1) Washing with water (2) 1 minute 00 seconds 35 ° C 30 ml Stability 40 seconds 38 ° C 20 ml Drying 1 minute 15 seconds 55 ℃ * Replenishment amount is 35 mm width 1.1 m per length (equivalent to 24 Ex. 1) Next, the composition of the treatment liquid is described. (Color developer) Tank liquid (g) Replenisher (g) Diethylenetriaminepentaacetic acid 1.0 1.1 1-Hydroxyethylidene-1,1-diphosphonic acid 2.0 2.0 Sodium sulfite 4.0 4.4 Potassium carbonate 30.0 37.0 Potassium bromide 1.4 0.7 Potassium iodide 1.5 mg-hydroxylamine sulfate 2.4 2.8 4- [N-ethyl-N- (β-hydroxyethyl) amino] -2-methylaniline sulfate 4.5 5.5 Add water 1.0 liter 1.0 liter pH (to potassium hydroxide and sulfuric acid 10.05 10.10 (bleaching solution) Common for tank solution and replenisher (unit: g) Ethylenediaminetetraacetic acid ammonium ferric dihydrate 120.0 Ethylenediaminetetraacetic acid disodium salt 10.0 Ammonium bromide 100.0 Ammonium nitrate 10.0 Bleaching accelerator 0.005 mol (CH _{3) 2 N-CH 2 -CH} 2 -SS-CH 2 -CH 2 -N (CH 3) 2 · 2HCl aqueous ammonia (27%) 15.0 ml water 1.0 liter pH (adjusted with ammonia water and nitric acid) 6.3 (bleach-fixer) tank solution (g) replenisher (g) ethylenediaminetetraacetic acid ammonium ferric dihydrate 50.0-ethylenediaminetetraacetic acid disodium salt 5.0 2.0 Sodium sulfite 12.0 20.0 Ammonium thiosulfate aqueous solution (700 g / l) 240.0 ml 400.0 ml Ammonia water (27%) 6.0 ml-1.0 liter 1.0 liter by adding water pH (adjusted with ammonia water and acetic acid) 7.2 7.3 (wash solution) Common for tank liquid and replenisher A mixed bed column in which tap water is filled with H-type strongly acidic cation exchange resin (Amberlite IR-120B manufactured by Rohm and Haas) and OH type anion exchange resin (Amberlite IR-400). Water concentration to reduce calcium and magnesium ion concentration to 3 mg / liter or less And then 20 mg / l of sodium isocyanurate dichloride and 0.15 g / l of sodium sulfate were added. The pH of this solution was in the range of 6.5 to 7.5. (Stabilizer) Tank liquid and replenisher are common (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether (Average degree of polymerization 10) 0.2 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 was added and 1.0 liter pH 8.5 A sample that had been treated was measured for concentration with a green filter. The results obtained are shown in Table 4 below. Sensitivity is fog density plus 0.
It was expressed as a relative value of 2. The pressure characteristics are evaluated by the range of increase in fogging density due to scratching with fine needles, and are shown in Table 4.

[0169]

[Table 6]

As is apparent from Table 4, in the emulsion immediately after the addition of the silver iodide fine grain emulsion, --NH ₂ groups were 30%.
The above chemically modified gelatin is added to the entire dispersion medium in an amount of 30
Emulsions C, D, F, G prepared so as to contain at least wt%
H and I have less increase in fog due to scratching pressure than the comparative emulsion A, and have high photographic sensitivity. It should be further noted that the effect of increasing the sensitivity according to the present invention is 1/10.
That is, the exposure for 10 seconds is significantly larger than the exposure for 0 seconds. As a result, according to the present invention, the loss of sensitivity at the time of exposure for 10 seconds is smaller than the sensitivity at the time of exposure for 1/100 second, and the reciprocity law characteristic is improved. Further, Comparative Emulsion A of Emulsion C and Emulsion F of the present invention
On the sensitivity, since the effect of improving the reciprocity characteristics and pressure characteristics are substantially equal, the content of gelatin -NH ₂ group is chemically modified immediately after the silver iodide fine grain emulsion added end meets the requirements of the present invention It is understood that there is no particular limitation as to when the gelatin is added to the host tabular emulsion, as long as it is provided. On the other hand, the fact that the effect of the present invention is not exhibited at all when the addition time of gelatin having the --NH ₂ group chemically modified is after the completion of the emulsion grain formation step means that the performance of emulsion A and emulsions N, O, and P is improved. It is clear by comparison. Although the effects of the present invention are exhibited in Emulsions H and I, the effects of the present invention are hardly exhibited in Emulsions J and K. Therefore, gelatin having a -NH ₂ group chemically modified is effective. In order to function, the ratio of the number of chemically modified —NH ₂ groups seems to be 30% or more. Further, there is almost no difference in performance between Emulsion L and Emulsion M, and the performance of Emulsions L and M is inferior to Emulsions C, D, F, G, H and I of the present invention. In the present invention, it is understood that addition of silver iodide fine particles in the emulsion grain forming step is an essential constituent requirement.
The emulsions A to P were observed with a 200 kV transmission electron microscope at liquid nitrogen temperature, and it was found that dislocation lines were present at high density in the fringe portion of the tabular grains in all the grains.

Example 2 In the emulsion manufacturing method of the present invention, it will be explained that it is advantageous that the composition of the outermost layer of the host tabular grain emulsion in the silver halide grain forming step is substantially silver bromide. .

(Preparation of emulsion Q) 35 g of seed emulsion a, KB
An aqueous solution 1200 containing 1.2 g of r and 35 g of gelatin 1.
The ml was kept at 75 ° C and stirred. AgNO ₃ (142.2
g) The aqueous solution and the KBr aqueous solution containing 5.7% by weight of KI were added over 45 minutes while accelerating the flow rate by the double jet method. At this time, the silver potential is 0 with respect to the saturated calomel electrode.
kept at mV. Sodium ethylthiosulfonate 10 mg
And a KBr aqueous solution were added to adjust the silver potential to -90 mV. An AgNO ₃ aqueous solution (AgNO ₃ 9.3 g) and a KI aqueous solution (KI 9.0 g) were added by a double jet method over 5 minutes, and 90 seconds after the addition was completed, AgNO ₃ (64.5 g) was added.
g) The aqueous solution was metered in over 12 minutes. The silver potential after the addition was -23 mV. After normal washing with water and adding 75g of gelatin 1, pH 5.8 at 40 ℃, pA
It was adjusted to g 8.8. This emulsion was designated as Emulsion Q. Emulsion Q
Had almost the same grain size and shape as Emulsion A.

(Production Method of Emulsion R) In the production method of Emulsion Q,
The total amount of gelatin 1 (35 g) added before starting the step of growing silver halide grains from seed emulsion a was replaced with gelatin 2, and further, an AgNO ₃ aqueous solution (9.3 g) was added.
g) and the KI aqueous solution (KI 9.0 g) were added by the double jet method over 5 minutes, the silver iodide fine grain emulsion i-1 (102 g) was rapidly added within 5 seconds. Emulsion R was prepared in the same manner except that the steps were performed. Emulsion R showed almost the same grain size and shape as Emulsion A.

Emulsions Q and R were chemically sensitized in the same manner as in Example 1, and thereafter coating and hardening were carried out in the same manner as in Example 1 to prepare Sample Nos. 17 and 18 of photographic materials. Simultaneously with these samples and the sample Nos. 4 and 12 produced in Example 1, the same test as that performed in Example 1 was performed.
In the above samples, Nos. 4 and 12 are samples coated with emulsions prepared under the conditions that are comparable to the emulsion production conditions of the present invention when the composition of the outermost layer of host tabular grains is silver bromide. is there. Sample Nos. 17 and 18 are samples in which the emulsions prepared under the comparative emulsion production conditions and the emulsion production conditions of the present invention were applied when the composition of the outermost layer of the host tabular grains was silver iodobromide. . The results are shown in Table 5.

[0175]

[Table 7]

As is clear from Table 5, when the composition of the outermost layer of the host tabular grain was silver bromide, the present invention was applied as compared with the case where the composition of the outermost layer was silver iodobromide. The range of improvement in performance due to the above is large, and the ultimate performance is excellent, which is preferable. (Example 3) It will be explained that the present invention can be expected to have a remarkable effect when applied to a tabular grain emulsion having reduction sensitized dislocation lines.

(Manufacturing Method of Emulsion AK) In the manufacturing method of Emulsion A, a step of adding 2 mg of thiourea dioxide is added immediately before starting the step of growing silver halide grains from seed emulsion a, and a silver halide grain forming step is carried out. Emulsion AK was prepared according to the production method in which the amount of sodium ethylthiosulfonate added during the procedure was increased to 44 mg. Emulsion AK
Is an emulsion obtained by subjecting emulsion A to reduction sensitization during the step of forming host tabular grains. Emulsion AK had almost the same grain size and shape as Emulsion A.

(Production Method of Emulsion DK) In the production method of Emulsion D, a step of adding 2 mg of thiourea dioxide is added immediately before starting the step of growing silver halide grains from seed emulsion a, and a silver halide grain formation step is carried out. Emulsion DK was prepared according to the production method in which the amount of sodium ethylthiosulfonate added during the procedure was increased to 44 mg. Emulsion DK
Is an emulsion obtained by subjecting emulsion D to reduction sensitization during the step of forming host tabular grains. Emulsion DK had almost the same grain size and shape as Emulsion A.

(Production Method of Emulsion LK) In the production method of Emulsion L, a step of adding 2 mg of thiourea dioxide is added immediately before starting the step of growing silver halide grains from seed emulsion a, and a silver halide grain formation step is carried out. Emulsion LK was prepared by the production method in which the amount of sodium ethylthiosulfonate added in the course of step was increased to 44 mg. Emulsion U is an emulsion obtained by subjecting emulsion L to reduction sensitization in the step of forming host tabular grains. Emulsion LK had almost the same grain size and shape as Emulsion A.

(Production Method of Emulsion MK) In the production method of Emulsion M, a step of adding 2 mg of thiourea dioxide is added immediately before starting the step of growing silver halide grains from seed emulsion a, and a step of forming silver halide grains is provided. Emulsion MK was prepared according to the production method in which the amount of sodium ethylthiosulfonate added during the procedure was increased to 44 mg. Emulsion MK
Is an emulsion obtained by subjecting emulsion M to reduction sensitization in the step of forming host tabular grains. Emulsion MK had almost the same grain size and shape as Emulsion A.

Emulsions AK, DK, LK and MK were chemically sensitized in the same manner as in Example 1, and thereafter coating and hardening were carried out in the same manner as in Example 1 to prepare Sample Nos. 19 to 22 of the light-sensitive material.
Was prepared. These samples and the sample N produced in Example 1
o. Simultaneously with 1, 4, 12 and 13, tests similar to those performed in Example 1 were performed. Table 6 shows the results.

[0182]

[Table 8]

As is clear from Table 6, the present invention is effective even when reduction sensitization is performed. In particular, with respect to the range of increase in fogging due to pressure, the effect of the present invention is remarkably exhibited as compared with the case where reduction sensitization is not performed.

Example 4 In the emulsion manufacturing method of the present invention, if a radical scavenger is added during the emulsion manufacturing process,
It will be described that the effect of improving the reciprocity law characteristic and the pressure characteristic, which is the effect of the present invention, is further promoted.

(Preparation of Emulsion AS-B3) In the preparation of Emulsion A, immediately before starting the step of growing silver halide grains from seed emulsion a, the radical scavenger compound B exemplified in the text of the present specification is used. -3 to 6.5 x 10
^-By the manufacturing method that changed by providing the step of adding ⁴ mol,
Emulsion AS-B3 was prepared. Emulsion AS-B3 showed almost the same grain size and shape as Emulsion A.

(Preparation of Emulsion DS-A20) In the preparation of Emulsion D, immediately before starting the step of growing silver halide grains from seed emulsion a, the radical scavenger compound A exemplified in the text of the present specification is used. Emulsion DS-A2 was prepared according to a modified manufacturing method including the step of adding -20.
0 was prepared. Emulsion DS-A20 showed almost the same grain size and shape as Emulsion A.

(Production Method of Emulsion DS-B3) In the production method of Emulsion D, immediately before starting the step of growing silver halide grains from seed emulsion a, the radical scavenger compound B exemplified in the text of the present specification is used. Emulsion DS-B3 was prepared according to the production method modified to include the step of adding -3. Emulsion DS-B3 showed almost the same grain size and shape as Emulsion A.

(Preparation of Emulsion DS-C14) In the preparation of Emulsion D, immediately before starting the step of growing silver halide grains from seed emulsion a, the radical scavenger compound C exemplified in the text of the present specification is used. Emulsion DS-C1 was prepared according to the production method modified to include the step of adding -14.
4 was prepared. Emulsion DS-C14 had almost the same grain size and shape as Emulsion A.

(Production Method of Emulsion LS-B3) In the production method of Emulsion L, immediately before starting the step of growing silver halide grains from seed emulsion a, the radical scavenger compound B exemplified in the text of the present specification is used. -3 to 6.5 x 10
^-By the manufacturing method that changed by providing the step of adding ⁴ mol,
Emulsion LS-B3 was prepared. Emulsion LS-B3 showed almost the same grain size and shape as Emulsion A.

(Preparation of Emulsion MS-B3) In the preparation of Emulsion M, immediately before starting the step of growing silver halide grains from seed emulsion a, the radical scavenger compound B exemplified in the text of the present specification is used. -3 to 6.5 x 10
^-By the manufacturing method that changed by providing the step of adding ⁴ mol,
Emulsion MS-B3 was prepared. Emulsion MS-B3 showed almost the same grain size and shape as Emulsion A.

Emulsions AS-B3, DS-A20, DS-B
3, DS-C14, LS-B3 and MS-B3 were chemically sensitized in the same manner as in Example 1, and then coating and film hardening were performed in the same manner as in Example 1 to prepare Sample Nos. 23 to 2 of the photosensitive material.
No. 8 was produced. These samples and the sample prepared in Example 1
Simultaneously with Nos. 1, 4, 12, and 13, the same test as that performed in Example 1 was performed. Table 7 shows the results.

[0192]

[Table 9]

[0193]

[Table 10]

As is clear from Table 7, the effect of the present invention can be more remarkably exhibited by adding the radical scavenger compound specified in the present specification in the emulsion manufacturing process.

(Example 5) Emulsion EM-I of the tenth layer (high-sensitivity green-sensitive emulsion layer) of the following silver halide multilayer light-sensitive material.
Samples were prepared by substituting the same amount of the emulsions prepared in Examples 1 to 4 and the performances were compared. As a result, the same effects as those of the present invention shown in Examples 1 to 4 were confirmed. That is, in the silver halide multilayer light-sensitive material using the emulsion of the present invention in the high-sensitivity green-sensitive emulsion layer, the green-sensitive emulsion layer had high sensitivity and excellent pressure characteristics and reciprocity law characteristics. 1) Support The support used in this example was prepared by the following method. Polyethylene-2,6-naphthalate polymer 100
After drying 2 parts by weight and 2 parts by weight of Tinuvin P.326 (manufactured by Ciba-Geigy Co.) as an ultraviolet absorber, 300 ° C.
After being melted at, it was extruded from a T-die, stretched 3.3 times at 140 ° C, then stretched 3.3 times at 130 ° C, and heat-fixed at 250 ° C for 6 seconds to form a 90 μm thick PEN.
I got a film. The PEN film has a blue dye, a magenta dye, and a yellow dye (public technical report: I-1, I-4, I-6, I-24, I-26, I-26 described in the official gazette number 94-6023). 27, II-5)
Was added in an appropriate amount. Further, the support was wound around a stainless steel core having a diameter of 20 cm to give a heat history of 110 ° C. and 48 hours, thereby providing a support that was not easily curled.

2) Coating of undercoat layer The above-mentioned support was subjected to corona discharge treatment, UV discharge treatment, and glow discharge treatment on both sides thereof, and then gelatin 0.1 g / m ² and sodium α-sulfodione on each side. -2-ethylhexyl succinate 0.01 g / m ² , salicylic acid 0.04 g / m ² , p
-Chlorophenol 0.2 g / m ² , (CH ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂
CH ^₂ 0.012g / m _2, polyamide - epichlorohydrin polycondensate was coated an undercoat solution ^{0.02g / m 2 (10cc / m} 2, a bar coater used), provided with a subbing layer hotter side at the time of stretching. Dry 1
The test was carried out at 15 ° C for 6 minutes (all rollers and transport devices in the drying zone were at 115 ° C). 3) Coating of Back Layer An antistatic layer, a magnetic recording layer and a sliding layer having the following composition were coated as a back layer on one surface of the support after the undercoat.

3-1) Coating of antistatic layer A tin oxide-antimony oxide composite having an average particle size of 0.005 μm has a specific resistance of 5 Ω · cm and is a dispersion of fine particle powder (secondary agglomerated particle size of about 0.08 μm). 0.2 g / m ^2, gelatin 0.05g / m ^2, (C
H ₂ = CHSO ₂ CH ₂ CH ₂ NHCO) ₂ CH ₂ 0.02 g / m ² , poly (degree of polymerization 1
0) Oxyethylene-p-nonylphenol 0.005 g / m ²
And resorcinol. 3-2) Coating of magnetic recording layer 3-poly (degree of polymerization: 15) Cobalt-γ-iron oxide coated with oxyethylene-propyloxytrimethoxysilane (15% by weight) (specific surface area: 43 m ² / g; Long axis 0.14μm, single axis 0.03μm, saturation magnetization 89emu / g, Fe ^{+ 2} / Fe ⁺³ = 6/94, the surface is treated with silicon oxide aluminum oxide with 2% by weight of iron oxide) 0.06g / m ² diacetyl cellulose 1.2 g / m ² (dispersion of the iron oxide was carried out using an open kneader and a sand _{mill), C 2 H 5 C (} CH 2 OCONH-C 6 H 3 (CH 3) NCO) as a curing agent ₃
0.3 g / m ² was applied with a bar coater using acetone, methyl ethyl ketone, cyclohexanone as a solvent,
A magnetic recording layer having a thickness of 1.2 μm was obtained. Abrasive aluminum oxide (0.15 μm) coated with silica particles (0.3 μm) and 3-poly (degree of polymerization 15) oxyethylene-propyloxytrimethoxysilane (15% by weight) as matting agents, respectively
It was added to 10 mg / m ² . Drying was carried out at 115 ° C for 6 minutes.
° C). X- write saturation magnetization moment of the magnetic recording layer of the D color density increment of about 0.1 of ^B, also the magnetic recording layer is 4.2 emu / g, coercive force 7.3 × 10 ⁴ A / m, the squareness ratio in (blue filter) Was 65%.

3-3) Preparation of sliding layer Diacetyl cellulose (25 mg / m ² ), C ₆ H ₁₃ CH (OH) C ₁₀ H ₂₀ C
OOC ₄₀ H ₈₁ (Compound a, 6 mg / m ² ) / C ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H
(Compound b, 9 mg / m ² ) mixture was applied. This mixture was melted at 105 ° C in xylene / propylene glycol monomethyl ether (1/1), poured and dispersed in propylene glycol monomethyl ether (10 times the volume) at room temperature, and then dispersed in acetone. (Average particle size: 0.01 μm). Silica particles (0.3 μm) as a matting agent and 3-poly (polymerization degree 15) oxyethylene-propyloxytrimethoxysilane (aluminum oxide coated with 15% by weight (0.15 μm) as a polishing agent were used as 15 mg / m ² and Drying was carried out at 115 ° C for 6 minutes (all the rollers and conveying devices in the drying zone were 115 ° C). The sliding layer had a dynamic friction coefficient of 0.06 (5 mmφ stainless hard ball, load 100 g, speed).
6 cm / min), the coefficient of static friction was 0.07 (clip method), and the coefficient of kinetic friction between the emulsion surface and the sliding layer described later was 0.12, which were excellent characteristics.

4) Coating of Photosensitive Layer Next, on the opposite side of the back layer obtained above, each layer having the following composition was multilayer coated to prepare a color negative film.
This is used as a sample.

(Photosensitive layer composition) The main materials used for each layer are classified as follows: ExC: Cyan coupler UV: UV absorber ExM: Magenta coupler HBS: High boiling organic solvent ExY: Yellow coupler H: Gelatin hardening agent ExS: Sensitizing dye The numeral corresponding to each component indicates the coating amount expressed in g / m ² unit, and for silver halide, the coating amount in terms of silver. However, for the sensitizing dye, the coating amount is shown in mol units with respect to 1 mol of silver halide in the same layer.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.08 Gelatin 0.70 Second Layer (Second Antihalation Layer) Black Colloidal Silver Silver 0.09 Gelatin 1.00 ExM-1 0.12 ExF-1 2.0 × 10 ^-3 Solid Disperse dye ExF-2 0.030 Solid disperse dye ExF-3 0.040 HBS-1 0.15 HBS-2 0.02

Third layer (intermediate layer) ExC-2 0.05 Polyethyl acrylate latex 0.20 Gelatin 0.70

4th layer (low-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion EM-A silver 0.20 Silver iodobromide emulsion EM-B silver 0.23 Silver iodobromide emulsion EM-C silver 0.10 ExS-1 3.8 × 10 ^-4 ExS-2 1.6 x 10 ^-5 ExS-3 5.2 x 10 ^-4 ExC-1 0.17 ExC-2 0.02 ExC-3 0.030 ExC-4 0.10 ExC-5 0.020 ExC-6 0.010 Cpd-2 0.025 HBS-1 0.10 Gelatin 1.10

Fifth layer (medium-speed red-sensitive emulsion layer) Silver iodobromide emulsion EM-C silver 0.15 Silver iodobromide emulsion EM-D silver 0.46 ExS-1 4.0 × 10 ^-4 ExS-2 2.1 × 10 ^-5 ExS-3 5.7 × 10 ^-4 ExC-1 0.14 ExC-2 0.02 ExC-3 0.03 ExC-4 0.090 ExC-5 0.02 ExC-6 0.01 Cpd-4 0.030 Cpd-2 0.05 HBS-1 0.10 Gelatin 0.75

Layer-2 (high-sensitivity red-sensitive emulsion layer) Silver iodobromide emulsion EM-E Silver 1.30 ExS-1 2.5 × 10 ^-4 ExS-2 1.1 × 10 ^-4 ExS-3 3.6 × 10 ^-4 ExC- 1 0.12 ExC-3 0.11 ExC-6 0.020 ExC-7 0.010 Cpd-2 0.050 Cpd-4 0.020 HBS-1 0.22 HBS-2 0.050 Gelatin 1.40

Seventh layer (intermediate layer) Cpd-1 0.060 Solid disperse dye ExF-4 0.030 HBS-1 0.040 Polyethyl acrylate latex 0.15 Gelatin 1.10

Eighth Layer (Low Sensitivity Green Sensitive Emulsion Layer) Silver iodobromide emulsion EM-F Silver 0.22 Silver iodobromide emulsion EM-G Silver 0.35 ExS-7 6.2 × 10 ^-4 ExS-8 1.4 × 10 ^-4 ExS-4 2.7 × 10 ^-5 ExS-5 7.0 × 10 ^-4 ExS-6 2.7 × 10 ^-4 ExM-3 0.410 ExM-4 0.086 ExY-1 0.070 ExY-5 0.0070 HBS-1 0.30 HBS-3 0.015 Cpd- 4 0.010 Gelatin 0.95

Ninth layer (medium-speed green emulsion layer) Silver iodobromide emulsion EM-G silver 0.48 Silver iodobromide emulsion EM-H silver 0.48 ExS-4 4.8 × 10 ^-5 ExS-7 9.3 × 10 ^-4 ExS-8 2.1x10 ^-4 ExC-8 0.0020 ExM-3 0.115 ExM-4 0.035 ExY-1 0.010 ExY-4 0.010 ExY-5 0.0050 Cpd-4 0.011 HBS-1 0.13 HBS-3 4.4x10 ^-3 gelatin 0.80

Tenth layer (high-sensitivity green-sensitive emulsion layer) Silver iodobromide emulsion EM-I Silver 1.30 ExS-4 4.5 × 10 ^-5 ExS-7 5.3 × 10 ^-5 ExS-8 1.2 × 10 ^-4 ExC- 1 0.021 ExM-1 0.010 ExM-2 0.030 ExM-5 0.0070 ExM-6 0.0050 Cpd-3 0.017 Cpd-4 0.040 HBS-1 0.25 Polyethyl acrylate latex 0.15 Gelatin 1.33

Eleventh layer (yellow filter layer) Yellow colloidal silver Silver 0.015 Cpd-1 0.16 Solid disperse dye ExF-5 0.060 Solid disperse dye ExF-6 0.060 Oil-soluble dye ExF-7 0.010 HBS-1 0.60 Gelatin 0.60

Twelfth layer (low-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion EM-J silver 0.09 Silver iodobromide emulsion EM-K silver 0.10 Silver iodobromide emulsion EM-L silver 0.25 ExS-9 8.4 × 10 ^-4 ExC-1 0.03 ExC-8 7.0 × 10 ^-3 ExY-1 0.050 ExY-2 0.75 ExY-3 0.40 ExY-4 0.040 Cpd-2 0.10 Cpd-4 0.01 Cpd-3 4.0 × 10 ^-3 HBS-1 0.28 Gelatin 2.10

Thirteenth layer (high-sensitivity blue-sensitive emulsion layer) Silver iodobromide emulsion EM-M Silver 0.58 ExS-9 3.5 × 10 ^-4 ExY-2 0.070 ExY-3 0.070 ExY-4 0.0050 Cpd-2 0.10 Cpd- 3 1.0 x 10 ^-3 Cpd-4 0.02 HBS-1 0.075 Gelatin 0.55

14th layer (first protective layer) Silver iodobromide emulsion EM-N Silver 0.10 UV-1 0.13 UV-2 0.10 UV-3 0.16 UV-4 0.025 ExF-8 0.001 ExF-9 0.002 HBS-1 5.0 × 10 ^-2 HBS-4 5.0 × 10 ^-2 Gelatin 1.8

Fifteenth layer (second protective layer) H-1 0.40 BT-1 (diameter 1.7 μm) 0.06 BT-2 (diameter 1.7 μm) 0.09 BT-3 0.13 ES-1 0.20 Gelatin 0.70

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-3, BT-4 to BT- may be used.
6, F-1 to F-17, and iron salt, lead salt, gold salt, platinum salt, palladium salt, iridium salt, and rhodium salt.

[0216]

[Table 11]

In Table 8, (1) Emulsions EM-J to M were reduction-sensitized at the time of grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-91938. (2) Emulsions EM-C to E, GI to M are described in JP-A-3-237450.
Gold sensitization, sulfur sensitization and selenium sensitization were carried out in the presence of the spectral sensitizing dye and sodium thiocyanate described in each photosensitive layer. (3) For the preparation of tabular grains, low molecular weight gelatin is used according to the example of JP-A 1-158426. (4) Dislocation lines as described in JP-A-3-237450 are observed on the tabular grains by using a high voltage electron microscope. (5) Emulsions EM-A to E, G, H, and J to M are Rh and I.
It contains r and Fe in optimum amounts. The tabularity is defined as Dc / t ² , where Dc is the average equivalent circle diameter in the projected area of the tabular grains and t is the average thickness of the tabular grains.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 shown below was dispersed by the following method. That is, water 21.7
3 ml of 5% sodium p-octylphenoxyethoxyethoxyethane sulfonate and 5% aqueous solution
0.5 g of p-octylphenoxypolyoxyethylene ether (degree of polymerization: 10) of the aqueous solution was put in a 700 ml pot mill, and 5.0 g of dye ExF-2 and 500 ml of zirconium oxide beads (diameter 1 mm) were added. The material was dispersed for 2 hours. For this dispersion, a BO type vibration ball mill manufactured by Chuo Koki was used. After dispersion, the contents were taken out, added to 8 g of a 12.5% gelatin aqueous solution, and the beads were removed by filtration to obtain a gelatin dispersion of the dye. The average particle size of the dye particles is 0.44
μm.

Similarly, solid dispersions of ExF-3, ExF-4 and ExF-6 were obtained. The average particle diameters of the fine dye particles were 0.24 μm, 0.45 μm, and 0.52 μm, respectively.
ExF-5 was dispersed by the microprecipitation dispersion method described in Example 1 of European Patent Application Publication (EP) 549,489A. The average particle size was 0.06 μm.

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─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display area G03C 1/047 G03C 1/047 1/34 1/34 7/00 510 7/00 510

Claims (8)

[Claims] 1. A host tabular grain composed of silver iodobromide or silver bromide having an aspect ratio of 3 or more in a dispersion medium solution containing water and a dispersion medium and having parallel main planes of (111) planes. In the silver halide grain forming step, which comprises a step of adding an emulsion containing a slightly soluble silver halide grain which is more insoluble than the host tabular grain to an emulsion which occupies 50% or more of the area, said hardly soluble silver halide grain A silver halide photographic emulsion characterized in that 30 to 100% by weight of the dispersion medium immediately after the addition step is a modified gelatin in which the ratio of the number of chemically modified --NH ₂ groups in gelatin is 30% or more. Manufacturing method. 2. The silver halide photographic emulsion according to claim 1, wherein the host tabular grains have a structure inside the grains, and the outermost layer of the host tabular grains consists essentially of silver bromide. Manufacturing method. 3. The production of a silver halide photographic emulsion according to claim 1, wherein the hardly soluble silver halide grains are silver iodide fine grains having an equivalent spherical diameter of 0.1 μm or less. Method. 4. The method for producing a silver halide photographic emulsion according to claim 1, wherein the host tabular grains are subjected to reduction sensitization. 5. The method for producing a silver halide emulsion according to claim 1, further comprising the step of adding at least one radical scavenger.
A method for producing a silver halide photographic emulsion according to claim 2, claim 3 or claim 4. 6. The method for producing a silver halide photographic emulsion according to claim 5, wherein the radical scavenger is a compound represented by the general formula [A], [B] or [C]. Embedded image In the general formula [A], R and R'may be the same or different and each represents an alkyl group or an aryl group. In the general formula [B], R ₁ and R ₂ may be the same or different and each is a hydroxylamino group, a hydroxyl group, an amino group, an alkylamino group, an arylamino group, an alkoxy group, an aryloxy group, an alkylthio group, It represents an arylthio group, an alkyl group or an aryl group. In formula [C], R _{a1 to} R _a5 may be the same or different and each is a hydrogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an acyl group or a sulfonyl group. Represents a group, a carboxyl group, a carbamoyl group, a sulfamoyl group, a halogen atom or -X-R _a0 . X-
Represents -O-, -S- or -N (R _a6 )-. R
_a0 represents an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, an acyl group or a sulfonyl group, and R _a6 represents a hydrogen atom or a group defined by R _a0 . Of the groups R _{a1 to} R _a5 , the substituents in the ortho positions are bonded to each other, and
A 7-membered ring may be formed, which may form a spiro ring or a bicyclo ring. However, each group of R _{a1 to} R _a5 is not a hydrogen atom at the same time, and when R _a3 is a halogen atom, —O—R _a0 or —S—R _a0 , at least one of R _a1 and R _a5 is It is an alkyl group. 7. The method according to claim 1, further comprising the step of adding an emulsion containing sparingly soluble silver halide grains or silver iodide fine grains, followed by silver bromide or iodide. A method for producing a silver halide photographic emulsion in which a region made of silver bromide is grown. 8. A silver halide color photographic light-sensitive material comprising a silver halide photographic emulsion produced by the method according to any one of claims 1 to 7 in a light-sensitive silver halide emulsion layer. material.