JP2001100343A - Method for manufacturing silver halide photographic emulsion and silver halide photographic sensitive material using same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic emulsion good in sensitivity and graininess and sharpness. SOLUTION: The silver halide photographic emulsion is manufactured by incorporating flat silver halide grains produced through each process of nucelus formation and ripening and grain growth in a dispersion medium, and these flat silver halide grains have an average aspect ratio of 5-100, and at least the growth of the grains is characterized by being carried out in the presence of the dispersion medium, >=40 weight % of which is a chemically modified gelatin represented by the following general formula I or in the presence of a low molecular weight gelatin having a weight average molecular weight of 1,000-7,000, and general formula I is as follows: Gel-NH-L-COOH, in which Gel is a gelatin polypeptide; -NH- is a group derived from an amino group in the above gelatin polypeptide; and L is a divalent bonding group selected from a group consisting of (i) a 1-5C optionally substituted alkylene group or a 2-5C optionally substituted alkenylene group, and (ii) -C(=O)-R- where R is a 1-4C optionally substituted alkylene group or a 2-4C optionally substituted alkenylene group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a silver halide photographic emulsion and a silver halide photographic material containing the same.

[0002]

2. Description of the Related Art Aspect ratio of emulsion grains (diameter / thickness)
When a silver halide photographic emulsion containing tabular grains having a large size is coated on a support and used for a photographic light-sensitive material, sharpness is reduced particularly by using a tabular emulsion in the upper layer to reduce light scattering to the lower layer. It is known that a large amount of the spectral sensitizing dye can be adsorbed due to the improvement of the surface / volume ratio, and the merit such as improvement of the sensitivity granularity ratio due to the improvement of the light absorptivity can be obtained. It has been widely used in many photographic light-sensitive materials. However, when the tabular grains were produced by a conventional method, the higher the aspect ratio, the more polydispersed, and there were problems such as the inability to perform optimal chemical sensitization.

Heretofore, many technical studies have been made to improve this drawback. For example, Japanese Patent Application Laid-Open No. 52-1534
No. 28, No. 55-142329, 61-112142
Discloses a technique for monodispersing tabular grains, but the effect of monodispersion was insufficient. Also, US Pat. Nos. 5,147,771 and 5,716,659,
Nos. 47772 and 5147773 disclose a method for producing monodisperse tabular grains by allowing a polyalkylene oxide block copolymer to be present during nucleation. European Patent No. 514742A discloses a monodisperse tabular grain emulsion having a coefficient of variation of 10% or less.
Also in this patent, all the examples use the above-mentioned polyalkylene oxide block copolymer.

Although it was confirmed that monodisperse tabular grains could be obtained by using the above technique, the monodispersity of the grain size distribution was not satisfactory.

JP-A-8-82883 and JP-A-9-2
No. 51193 and JP-A-11-143002 disclose a particle forming method using a chemically modified gelatin, but the modified gelatin disclosed herein has a particularly low pH.
Since the solubility in water in the region is low and the amount used is limited, none of the results have been satisfactory.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic emulsion having good sensitivity, granularity and sharpness.

[0007]

The object of the present invention has been attained by the following means and photosensitive material. (1) In a method for producing a silver halide photographic emulsion containing tabular grains which form grains through nucleation, ripening, and grain growth steps in a dispersion medium, the tabular grains have an average aspect ratio of 5 or more. 100 or less, and at least the particle growth is
40% by weight or more of the dispersion medium, chemically modified gelatin represented by the following general formula 1, or a weight average molecular weight of 1,000 to 7000:
A method for producing a silver halide photographic emulsion, which is carried out in the presence of gelatin having a low molecular weight of 0 or less.

Formula 1 Gel-NH-L-COOH Here, Gel represents a gelatin polypeptide. -NH-
Represents a group derived from an amino group in the gelatin polypeptide. L is (i) a substituted or unsubstituted alkylene having 1 to 5 carbon atoms or a substituted or unsubstituted alkenylene group having 2 to 5 carbon atoms, (ii) -C (= O) -R- (where R Represents a divalent linking group selected from the group consisting of substituted or unsubstituted alkylene having 1 to 4 carbon atoms or a substituted or unsubstituted alkenylene group having 2 to 4 carbon atoms).

(2) The method for producing a silver halide photographic emulsion according to (1), wherein the chemical modification ratio of amino groups of the chemically modified gelatin with -L-COOH is 15% or more and 100% or less. .

(3) The chemically modified gelatin or low molecular weight gelatin is added at least twice from the start of nucleation to the end of grain growth. (1) or (2)
The method for producing a silver halide photographic emulsion described in 1 above.

(4) In a silver halide photographic light-sensitive material having at least one light-sensitive silver halide emulsion layer on a support, (1) to (3)
A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion produced by the method described in any one of the above.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. According to the present invention, in the method for producing a silver halide photographic emulsion containing tabular grains which form grains through the steps of nucleation, ripening and grain growth in a dispersion medium, at least the grain growth is at least 40% by weight of the dispersion medium. Chemically modified gelatin represented by the following general formula 1 or a weight average molecular weight of 1,000 or more:
It is performed in the presence of low molecular weight gelatin of 0000 or less.

General Formula 1 Gel-NH-L-COOH Here, Gel represents a gelatin polypeptide. -NH-
Is an amino group to be modified in the gelatin polypeptide, mainly an amino-terminal α-amino group originally present in the gelatin polypeptide, a lysine residue, a ε-amino group in a side chain of a hydroxylysine residue, If the δ-guanidino group on the side chain of the arginine residue or the guanidino group on the side chain of the arginine residue has been converted to an ornithine residue by hydrolysis, it is an imino group from the δ-amino group. .

L is (i) a substituted or unsubstituted alkylene having 1 to 5 carbon atoms or a substituted or unsubstituted alkenylene group having 2 to 5 carbon atoms, (ii) -C (= O) -R-
(Here, R represents a substituted or unsubstituted alkylene having 1 to 4 carbon atoms or a substituted or unsubstituted alkenylene group having 2 to 4 carbon atoms), and represents a divalent linking group selected from the group consisting of:

First, the chemically modified gelatin used in the present invention will be described. Chemical modification of the -NH ₂ group in said gelatin, adding a reaction reagent to gelatin, the -NH ₂
It is performed by reacting with a group to form a covalent bond. The -NH ₂ group in gelatin is chemically modified by -L-COOH, amino terminus of α- amino groups predominantly originally present in the gelatin polypeptide, lysine residues, of a side chain of hydroxylysine residues ε -Amino group, δ-guanidino group in the side chain of an arginine residue, if the guanidino group in the side chain of an arginine residue has been converted to an ornithine residue by hydrolysis, mention may be made of the δ-amino group. it can.

Specifically, for example, acid anhydrides (maleic acid,
Succinic anhydride, etc.), acid halides (R-COX, R
—SO ₂ X, RO—COX, etc.), a compound having an aldehyde group (R-CHO, etc .; but having a carboxyl group as a substituent), a compound having an epoxy group (however, having a carboxyl group as a substituent) ), Active ester compounds (such as isopropenyl acetate), active halogen compounds such as β-ketohalide,
A compound having an acryl-type active double bond group (maleimide, acrylamide, methyl methacrylate, etc .; however, having a carboxyl group in the amide portion or the alcohol portion of the ester), and the like, It can be achieved by reacting.

In this case, the —OH group or —COO of gelatin
A reagent that mainly reacts with the —NH ₂ group of gelatin is more preferable than a reagent that also reacts with the H group to form a covalent bond. Mainly, 60% or more of the number of chemically modified groups,
Preferably 80 to 100%, more preferably 95 to 10
Indicates 0%. Further, the reaction product is a group in which oxygen of an ether group or ketone group is replaced with a chalcogen atom (for example,-
(S-, thione group) is substantially not preferred. Here, “substantially not contained” refers to preferably 10% or less, more preferably 0 to 3% of the number of the chemically modified groups. Accordingly, among the above, acid anhydrides, sultones, compounds having an active double bond group, carbamoylating agents, active halogen compounds, isocyanate compounds, active ester compounds, compounds having aldehydes, and deamino groups are more preferred. It is more preferable that the chemical modification does not substantially crosslink gelatin molecules. Here, "substantially not possible" means that the content of the chemically modified group is preferably 10% or less, more preferably 0 to 3%.

For the details of the chemical modifying agent and the method of chemically modifying gelatin, see the following reference, Japanese Patent Laid-Open No. 4-2.
No. 26449, JP-A-50-3329, U.S. Pat.
No. 525753, No. 2614928, No. 261492
No. 9, No. 2763639, No. 2594293, No. 3
132945, edited by Yoshiko Abiko, glue and gelatin, No.
Chapter II, Japan Niwa Gelatin Industry Association (1987),
Ward et al., The Scienceand Technology of Gelatin,
The description in Chapter 7, Academic Press (1977) can be referred to.

The chemically modified gelatin of the present invention comprises -L-CO
The percentage of chemical modification of the amino group by OH is preferably 15% or more, more preferably 50% or more, and 7% or more.
It is more preferably 0% or more, and particularly preferably 90% or more.

The% of the chemically modified —NH ₂ group of the chemically modified gelatin can be determined as follows. Prepare unmodified gelatin and modified gelatin,
Request -NH ₂ groups of them as each e1, e2. The percentage of chemical modification can be determined from 100 × (e1 -e2) / e1. e1 and e2, in the present invention will be used a value determined by the color reaction of the -NH ₂ group by glutaraldehyde. This method is based on The Science and Te
chnology of Gelatin, Chapter 15, Academic Press (1
977) and a good correlation with the formol titration method II night results described.

The methionine content of the chemically modified gelatin of the present invention is not particularly limited, but is preferably 30 μmol / g or more, more preferably 35 μmol / g or more. The methionine content of the gelatin was determined by completely decomposing the gelatin into amino acids by an alkaline hydrolysis method and analyzing the amino acids with an amino acid analyzer.
It can be determined by determining the amount of methionine relative to the amount of glycine. For details, the description of Japanese Patent Application No. 6-102485 can be referred to.

The low-molecular-weight gelatin used in the present invention has a weight average molecular weight of 1,000 to 70,000, preferably 30 to 70,000.
00 to 40000. 70,000 weight average molecular weight
If it is more than 1,000 or less than 1,000, the effect of the present invention will be reduced. That is, as long as low-molecular-weight gelatin having a weight-average molecular weight of 1,000 to 70,000 is present at least during the grain growth process, the effects of the present invention can be exerted even without the above-mentioned chemically modified gelatin. As the weight average molecular weight of the gelatin of the present invention, a value measured by the PAGI method is used. As the kind of gelatin, alkali-treated gelatin is usually used, but oxidized gelatin can also be used.

Next, the method for producing the silver halide emulsion of the present invention will be described. For the nucleation of the silver halide photographic emulsion of the present invention, it is preferable to use a low molecular weight gelatin having a weight average molecular weight of 1,000 to 70,000 as a dispersing medium and to form a dispersing medium under conditions of pBr 1.0 to 3.0. It is more preferable to form a dispersion medium under the condition of 2.5. It is preferable that 35% by weight or more, preferably 50% by weight or more, more preferably 70% by weight or more of the dispersion medium is the low molecular weight gelatin.

The temperature at the time of nucleation is preferably 60 ° C. or less,
10 to 50C is more preferable. The dispersion medium concentration is 0.01 to
5% by weight is preferable, and 0.01 to 1% by weight is more preferable.
And more preferably 0.03 to 0.6% by weight. X⁻Salt
Degree is 10^-0.8-10^―3Mol / l is preferred
10^-1.2-10^-2.7Mol / l is better
Best 10^-1.6-10^-2.7Mole / liter
Preferred. Ag to be added⁺Liquid and / or X⁻Liquid
An embodiment containing a dispersion medium is preferable, and the concentration is 0.01 to 1 layer.
% Is preferable, and 0.03 to 0.6% by weight is more preferable.
No. The pH of the reaction solution is preferably 1 to 11, more preferably 2 to 6.
Is more preferable. AgNO added during nucleation ₃Aqueous solution and c
One or both aqueous solutions of the alkali halogenated aqueous solution
More preferably, it contains gelatin. Add during nucleation
30% or more, preferably 60 to 100%, of the amount of silver salt
More preferably, 80-100% is X⁻ Simultaneous addition with salt solution
Is preferably added.

The ripening process of the silver halide emulsion of the present invention will be described. Of the nuclei generated by nucleation, non-tabular grain nuclei are preferably 75 to 100%, more preferably 90 to 100%, even more preferably 100% by number during this ripening process.
And the projected area ratio of tabular grains is increased. Specifically, the solubility of the reaction solution is 1.1 times or more, preferably 1.
Aged 5 to 30 times for aging. As a method for increasing the solubility, the following method can be mentioned. (1) Set the temperature to 5
C. or higher, preferably 10-60.degree. (2) X
^- add salt or silver. (3) Add AgX solvent.
(4) A combination method of two or more of the above (1) to (3). The ripening proceeds more rapidly as the concentration of the dispersion medium during ripening is lower and the pH is lower. It is understood that this is because the adsorbing power of the dispersion medium to the AgX particles becomes weak, the growth alienation factor of the tabular grains is removed, and the dissolution of the non-tabular grains is promoted. Regarding the concentration of the dispersion medium during aging, the molecular weight of the dispersion medium, the pH of the reaction solution, and the type of the dispersion medium, the description of the nucleation conditions can be referred to. X ^- salt concentration is ^10-0.8
It is preferably from 10 to ^2.5 mol / liter, ^{and 10-1.2.}
-10 ^-2 mol / l is more preferred.

Next, the growth conditions for the silver halide photographic emulsion of the present invention will be described.

In the present invention, 40 to 100% by weight, preferably 60 to 100% by weight, more preferably 75 to 100% by weight, and most preferably 80 to 100% by weight of the dispersion medium in the dispersion medium solution during the growth process. The amino group is -L-COOH
Or a low molecular weight gelatin having a weight average molecular weight of 1,000 or more and 70,000 or less. The chemically modified gelatin of the present invention or the low molecular weight gelatin having a weight average molecular weight of 1,000 or more and 70,000 or less may be present in all steps during grain formation, but is contained in the dispersion medium solution at least during the grain growth process as described above. The addition is preferably performed after the nucleation, and more preferably after the aging step. Further, it is preferably added twice or more in the particle forming step according to the growth of the particles.

The growth temperature is preferably at least 30 ° C.
90 ° C. is more preferred. The most preferred temperature can be selected and used. The growth pH is 6-11, preferably 6-
10 has more advantages.

For the growth of tabular grains contained in these silver halide photographic emulsions, it is preferable to select the most preferred degree of supersaturation according to the purpose and grow. Critical supersaturation is 1
00, when supersaturation without addition of solute is 0,
5-90 is preferable and 10-80 is more preferable. Here, the critical supersaturation refers to the supersaturation in a state where a new nucleus is generated when an AgNO ₃ aqueous solution and an X ^- salt aqueous solution are simultaneously mixed and added at a higher addition rate. When the degree of supersaturation is increased, the obtained tabular grains are more monodispersed, but also grow in the thickness direction and have a lower aspect ratio. Lowering the degree of supersaturation increases the aspect ratio, but broadens the size distribution. The concentration of the dispersion medium during growth is 0.1 to 7
% By weight, more preferably 0.3 to 3% by weight.
The chemically modified gelatin has a weight average molecular weight of 3,000.
２０200,000, preferably 6,000 to 120,000. The pH of the solution is preferably equal to or higher than the isoelectric point of the chemically modified gelatin, more preferably (isoelectric point pH + 0.2) to pH11, and further preferably (isoelectric point pH + 0.4) to pH10. When tabular grains are grown under the same conditions, the lower the pH, the lower the gelatin concentration, and the lower the molecular weight, the higher the aspect ratio of the resulting tabular grains. The most preferable combination can be selected and used according to the purpose.

Regarding the other details of the silver halide grains of the present invention, the description of the literature described in the above-mentioned "Conventional Technology" and JP-A-3-288143 and JP-A-3-2126 are referred to.
No. 39, No. 3-116133, No. 2-301742
No. 2-34, No. 6-59360, Japanese Patent Application No. 6-4
No. 7991, No. 5-248218, No. 5-26405
Nos. 9 and 5-96250 can be referred to.

The gelatin of the present invention is disclosed in US Pat.
No. 771, No. 571659, No. 5147772,
Polyalkylene oxide block copolymers as described in JP-A-5147773 and European Patent No. 514742A can also be preferably used in combination.

The tabular grain in the present invention means having two substantially parallel surfaces, and the thickness of the grain is represented by the distance between the two parallel faces. The diameter of the particle is represented by the diameter of a circle having an area equal to the projected area of the particle. The aspect ratio of the particles means the ratio between the diameter and the thickness of the particles. The average aspect ratio of the tabular grains produced by the present invention is 5 or more and 100 or less.
The number is preferably from 50 to 50, more preferably from 5 to 20 and particularly preferably 8 or more.

The silver halide emulsion of the present invention has a coefficient of variation vc of 30% or less obtained by dividing the standard deviation S of the diameter of a circle equal to the projected area of all the grains contained in the emulsion by the average grain diameter r. However, it is preferably at most 20%, more preferably at most 15%. The above particle size is described, for example, in "Theory of Photographic Process" by Mies and James, Third Edition,
It can be measured by the method described in Chapter 2 of Kumamiran (1966).

The latent image forming site of the photosensitive emulsion may be mainly on the surface or the inside, or may be on both the surface and the inside. However, it is necessary that the emulsion is a negative emulsion. Of the internal latent image type, Japanese Patent Laid-Open No. 63-264740
Or the core / shell type internal latent image type emulsion described in (1). The method of preparing this core / shell type internal latent image type emulsion is described in JP-A-59-133542. The thickness of the shell of this emulsion varies depending on the development process and the like.
nm is preferable, and 5 to 20 nm is particularly preferable.

In the present invention, a silver halide solvent can be used. Examples of the silver halide solvent which can be used in the present invention include, for example, US Pat. No. 3,271,1.
No. 57, No. 3,531,289, No. 3,574
No. 628, JP-A-54-1019 and JP-A-54-1589.
(A) Organic thioethers described in JP-A No. 17-82408, 55-77737 and 55-2982, and (b) thiourea derivatives described in JP-A-53-144319. (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; ) Sulfite, (f)
And thiocyanates.

Particularly preferred solvents include thiocyanate and tetramethylthiourea. Although the amount of the solvent used varies depending on the kind, for example, in the case of thiocyanate, the preferable amount is 1 × per mole of silver halide.
10 ^-4 mol or more 1 × 10 ^- is ² mol or less.

The silver halide photographic emulsion of the present invention uses sulfur sensitization and / or gold sensitization in chemical sensitization.

The sulfur sensitization is usually carried out by adding a sulfur sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain time. Further, gold sensitization is usually performed by adding a gold sensitizer and stirring the emulsion at a high temperature, preferably at 40 ° C. or higher for a certain period of time.

For the above-mentioned sulfur sensitization, known sulfur sensitizers can be used. For example, thiosulfate, thiourea acid, allyl isothiocyanate, cystine, p-toluenethiosulfonate, and rhodanine are exemplified. Others such as U.S. Pat. Nos. 1,574,944 and 2,
Nos. 410,689, 2,278,947, 2,728,668, 3,501,313, and 3,656,955, German Patent 1,42.
No. 2,869, JP-B-56-24937, and JP-A-55-55.
Sulfur sensitizers described in -45016 can also be used. The addition amount of the sulfur sensitizer may be an amount sufficient to effectively increase the sensitivity of the emulsion. This quantity is
It varies over a considerable range under various conditions such as H, temperature, and the size of silver halide grains, but is preferably 1 × 10 ⁻⁷ mol or more and 5 × 10 ⁻⁴ mol or less per mol of silver halide. .

As the gold sensitizer for gold sensitization, the oxidation number of gold may be +1 or +3, and gold compounds usually used as gold sensitizers can be used. Representative examples include, for example, chloroaurate, potassium chloroaurate,
Auric trichloride, potassium auric thiocyanate, potassium iodoaurate, tetracyano auric acidide, ammonium aurothiocyanate,
Pyridyl trichlorogold.

Although the amount of the gold sensitizer to be added varies depending on various conditions, the standard is 1 × 10 5 per mol of silver halide.
^It is preferably from ^-7 mol to 5 × 10 ^-4 mol.

In the chemical ripening, for example, a silver halide solvent and a selenium sensitizer or a selenium sensitizer can be used in combination. There is no particular limitation on the timing and order of addition of the sulfur sensitizer and / or the gold sensitizer. For example, the compounds may be added simultaneously (preferably) at the beginning of chemical ripening (preferably) or during chemical ripening, or at the time of addition. Can be added differently. In addition, the compound may be added by dissolving the above compound in water or an organic solvent miscible with water, for example, a single solution or a mixture of methanol, ethanol, and acetone.

In the present invention, chemical sensitization can be carried out in the presence of a chemical sensitization auxiliary. As the chemical sensitization aid to be used, compounds such as azapyridazine and azapyrimidine which are known to suppress fog and increase sensitivity in the process of chemical sensitization are used. Examples of chemical sensitization aid modification are described in U.S. Pat. Nos. 2,131,038 and 3,411,
Nos. 914 and 3,554,757, JP-A-58-12
No. 6526 and the above-mentioned "Photographic Emulsion Chemistry" by Duffin, 1
38-143. In addition to chemical sensitization,
Alternatively, it can be reduction sensitized with, for example, hydrogen, as described in US Pat. Nos. 3,891,446 and 3,984,249; 698, 2,743,182 and 2,743,183.
Reduction sensitization can be achieved with tin, thiourea dioxide, polyamines and such reducing agents or by treatment at high pH (eg, greater than 8). U.S. Pat.
Color sensitization can also be improved by the chemical sensitization methods described in 917,485 and 3,966,476.

The emulsion grains of the present invention are preferably silver iodobromide or silver chloroiodobromide.

The emulsion grains of the present invention contain at least one of a silver iodide phase, a silver iodobromide phase, a silver chloroiodobromide phase and a silver chloroiodide phase. Other silver salts, for example, silver rhodan, silver sulfide, silver selenide, silver carbonate, silver phosphate, and organic acid silver may be contained as separate grains or as a part of silver halide grains.

The preferred silver iodide content of the emulsion grains of the present invention is 0.1 to 20 mol%, more preferably 0.3 to 15 mol%, and particularly preferably 1 to 10 mol%. The tabular grains of the present invention are characterized in that the relative standard deviation of the silver iodide content distribution of each grain is 20% or less, 1% or more, and more preferably 10% or less.

The silver iodide content of each emulsion grain is, for example, X
It can be measured by analyzing the composition of individual particles using a line microanalyzer. The "relative standard deviation of the silver iodide content of each grain" as used herein means, for example, the silver iodide content when at least 100 emulsion grains were measured for the silver iodide content by an X-ray microanalyzer. This is a value obtained by multiplying the value obtained by dividing the standard deviation of the ratio by the average silver iodide content by 100. A specific method for measuring the silver iodide content of individual emulsion grains is described, for example, in EP 147,868A.

The number of dislocation lines of the particles of the present invention is 1
It is preferable that particles containing 0 or more dislocation lines be present in 50% by number or more. More preferably, the number of particles containing 10 or more dislocation lines is 80% by number or more, and particularly, the number of particles containing 20 or more dislocation lines is 80% by number or more.

A dislocation line is a linear lattice defect on the slip plane of a crystal at a boundary between a region already slipped and a region not yet slipped.

Dislocations of silver halide grains are described, for example, in J. Am.
F. Hamilton, Photo. Sci. En
g. , 11, 57, (1967); Shiozaw
a, J. et al. Soc. Photo. Sci. Japan, 3
5, 213, (1972) and can be observed by a direct method using a transmission electron microscope at a low temperature. That is, the silver halide grains taken out from the emulsion so as not to apply enough pressure to generate dislocations on the grains are placed on a mesh for observation with an electron microscope, and the sample is prepared so as to prevent damage (print-out, etc.) by an electron beam. Observation is performed by a transmission method in a state of cooling. From the photograph of the particles obtained by such a method, the number and position of dislocation lines of each particle can be obtained.

The dislocation lines of the silver halide grains of the present invention can be controlled by providing a specific high iodine phase inside the grains. Specifically, adjust the substrate particles,
Then, a high iodine phase is provided, and the outside thereof is covered with a phase having a lower iodine content than the high iodide phase. Here, in order to make the silver iodide content of each grain uniform, it is important to appropriately select the conditions for forming the high iodide phase. The internal high iodine phase refers to a silver halide solid solution containing iodine. The silver halide in this case is preferably silver iodide, silver iodobromide, or silver chloroiodobromide, but is preferably silver iodide or silver iodobromide (iodine content: 10 to 40 mol%). More preferably, silver iodide is particularly preferred.

It is important that the internal high iodine phase is not uniformly deposited on the plane of the substrate grains, but rather exists locally. Such localization may occur anywhere on the plane, side, or corner of the substrate particle. Further, the internal high iodine phase may be selectively epitaxially coordinated at such a site.

As a method for this, a so-called conversion method in which an iodide salt is added alone, for example, a method described in
The epitaxial junction method described in JP-A-9-133540, JP-A-58-108526, and JP-A-59-162540 can be used. At that time, it is effective to select the following conditions in order to make the silver iodide content of each grain uniform. That is, the pAg at the time of adding an iodide salt is more preferably in the range of 8.5 to 10.5.
The range of 9.0 to 10.5 is particularly preferred. The temperature is 5
It is preferable to keep the temperature in the range of 0 ° C to 30 ° C. The addition of the iodide salt is 1% based on the total silver under sufficiently stirred conditions.
Preferably, the mole% iodide salt is added over a period of 30 seconds to 5 minutes. The silver iodide content of the substrate grains is lower than that of the high iodide phase, preferably 0 to 12 mol%, more preferably 0 to 10 mol%. The outer phase covering the high iodine phase is lower than the iodine content of the high iodide phase, preferably 0 to 12 mol%, more preferably 0 to 10 mol%, and most preferably 0 to 3 mol%. Mol%.

The internal high iodine phase preferably exists in the range of 5 mol% to 80 mol%, and more preferably in the range of 20 mol% to 70 mol%, of the total silver amount from the center of the silver halide grains. More preferably present, 30 mol%
It is particularly preferred that it is present in the range of from 70 to 70 mol%.
The iodine content of the internal high iodine phase is higher than the average iodide content of silver iodide, silver iodobromide or silver chloroiodobromide present on the grain surface, preferably 5 times or more, particularly preferably. 20
More than double. Further, the amount of silver halide forming the internal high iodide phase is not more than 50 mol%, more preferably not more than 10 mol%, particularly preferably not more than 5 mol% of the silver amount of the whole grains in terms of silver amount. .

Further, an iodide ion releasing agent can be preferably used. The iodide ion releasing agent is described in, for example, JP-A-6-138595.

The emulsion grains of the present invention preferably have a structure based on a halogen composition. 1 for base particles
Particles having a coating shell having more than two layers, for example, particles having a double structure, a triple structure, a quadruple structure, a quintuple structure,...

Particles obtained by depositing one or more layers that do not completely cover the base particles, for example, particles having a two-layer structure, a three-layer structure, a four-layer structure, a five-layer structure,... Can be

The properties of silver halide grains can be controlled by allowing various compounds to be present during the process of silver halide precipitation. Such compounds may be initially present in the reactor or may be added simultaneously with the addition of one or more salts according to conventional methods. U.S. Pat. Nos. 2,448,060 and 2,628,
167, 3,737,313, 3,772,0
No. 31, Research Disclosure, 134
Vol., June 1975, 13452, copper, iridium, lead, bismuth, cadmium, zinc,
(Chalcogen compounds such as sulfur, selenium and tellurium),
The properties of silver halide can be controlled by the presence of compounds such as gold and Group VII noble metal compounds during the silver halide precipitation process. 58-1
No. 410, Moisar et al., Journal of Photographic Science, 25, 1
As described on pages 977, pp. 19-27, silver halide emulsions can reduce and sensitize the inside of grains during precipitation.

The silver halide photographic light-sensitive material according to the present invention has at least one photosensitive silver halide emulsion layer on a support, and the silver halide emulsion layer is prepared by the above-mentioned method. Contains photographic emulsion.

The silver halide photographic emulsion prepared according to the present invention may be used together with an emulsion comprising ordinary chemically sensitized silver halide grains (hereinafter referred to as non-tabular grains) in the same silver halide emulsion layer. Can be. Particularly in the case of color photographic light-sensitive materials, tabular grain emulsions and non-tabular grain emulsions can be used in different emulsion layers and / or in the same emulsion layer. Here, examples of the non-tabular grains include regular grains having regular crystals such as cubic, octahedral, and tetradecahedrons, and grains having irregular crystal forms such as spheres and potatoes. be able to. As the silver halide of these non-tabular grains, any of silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride may be used. Preferred silver halide is silver iodobromide or silver iodochlorobromide containing 30 mol% or less of silver iodide. Particularly preferred is silver iodobromide containing from 2 mol% to 25 mol% of silver iodide.

The additives used in the chemical ripening and spectral sensitization of the emulsion used in the present invention are described in Research Disclosure No. 17643 (December, 1978) and No. 17643.
18716 (November 1979).

Here, the spectral sensitizing dye, antifoggant and stabilizer can be used in any step of the photographic emulsion production process, or can be present at any stage after the production and immediately before coating. Examples of the former include, for example, a silver halide grain forming step, a physical ripening step, and a chemical ripening step. That is, spectral sensitizing dyes, antifoggants and stabilizers can be used to limit the formation position of chemical sensitization nuclei or use different halogens by utilizing other properties such as strong adsorption to emulsions in addition to their original functions. It is also used for the purpose of stopping excessive halogen exchange when obtaining bonded structure particles having a composition and maintaining a bonded structure of different types of halogens. These are disclosed in JP-A-55-26589 and JP-A-58-58589.
111935, JP-A-58-28738, JP-A-58-28738
Nos. 2-7040 and U.S. Pat. Nos. 3,628,960 and 4,225,666 can be referred to.

When a part or all of the spectral sensitizing dye, antifoggant and stabilizer to be added is added before adding the chemical sensitizer, and then the chemical sensitizer is added to perform chemical ripening. Since the position where the chemical sensitizing nucleus is formed on the silver halide grains is limited to the place where the sensitizing dye, antifoggant and stabilizer are not adsorbed, the latent image dispersion is prevented,
It is particularly preferable because photographic characteristics are improved. In particular, when sensitizing dyes, antifoggants and stabilizers which are selectively adsorbed on the (111) plane of silver halide grains are added, the chemical sensitizing nucleus is limited to the edge portion only when hexagonal tabular grains are used. It is particularly preferable because it is formed by forming.

It is also effective to carry out the chemical sensitization in the presence of a silver halide solvent. The types of silver halide solvents used are thiocyanate and JP-A-63-15161.
The solvent described in No. 8 can be used. The concentration of the solvent used is preferably 10 ^-5 to 10 ^-1 mol / l. Removal of the soluble silver salt from the emulsion before and after physical ripening involves washing with Nudel, flocculation sedimentation or ultrafiltration.

The emulsions prepared according to the invention have the same layer,
A known emulsion other than the emulsion prepared according to the present invention may be introduced into the adjacent layer or other layers.
When an emulsion other than the emulsion produced according to the present invention is mixed in the same layer, the mixing ratio can be appropriately changed depending on the surface silver iodide content, the purpose of use, and the like. When the emulsion prepared according to the present invention and two known emulsions other than the emulsion are mixed, it is preferable to use them in a weight ratio of 3:97 to 97: 3.

In the emulsion produced according to the present invention, for example, two or more kinds of emulsions having different halogen compositions, halogen particle distributions, sizes, size distributions, crystal forms, crystal habits, and latent image distributions may be used in the same layer. It can be used in combination with an adjacent layer or other layers. Monodisperse emulsions can be mixed, polydisperse emulsions can be mixed, and monodisperse and polydisperse can be mixed. Preferably, the silver halide emulsion of the invention contains at least 50% or more of the total projected area.

The silver halide photographic emulsion of the present invention is preferably used after spectral sensitization.

As the spectral sensitizing dye used in the present invention, a methine dye is usually used. Examples thereof include a cyanine dye, a merocyanine dye, a complex cyanine dye, a complex merocyanine dye, a holopolar cyanine dye, a hemicyanine dye, a styryl dye and Hemioxonol dyes are included. Any of nuclei usually used for cyanine dyes as base heterocyclic nuclei can be applied to these dyes. That is, for example, pyrroline, oxazoline, thiazoline, pyrrole, oxazole, thiazole, selenazole, imidazole, tetrazole, pyridine; a nucleus in which an alicyclic hydrocarbon ring is fused to these nuclei; and an aromatic hydrocarbon ring is fused to these nuclei. For example, indolenine, benzindolenin, indole, benzoxadol, naphthoxadol, benzothiazole, naphthothiazole, benzoselenazole, benzimidazole, and quinolene can be applied. These nuclei may be substituted on carbon atoms.

In the merocyanine dye or the complex merocyanine dye, nuclei having a ketomethylene structure such as pyrazolin-5-one, thiohydantoin, 2-thiooxazolidine-2,4-dione, and thiozolidine-2,4-
5-6 membered heterocyclic nuclei of dione, rhodanine, thiobarbituric acid can be applied. Among the above dyes, sensitizing dyes particularly useful in the present invention are cyanine dyes.

As the spectral sensitizing dye, those described in the following in addition to the above are used. For example, German Patent 929,080, US Patent 2,493,748
No. 2,503,776 and 2,519,001
Nos. 2,912,329 and 3,656,959
Nos. 3,672,897, 3,694,217
Nos. 4,025,349 and 4,046,572
No. 2,688,545 and 2,977,229
No. 3,397,060 and 3,522,052
No. 3,527,641, No.3,617,293
No. 3,628,964 and 3,666,480
Nos. 3,672,898 and 3,679,428
Nos. 3,703,377 and 3,814,609
No. 3,837,862, No. 4,026,707
No. 1,242,588, 1,344,2
No. 81, No. 1, 507, 803, Tokiko 44-14,
No. 030, No. 52-24, 844, No. 43-4936
Nos. 53-12,375 and JP-A-52-110,6.
No. 18, No. 52-109, 925, No. 50-80, 8
The dye described in No. 27 can be used.

The silver halide emulsion of the present invention may be a system which is spectrally sensitized with an antenna dye. The spectral sensitization by an antenna dye is described in JP-A-62-29595.
No. 32, No. 63-138341, No. 63-13834
The description in No. 2 can be referred to.

The amount of the sensitizing dye added during the preparation of the silver halide emulsion cannot be unambiguously described depending on the type of the additive, the amount of the silver halide, or the like. Almost the same amount can be used.

That is, the amount of the sensitizing dye to be added is preferably 0.001 to 100 mmol, more preferably 0.01 to 10 mmol, per 1 mol of silver halide.

The sensitizing dye is added after or before chemical ripening. The sensitizing dye is most preferably added to the silver halide grains of the present invention during or before chemical ripening (for example, during grain formation or physical ripening).

In addition to the sensitizing dye, the emulsion may contain a dye which does not itself have a spectral sensitizing effect or a substance which does not substantially absorb visible light and exhibits supersensitization. For example, aminostil compounds substituted with a nitrogen-containing heterocyclic group (for example, those described in US Pat. Nos. 2,933,390 and 3,635,721), and aromatic organic acid formaldehyde condensate (for example, US Pat. 3,743,
510), cadmium salts and azaindene compounds. US Patent 3,615,613
Nos. 3,615,641 and 3,617,295
No. 3,635,721 are particularly useful.

The photographic emulsion produced according to the present invention may contain various compounds for the purpose of preventing fog during the production process of the photographic material, during storage or during photographic processing, or for stabilizing photographic performance. it can. That is, for example, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (especially nitro or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiazoles, mercaptotetrazoles (especially 1-phenyl-5
-Mercaptotetrazole), mercaptopyrimidines; for example, the above-mentioned heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds such as oxazolinethione; azaindenes such as tetraazaindenes (particularly 4-hydroxy-substituted (1 , 3,3a, 7) Tetraazaindenes); benzenethiosulfonic acids; benzenesulfinic acid; and many other compounds known as antifoggants or stabilizers.

The addition time of these antifoggants or stabilizers is usually carried out after chemical sensitization, but can be more preferably selected during chemical ripening or before chemical ripening. That is, in the course of silver halide emulsion grain formation, even during the addition of the silver salt solution or during the period from the addition to the start of chemical ripening, during chemical ripening (during the chemical ripening time, preferably within 50% from the start) More preferably, the time may be up to 20%).

Specific examples include a hydroxyazaindene compound, a benzotriazole compound, and a heterocyclic compound substituted with at least one mercapto group and having at least two aza nitrogen atoms in the molecule.

The addition amount of the above antifoggant or stabilizer used in the present invention cannot be univocally determined by the addition method or the amount of silver halide, but is preferably from 10 ^-7 mol to 1 mol of silver halide. It is 10 ^-2 mol, more preferably 10 ^-5 to 10 ^-2 mol.

The above-mentioned various additives are used in the light-sensitive material according to the present invention. In addition, various additives can be used according to the purpose.

These additives are described in more detail in Research Disclosure Item 17, or in EP 436,938 A2 at the following places and in the patents cited below.

The various techniques and inorganic and organic materials which can be used for the silver halide photographic emulsion of the present invention and silver halide photographic light-sensitive materials using the same are generally described in Research Disclosure No. 308119 (19).
89) can be used.

The emulsion of the present invention can be used for various light-sensitive materials, but is preferably used for color light-sensitive materials. More specific techniques and inorganic / organic materials when the emulsion of the present invention is used for a color photographic light-sensitive material are described in the following portions of European Patent 436,938A2 and the patents cited below.

Item The present section 1) Layer structure Page 146, line 34 to page 147, line 25 2) Can be used in combination Page 147, line 26 to page 148, line 12 Silver halide emulsion 3) Yellow coupler, page 137, line 35 to page 146, line 33, page 149, lines 21 to 23 4) Magenta coupler, page 149, lines 24 to 28; EP 421,453A1 No. 3, page 25 to line 55 5) Cyan Coupler, page 149, lines 29 to 33; EP 432,804A2, page 3, line 28 to page 40, line 2 Item 6) Polymer coupler, page 149, lines 34 to 38; EP 113,334A2, page 113, line 39 to page 123, line 37 7) Colored coupler page 53, lines 42 to 137 Page 34, line 149, line 39 Line 45 to 8) Other functionality, page 7, line 1 to page 53, line 41, page 149, 46 coupler line to page 150, line 3; EP 435,334A2, line 3 Page 1 line to page 29 line 50 9) Preservative and fungicide page 150 line 25 to line 28 10) Formalin page 149 lines 15 to 17 Scavenger 11) Other additives No. 153 Page 38, line 47 to page 47; page 75, line 21 to page 84, line 56, page 27, line 40 to page 37, line 40 of EP 421,453A1 12) Dispersion method 150 Lines 4 to 24 on page 13) Support, page 150, lines 32 to 34 14) Film thickness and film properties Page 150, lines 35 to 49 15) Color development, black and white, page 150, line 50 Line 47 to page 151, line 47; European Patent Developing / Fogging Step No. 442, 323A2, page 34, 11 Lines 54 to 54, page 35, lines 14 to 22 16) Desilvering process Page 151, line 48 to page 152, line 53 17) Automatic developing machine Page 152, line 54 to page 153 2nd line 18) Washing / stabilizing step, page 153, lines 3 to 37 The silver halide color photographic light-sensitive material of the present invention is described in
It is also effective for a film unit with a lens described in JP-A-32615, JP-B-3-39784 and the like.

The silver halide photographic light-sensitive material of the present invention includes:
A transparent magnetic recording layer can be used. Used in the present invention
The transparent magnetic recording layer is a
Apply the dispersed aqueous or organic solvent-based coating solution on the support
It was established. The magnetic particles used in the present invention
ΓFe₂O₃Such as ferromagnetic iron oxide, Co-coated γFe
₂O ₃, Co-coated magnetite, Co-containing magnetite, strong
Magnetic chromium dioxide, ferromagnetic metal, ferromagnetic alloy, hexagonal
Ba ferrite, Sr ferrite, Pb ferrite, Ca ferrite
Lights can be used. Magnetic particles used in the present invention
In particular, Co-coated γFe₂O₃Co-coated ferromagnetic
Iron oxide is preferred. The shape of the magnetic particles is a needle.
Shape, rice grain, sphere, cube, plate, etc.
S for specific surface area_{BE T} At 20m²/ g or more is preferable, and 30 m²/ g
The above is particularly preferred. The saturation magnetization (σs) of a ferromagnetic material is
Preferably 3.0 × 10⁴~ 3.0 × 10⁵A / m, especially good
Preferably 4.0 × 10⁴ ~ 2.5 × 10⁵A / m. Ferromagnetic material
Particles made of silica and / or alumina or organic materials
Surface treatment. Furthermore, magnetic particles are disclosed in
Silane cup on the surface as described in Hei 6-61032
It may be treated with a ring agent or a titanium coupling agent.
No. In addition, JP-A-4-259911, the surface described in 5-81652
Magnetic particles coated with an inorganic or organic substance can also be used.

Next, the binder used for the magnetic particles is as follows:
JP-A-4-219569 thermoplastic resin, thermosetting resin, radiation-curable resin, reactive resin, acid, alkali or biodegradable polymer, natural polymer (cellulose derivative,
Sugar derivatives) and mixtures thereof. The resin has a Tg of -40 ° C to 300 ° C and a weight average molecular weight of 2,000 to 1,000,000. For example, vinyl copolymer,
Cellulose diacetate, cellulose triacetate,
Examples include cellulose derivatives such as cellulose acetate propionate, cellulose acetate butyrate, and cellulose tripropionate, acrylic resins, and polyvinyl acetal resins, and gelatin is also preferable. Particularly, cellulose di (tri) acetate is preferable. The binder can be cured by adding an epoxy-based, aziridine-based, or isocyanate-based crosslinking agent. Examples of the isocyanate-based crosslinking agent include isocyanates such as tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, and xylylene diisocyanate, and reaction products of these isocyanates with polyalcohol (for example, tolylene diisocyanate). 3 mol of isocyanate and 1 m of trimethylolpropane
ol reaction product), and polyisocyanates formed by condensation of these isocyanates.
For example, it is described in JP-A-6-59357.

As a method for dispersing the above-mentioned magnetic material in the binder, a kneader, a pin type mill, an annular type mill and the like are preferably used, as in the method described in JP-A-6-35092. Dispersants described in JP-A-5-088283 and other known dispersants can be used. The thickness of the magnetic recording layer is 0.1 μm to 10 μm, preferably 0.2 μm to 5 μm.
μm, more preferably 0.3 μm to 3 μm. The weight ratio between the magnetic particles and the binder is preferably 0.5: 100 to 60: 1.
00, more preferably from 1: 100 to 30: 100. The coating amount of the magnetic particles 0.005~ 3g / m ^2, preferably 0.01 to
It is 2 g / m ² , more preferably 0.02 to 0.5 g / m ² . The magnetic recording layer used in the light-sensitive material of the present invention can be provided on the entire back surface or in the form of stripes by coating or printing on the back surface of a photographic support. Methods for applying the magnetic recording layer include air doctor, blade, air knife, squeeze, impregnation, reverse roll, transfer roll, gravure, kiss, cast, spray, dip, bar,
Extrusion and the like can be used, and a coating solution described in JP-A-5-341436 is preferable.

The magnetic recording layer is provided with lubricity improvement, curl control,
It may have functions such as antistatic, anti-adhesion, and head polishing, or may provide another functional layer to provide these functions. At least one of the particles has a Mohs hardness of 5 or more. It is preferable that the abrasive is a non-spherical inorganic particle abrasive. As the composition of the non-spherical inorganic particles, oxides such as aluminum oxide, chromium oxide, silicon dioxide, titanium dioxide and silicon carbide, carbides such as silicon carbide and titanium carbide, and fine powders such as diamond are preferable. These abrasives may have their surfaces treated with a silane coupling agent or a titanium coupling agent. These particles may be added to the magnetic recording layer, or may be overcoated (for example, a protective layer, a lubricant layer, etc.) on the magnetic recording layer. As the binder used at this time, the above-mentioned binders can be used, and preferably the same binder as that of the magnetic recording layer is used.
For a light-sensitive material having a magnetic recording layer, see US Pat. No. 5,336,589,
5,250,404, 5,229,259, 5,215,874, EP
No. 466,130.

Next, the polyester support used in the light-sensitive material of the present invention will be described. For details including the light-sensitive material, processing, cartridges and examples described later, see Japanese Patent Publication No. Association; 1994.3.15.). The polyester used for the support is formed with diol and aromatic dicarboxylic acid as essential components, and 2,6-, 1,5-, 1,4-, aromatic dicarboxylic acid.
And 2,7-naphthalenedicarboxylic acid, terephthalic acid,
Examples of isophthalic acid, phthalic acid, and diol include diethylene glycol, triethylene glycol, cyclohexane dimethanol, bisphenol A, and bisphenol. Examples of the polymer include homopolymers such as polyethylene terephthalate, polyethylene naphthalate, and polycyclohexanedimethanol terephthalate. Particularly preferred are polyesters containing 50 to 100 mol% of 2,6-naphthalenedicarboxylic acid. Among them, particularly preferred is polyethylene-
2,6-naphthalate. The weight average molecular weight ranges from about 5,000 to 200,000. The Tg of the polyester of the present invention is 50 ° C. or higher, preferably 90 ° C. or higher.

Next, the polyester support is subjected to a heat treatment at a heat treatment temperature of 40 ° C. or more and less than Tg, more preferably Tg−20 ° C. or more and less than Tg in order to make it difficult to form a curl. The heat treatment may be performed at a constant temperature within this temperature range, or may be performed while cooling. The heat treatment time is 0.1 to 1500 hours, more preferably 0.5 to 200 hours. The heat treatment of the support may be performed in the form of a roll, or may be performed while being transported in the form of a web.
Irregularities may be imparted to the surface (for example, conductive inorganic fine particles such as SnO ₂ or Sb ₂ O ₅ may be applied) to improve the surface state.
It is also desirable to take measures such as applying knurls to the ends and making the ends slightly higher so as to prevent the cut end of the core from appearing. These heat treatments may be performed at any stage after the formation of the support, after the surface treatment, after the application of the back layer (antistatic agent, slip agent, etc.), and after the application of the undercoat. Preferably after application of the antistatic agent. An ultraviolet absorber may be incorporated into this polyester. To prevent light piping, the purpose can be achieved by kneading a commercially available dye or pigment for polyester, such as Diaresin manufactured by Mitsubishi Kasei or Kayaset manufactured by Nippon Kayaku.

Next, in the present invention, it is preferable to perform a surface treatment in order to bond the support and the light-sensitive material constituting layer. Surface activation treatments such as chemical treatment, mechanical treatment, corona discharge treatment, flame treatment, ultraviolet irradiation treatment, high frequency treatment, glow discharge treatment, active plasma treatment, laser treatment, mixed acid treatment, ozone oxidation treatment, and the like. Among the surface treatments, preferred are ultraviolet irradiation treatment, flame treatment, corona discharge treatment,
This is a glow discharge process.

Next, the undercoating method will be described. The light-sensitive material of the present invention may have an undercoat layer on at least one of the emulsion layer side and the back side with the support interposed therebetween. The undercoat layer may be a single layer or two or more layers. As the binder for the undercoat layer, vinyl chloride, vinylidene chloride, butadiene, methacrylic acid, acrylic acid, itaconic acid, including copolymers starting from monomers selected from maleic anhydride, as a starting material, Examples include polyethyleneimine, epoxy resin, grafted gelatin, nitrocellulose, and gelatin.
Compounds that swell the support include resorcinol and p-chlorophenol. In the undercoat layer, chromium salts (such as chrome alum), aldehydes (such as formaldehyde and glutaraldehyde), isocyanates, and active halogen compounds (such as 2,4-dichloro-6) are used as gelatin hardeners.
-Hydroxy-S-triazine), epichlorohydrin resin, active vinyl sulfone compound and the like. SiO ₂ , TiO ₂ , inorganic fine particles or polymethyl methacrylate copolymer fine particles (0.01 to 10 μm)
May be contained as a matting agent.

In the present invention, antistatic agents are preferred.
It is used well. Carbohydrate is one of those antistatic agents.
Polymers containing acid, carboxylate and sulfonate,
Thionic polymers, ionic surfactant compounds
Can be. The most preferred antistatic agent is Z
nO, TiO₂, SnO₂, Al₂O₃ , In
₂O ₃, SiO₂, MgO, BaO, MoO₃, V₂O
₅At least one kind of volume resistivity selected from among 10⁷ 
Ωcm or less, more preferably 10⁵Particles less than Ωcm
0.001 to 1.0 μm crystalline metal oxide or metal oxide
These composite oxides (Sb, P, B, In, S, Si, C
Etc.) fine particles, or sol-like metal oxides or
These are fine particles of the composite oxide. As content in photosensitive material
Is 5-500mg / m^TwoIs preferable, particularly preferably 10 to 350 m
g / m^TwoIt is. Conductive crystalline oxide or its composite oxide
The weight ratio of the binder and the binder is preferably from 1/300 to 100/1.
More preferably, it is 1/100 to 100/5.

The light-sensitive material of the present invention preferably contains a slipping agent. It is preferable to use the slip agent-containing layer on both the emulsion layer side and the back side. A preferable slip property is a dynamic friction coefficient of 0.25 or less and 0.01 or more. The measurement at this time represents the value when transported at 60 cm / min against a stainless steel ball with a diameter of 5 mm.
(25 ° C., relative humidity (hereinafter referred to as RH) 60%). In this evaluation, even when the surface of the emulsion layer is replaced as the partner material, the values are almost the same level. Examples of the slip agent usable in the present invention include polyorganosiloxanes, higher fatty acid amides, higher fatty acid metal salts, esters of higher fatty acids and higher alcohols, and polyorganosiloxanes such as polydimethyl siloxane, polydiethyl siloxane, poly Styrylmethylsiloxane, polymethylphenylsiloxane, or the like can be used. Particularly, polydimethylsiloxane or an ester having a long-chain alkyl group is preferable. The additional layer is preferably the outermost layer of the emulsion layer or the back layer.

The light-sensitive material of the present invention preferably contains a matting agent. The matting agent may be added on either the emulsion layer side or the back side, but is particularly preferably added to the outermost layer on the emulsion layer side. The matting agent may be soluble in the processing solution or insoluble in the processing solution, and preferably both are used in combination. For example, polymethyl methacrylate, poly (methyl methacrylate / methacrylic acid = 9/1 or 5/5 (molar ratio)), polystyrene particles and the like are preferable. 0.8 ~ 10μm as particle size
It is preferable that the particle size distribution is narrower, and it is preferable that 90% or more of the total number of particles is contained between 0.9 and 1.1 times the average particle size. It is also preferable to simultaneously add fine particles having an average particle size of 0.8 μm or less in order to enhance the matting property. For example, polymethyl methacrylate (0.2 μm), poly (methyl methacrylate / methacrylic acid = 9/1 (molar ratio), 0.3 μm )), Polystyrene particles (0.25 μm) and colloidal silica (0.03 μm).

Next, the film cartridge which can be used for the light-sensitive material of the present invention will be described. The main material of the patrone that can be used in the light-sensitive material of the present invention may be metal or synthetic plastic. Preferred plastic materials are polystyrene, polyethylene, polypropylene, polyphenyl ether and the like. Further, the patrone that can be used in the present invention may contain various antistatic agents, and carbon black, metal oxide particles, nonionic, anionic, cationic and betaine-based surfactants or polymers can be preferably used. These antistatic patrones are disclosed in
Nos. 2537 and 1-312538. Especially 25 ℃, 25
The resistance at% RH is preferably 10 ¹² Ω or less. Usually, a plastic patrone is manufactured using a plastic into which carbon black, a pigment, or the like is kneaded to impart light-shielding properties. The size of the patrone can be the same as the current 135 size.
It is also effective to make the diameter of a 25 mm cartridge 22 mm or less. The volume of the patrone case is 30 cm ³ or less, preferably 25 cm ³ or less. The weight of the plastic used for the patrone and the patrone case is preferably 5 g to 15 g.

The patrone that can be used in the present invention further includes:
A patrone that rotates the spool and feeds the film may be used. Further, a structure may be employed in which the leading end of the film is housed in the cartridge body, and the leading end of the film is sent out from the port of the cartridge by rotating the spool shaft in the film sending direction. These are US 4,834,306,
No. 5,226,613. The photographic film used in the present invention may be a so-called raw film before development or a photographic film that has been subjected to development processing. Also, the raw film and the developed photographic film may be stored in the same new patrone or different patrones.

[0098]

Examples of the present invention will be described below. However, the present invention is not limited to this embodiment.

Example 1 Em-O was prepared from a silver halide photographic emulsion Em-A by the following production method.

(Preparation of Em-A) 1200 ml of an aqueous solution containing 0.90 g of low molecular weight gelatin having a molecular weight of 15,000 and 1.0 g of KBr was kept at 35 ° C. and stirred vigorously.
30 ml of an aqueous solution containing 1.9 g of AgNO ₃ , KBr
1.5 g and low molecular weight gelatin having a molecular weight of 15,000 0.7
30 ml of an aqueous solution containing g was added for 30 seconds by a double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. 6 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After ripening, gelatin 45 of molecular weight 100,000
g was added to adjust the pH to 5.0.

150 m of aqueous solution containing 30 g of AgNO ₃
and an aqueous KBr solution were added over 16 minutes by the double jet method. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode. Further, AgNO ₃ , 110 g
And KBr aqueous solution are accelerated by double jet method so that the final flow rate is 1.2 times the initial flow rate,
Added over 5 minutes. At this time, the size is 0.03μm
AgI fine grain emulsion was simultaneously added at an accelerated flow rate such that the silver iodide content was 3.8%, and the silver potential was -25.
mV. Aqueous solution 132 containing 35 g of AgNO ₃
ml and an aqueous KBr solution were added by a double jet method over 7 minutes. The addition of the aqueous KBr solution was adjusted so that the potential at the end of the addition became -20 mV. After the temperature was adjusted to 40 ° C., 5.6 g of Compound 1 was added in terms of KI, and the mixture was further added with 0.1 g.
64 cc of an 8M aqueous sodium sulfite solution was added. Further, an aqueous solution of NaOH was added to raise the pH to 9.0 and maintained for 4 minutes to rapidly generate iodide ions.
Was returned to 5.5. After the temperature was returned to 55 ° C., 1 mg of sodium benzenethiosulfonate was added, and 14 g of gelatin having a molecular weight of 100,000 was further added. After the addition is completed, A
250 ml of an aqueous solution containing 70 g of gNO ₃ and KBr
The aqueous solution was added over a period of 20 minutes while maintaining the potential at 60 mV. At this time, the yellow blood salt was added 1.0 × to 1 mol of silver.
^10-5 mol was added. After washing with water, calcium concentration 1
80 g of lime-treated gelatin at 40 ° C.
H5.8, pAg, and 8.7 were adjusted.

[0102]

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The contents of calcium, magnesium and strontium in the above emulsion were measured by ICP emission spectroscopy, and found to be 15 ppm, 2 ppm and 1 ppm, respectively.

The temperature of the above emulsion was raised to 56 ° C. First, 1 g of a pure AgBr fine grain emulsion having a size of 0.05 μm was added thereto in terms of Ag and shelled. Next, sensitizing dyes 1, 2, 3
In the form of a solid fine dispersion,
3.93 × 10 ⁻⁴ mol, 2.05 × 10 ⁻⁴ mol,
6.00 × 10 ⁻⁶ mol was added. Sensitizing dyes 1, 2, 3
Was prepared as follows. As shown in Table 1, the inorganic salt was dissolved in ion-exchanged water, a sensitizing dye was added, and the mixture was dispersed at 2,000 rpm for 20 minutes using a dissolver blade at 60 ° C., as shown in Table 1. A solid dispersion of sensitizing dyes 1, 2, and 3 was prepared.

When the sensitizing dye was added and the adsorption of the sensitizing dye reached 90% of the amount adsorbed in the equilibrium state, calcium nitrate was added so that the calcium concentration became 250 ppm. The amount of sensitizing dye adsorbed is determined by separating the solid layer and the liquid layer by centrifugal sedimentation, measuring the difference between the amount of sensitizing dye added first and the amount of sensitizing dye in the supernatant, and adsorbing the sensitizing dye. The amount of dye was determined. After addition of calcium nitrate, potassium thiocyanate,
Chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea and Compound 4 were added for optimal chemical sensitization.
N, N-dimethylselenourea is used in an amount of 3.
40 × 10 ⁻⁶ mol was added. At the end of the chemical sensitization, Compound 2 and Compound 3 were added to prepare Em-A.

[0106]

[Table 1]

[0107]

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[0108]

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[0109]

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[0110]

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[0111]

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[0112]

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(Preparation of Em-B) In the preparation of Em-A
The amount of KBr added after nucleation was changed to 5 g,
Methionine (35 gmol / g)
98% trimellitization rate with 100000 molecular weight
Compound 1 was replaced with Trimeritized Gelatin.
Compound 5 and the amount of Compound 5 added was 8.0 in terms of KI.
g and sensitize the amount of sensitizing dye added before chemical sensitization
6.50 × 10 for each of dyes 1, 2, and 3^-4Mo
3.40 × 10^-4Mol, 1.00 × 10^-5Mole
N, N-dimethyl added during chemical sensitization
The amount of selenoureas was 4.00 × 10 ^-6Change to mole
Except for the above, Em-B was prepared in the same manner as Em-A.

[0114]

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(Preparation of Em-C) In the preparation of Em-A, the amount of KBr added after nucleation was changed to 1.5 g.
The succinated gelatin was replaced with phthalated gelatin having a molecular weight of 100,000 and a phthalation rate of 97%, containing 35 μmol / g of methionine, compound 1 was replaced with compound 6, and the added amount of compound 6 was changed to 7.1 g in terms of KI. The amount of sensitizing dye added before chemical sensitization was changed to sensitizing dye 1,
2,3 to, respectively 7.80 × 10 ^{- 4} mol, 4.
08 × 10 ⁻⁴ mol and 1.20 × 10 ⁻⁵ mol, and the amount of N, N- ヂ methylselenourea added during chemical sensitization was changed to 5.00 × 10 ⁻⁶ mol. Em-C was prepared in the same manner as Em-A.

[0116]

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(Preparation of Em-E) In the preparation of Em-A
The amount of compound 1 added was changed to 8.0 g in terms of KI
And sensitizing dye 4, which is added before chemical sensitization,
5 and 6, and the amount of each added was 5.19 × 10
^-4Mol, 1.11 × 10^-4Mol, 4.16 × 10
^-5Em-E was converted to Em-A in the same manner as Em-A except that
Prepared.

[0118]

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[0119]

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[0120]

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(Preparation of Em-F) 1200 ml of an aqueous solution containing 1.0 g of low molecular weight gelatin having a molecular weight of 15,000, 1.0 g of KBr was kept at 35 ° C., and vigorously stirred. A
gNO ₃ , 30 ml of an aqueous solution containing 1.9 g, KBr1.
30 ml of an aqueous solution containing 5 g and 0.7 g of low molecular weight gelatin having a molecular weight of 15,000 was added over 30 seconds by a double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. 5 g of KBr was added, and the temperature was raised to 75 ° C. to ripen. After ripening, 20 g of succinated gelatin and 15 g of phthalated gelatin were added. The pH was adjusted to 5.5. 150 ml of an aqueous solution containing 30 g of AgNO ₃ and KB
The r aqueous solution was added over 16 minutes by the double jet method. At this time, the silver potential is set to −25 with respect to the saturated calomel electrode.
mV.

Further, an aqueous solution containing 110 g of AgNO ₃ and an aqueous KBr solution were added over a period of 15 minutes by double jet method with the flow rate accelerated so that the final flow rate was 1.2 times the initial flow rate. At this time, an AgI fine grain emulsion having a size of 0.03 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was maintained at −25 mV. 132 ml of an aqueous solution containing 35 g of AgNO ₃ and K
An aqueous Br solution was added over 7 minutes by the double jet method. After adjusting the potential to −60 mV by adding an aqueous KBr solution, 9.2 g of an AgI fine grain emulsion having a size of 0.03 μm in terms of KI was added. 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After the addition was completed, 250 ml of an aqueous solution containing 70 g of AgNO ₃ and an aqueous KBr solution were added over 20 minutes while maintaining the potential at 60 mV. At this time, yellow blood salt was added in an amount of 1.0 × 10 ⁻⁵ mol per mol of silver. After washing with water, 80 g of lime-treated gelatin having a calcium concentration of 1 ppm was added, and
The pH was adjusted to 5.8 and pAg to 8.7 at 0 ° C.

The content of calcium, magnesium and strontium in the above emulsion was measured by ICP emission spectroscopy to be 15 ppm, 2 ppm and 1 ppm, respectively.

For chemical sensitization, sensitizing dyes 1, 2, and 3 were replaced with sensitizing dyes 4, 5, and 6, and the added amount was 8.50 ×
10 ⁻⁴ mol, 1.82 × 10 ⁻⁴ mol, 6.82 × 1
0 ^- except that the ⁵ mole subjected to chemical sensitization in the same manner as Em-B, was prepared Em-F.

(Preparation of Em-G) 1200 ml of an aqueous solution containing 1.0 g of low molecular weight gelatin having a molecular weight of 15,000, 1.0 g of KBr was maintained at 35 ° C., and vigorously stirred.
30 ml of an aqueous solution containing 1.9 g of AgNO ₃ , KBr
1.5 g and low molecular weight gelatin having a molecular weight of 15,000 0.7
30 ml of an aqueous solution containing g was added for 30 seconds by a double jet method to form nuclei. At this time, the excess concentration of KBr was kept constant. 1.5 g of KBr was added, and 75 ° C.
And aged. After the ripening, 15 g of the above-mentioned trimellitized gelatin and 20 g of the above-mentioned phthalated gelatin were added. The pH was adjusted to 5.5. AgNO ₃ , 30g
And an aqueous KBr solution were added over 16 minutes by the double jet method. At this time, the silver potential was kept at -25 mV with respect to the saturated calomel electrode.

Further, an aqueous solution containing 110 g of AgNO ₃ and an aqueous KBr solution were added over a period of 15 minutes by a double jet method at an accelerated flow rate such that the final flow rate was 1.2 times the initial flow rate. At this time, an AgI fine grain emulsion having a size of 0.03 μm was simultaneously added at an accelerated flow rate such that the silver iodide content became 3.8%, and the silver potential was maintained at −25 mV. 132 ml of an aqueous solution containing 35 g of AgNO ₃ and K
An aqueous Br solution was added over 7 minutes by the double jet method. The addition of the aqueous KBr solution was adjusted so that the potential became -60 mV. 7.1 g of an AgI fine grain emulsion having a size of 0.03 μm in terms of KI was added. 1 mg of sodium benzenethiosulfonate was added, and 13 g of lime-treated gelatin having a calcium concentration of 1 ppm was further added. After completion of the addition, 250 ml of an aqueous solution containing 70 g of AgNO ₃
And an aqueous KBr solution were added over a period of 20 minutes while maintaining the potential at 60 mV. At this time, yellow blood salt was added in an amount of 1.0 × 10 ⁻⁵ mol per mol of silver. After washing with water, 80 g of lime-processed gelatin having a calcium concentration of 1 ppm was added,
The pH was adjusted to 5.8 and pAg to 8.7 at 40 ° C.

The content of calcium, magnesium and strontium in the above emulsion was measured by ICP emission spectroscopy to be 15 ppm, 2 ppm and 1 ppm, respectively.

Sensitizing dyes 1, 2, and 3 were replaced by sensitizing dyes 4, 5, and 6
The chemical sensitization was carried out in the same manner as in Em-C except that the addition amounts were changed to 1.00 × 10 ⁻³ mol, 2.15 × 10 ⁻⁴ mol, and 8.06 × 10 ⁻⁵ mol, respectively. Do, E
m-G was prepared.

(Preparation of Em-J) In the preparation of Em-B, the sensitizing dyes added before chemical sensitization were changed to sensitizing dyes 7 and 8, and the added amount of each was 7.65 × 10 ^−4. Mole,
Em-J was prepared in the same manner as Em-B except that the amount was 2.74 × 10 ⁻⁴ mol.

[0130]

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[0131]

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(Preparation of Em-L) (Preparation of Silver Bromide Seed Emulsion) An average sphere equivalent diameter of 0.6 μm, an aspect ratio of 9.0, and a bromide containing 1.16 mol of silver and 66 g of gelatin per kg of emulsion. A silver tabular emulsion was prepared.

(Growth process 1) 1.2 g of potassium bromide and 9
Aqueous solution 12 containing 8% phthalated gelatin
0.3 g of modified silicone oil was added to 50 g. 0.
After the silver bromide tabular emulsion containing 086 mol of silver was added, the mixture was stirred at 78 ° C. An aqueous solution containing 18.1 g of silver nitrate and the silver iodide fine particles having a particle size of 0.037 μm were added so as to be 5.4 mol with respect to silver to be added. Further, at this time, an aqueous potassium bromide solution was added while adjusting the pAg to be 8.1 with a double jet.

(Growth Process 2) After adding 2 mg of sodium benzenethiosulfonate, 0.45 g of 3,5-disulfocatechol disodium salt, thiourea dioxide 2.
5 mg was added.

Further, an aqueous solution containing 95.7 g of silver nitrate and an aqueous solution of potassium bromide were accelerated by a double jet to obtain an aqueous solution.
Added over minutes. At this time, the silver iodide fine particles of 0.037 μm were added in a molar amount of 7.0 mol with respect to the added silver. At this time, the amount of potassium bromide in the double jet was adjusted so that the pAg became 8.1. After the addition,
2 mg of sodium benzenethiosulfonate were added.

(Growth Process 3) An aqueous solution containing 19.5 g of silver nitrate and an aqueous potassium bromide solution were added by a double jet over 16 minutes. At this time, the amount of the aqueous potassium bromide solution was adjusted so that the pAg became 7.9.

(Addition of sparingly soluble silver halide emulsion 4) After adjusting the host grains to 9.3 with an aqueous potassium bromide solution, 25 g of the 0.037 μm silver iodide fine grain emulsion was added to 2 g of the emulsion.
Added rapidly within 0 seconds.

(Formation of outermost shell layer 5) 34.9 g of silver nitrate
Was added over 22 minutes. This emulsion was tabular grains having an average aspect ratio of 9.8 and an average equivalent sphere diameter of 1.4 μm, and the average silver iodide content was 5.5 mol.

(Chemical sensitization) After washing with water, the phthalation ratio was 98.
% Phthalated gelatin and calcium nitrate at 40 ° C
Was adjusted to PH, 5.8, pAg, 8.7. The temperature was raised to 60 ° C., and a silver bromide fine grain emulsion of 0.07 μm was added to 5 × 10 −3.
After 20 minutes, sensitizing dyes 9, 10, and 11 were added. Thereafter, potassium thiocyanate, chloroauric acid, sodium thiosulfate, N, N-dimethylselenourea, and compound 4 were added to optimize chemical sensitization. Compound 3 was added 20 minutes before the end of chemical sensitization, and Compound 7 was added at the end of chemical sensitization. Here, the optimal chemical sensitization means that the sensitizing dye and each compound are added in an amount of 10 ^-1 to 1 per ¹ mol of silver halide so that the sensitivity at the time of exposure at 1/100 is maximized.
It means that it was selected from the added amount range of ^0-8 mol.

[0140]

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[0141]

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[0142]

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[0143]

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(Preparation of Em-O) An aqueous gelatin solution (1250 ml of distilled water, 48 g of deionized gelatin, 0.75 g of KBr) was charged into a reaction vessel equipped with a stirrer, and the temperature of the solution was kept at 70 ° C. To this solution, 276 ml of an aqueous AgNO ₃ solution (including 12.0 g of AgNO ₃ ) and an aqueous KBr solution having an equimolar concentration were added by a controlled double jet addition method over 7 minutes while maintaining the pAg at 7.26. Then, the temperature was lowered to 68 ° C, and thiourea dioxide (0.
7.6 ml of the mixture (05 wt%) was added.

Subsequently, 592.9 ml of an AgNO ₃ aqueous solution
(Including 108.0 g of AgNO ₃ ) and equimolar K
A mixed aqueous solution of Br and KI (2.0 mol% KI) was added by a controlled double jet addition method over 18 minutes and 30 seconds while maintaining the pAg at 7.30. Also, 5 minutes before the end of the addition, thiosulfonic acid (0.1 wt%) was added to 18.
0 ml was added.

The obtained grains were cubic grains having an equivalent sphere diameter of 0.19 μm and an average silver iodide content of 1.8 mol%. E
m-O was re-dispersed by desalting and washing with a normal flocculation method, and then at 40 ° C., pH 6.2 and pAg.
Adjusted to 7.6. Subsequently, Em-O was subjected to the following spectral and chemical sensitization.

First, sensitizing dye 10, sensitizing dye 11 and sensitizing dye 12 were added in an amount of 3.37 × 10 3 per mol of silver.
^-4 mol / mol, KBr 8.82 × 10 ^-4 mol / mol, sodium thiosulfate 8.83 × 10 ^-5 mol / mol, aqueous potassium thiocyanate 5.95 × 10 ^-4 mol / mol and potassium chloroaurate 3.07 × 10 ⁻⁵ mol / mol was added and aging was performed at 68 ° C. The aging time was adjusted so that the sensitivity at the exposure of 1/100 second was the highest.

[0148]

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For the preparation of (Em-D, H, I, K, M, N) tabular grains, low molecular weight gelatin is used in accordance with the examples of JP-A-1-158426. Further, according to the examples of JP-A-3-237450, gold sensitization was carried out in the presence of the spectral sensitizing dyes shown in Table 2 and sodium thiocyanate.
Sulfur sensitization and selenium sensitization are applied. Emulsions D and H,
I and K contain optimum amounts of Ir and Fe. Emulsion M, N
Is subjected to reduction sensitization during grain preparation using thiourea dioxide and thiosulfonic acid according to the examples of JP-A-2-191938.

[0150]

[Table 2]

[0151]

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[0152]

[Table 3]

In Table 3, dislocation lines as described in JP-A-3-237450 are observed in the tabular grains using a high-pressure electron microscope.

Emulsions Em-A1 to Em-A5 and Em-E1 to Em-E5 were prepared by changing the gelatin added in the grain growth step of Em-A and Em-E to the gelatin shown in Table 4. The sensitizing dye amount of each emulsion was adjusted to an optimum amount.

It was found that the emulsion using the gelatin of the present invention had a small projected area distribution despite the small grain thickness.

[0156]

[Table 4]

[Example 2] The following photosensitive materials were prepared and evaluated.

1) Support The support used in this example was prepared by the following method.

1) First layer and undercoat layer For a polyethylene naphthalate support having a thickness of 90 μm, a treatment atmosphere pressure of 0.2 Torr was applied to both surfaces of each support.
r, partial pressure of H ₂ O in atmosphere gas 75%, discharge frequency 30
The glow discharge treatment was performed at a frequency of 2500 kHz, an output of 2500 W, and a treatment intensity of 0.5 kV · A · min / m ² . A coating solution having the following composition was applied as a first layer on the support at a coating amount of 5 mL / m ² using a bar coating method described in Japanese Patent Publication No. 58-4589.

Conductive fine particle dispersion (SnO ₂ / Sb ₂ O ₅ particle concentration 50 parts by weight 10% aqueous dispersion. Secondary aggregate having a primary particle diameter of 0.005 μm and an average particle diameter of 0.05 μm) Gelatin 0.5 parts by weight Water 49 parts by weight Polyglycerol polyglycidyl ether 0.16 parts by weight Poly (degree of polymerization 20) oxyethylene 0.1 parts by weight Sorbitan monolaurate.

Further, after the first layer was applied, it was wound around a stainless steel core having a diameter of 20 cm, and was heat-treated at 110 ° C. (Tg of the PEN support: 119 ° C.) for 48 hours, heat-treated, and annealed. Thereafter, a coating solution having the following composition was applied to the side opposite to the first layer side as an undercoat layer for the emulsion at a coating amount of 10 mL / m ² by using a bar coating method.

Gelatin 1.01 parts by weight Salicylic acid 0.30 parts by weight Resorcin 0.40 parts by weight Poly (degree of polymerization 10) oxyethylene nonylphenyl ether 0.11 parts by weight Water 3.53 parts by weight Methanol 84.57 parts by weight n -Propanol 10.08 parts by weight.

Further, a second layer and a third layer, which will be described later, are sequentially coated on the first layer, and finally, a color negative photosensitive material having a composition, which will be described later, is overlaid on the opposite side to form a silver halide emulsion. A transparent magnetic recording medium with a layer was produced.

2) Second layer (transparent magnetic recording layer) Dispersion of magnetic material Co-coated γ-Fe ₂ O ₃ magnetic material (average major axis length: 0.25 μm)
m, S _BET : 39 m ² / g, Hc: 831 Oe, σs
: 77.1 emu / g, σr: 37.4 emu / g)
1100 parts by weight, 220 parts by weight of water and 165 parts by weight of a silane coupling agent [3- (poly (degree of polymerization 10) oxyethynyl) oxypropyl trimethoxysilane] were added and kneaded well with an open kneader for 3 hours. The coarsely dispersed viscous liquid was dried at 70 ° C. for 24 hours to remove water, and then heat-treated at 110 ° C. for 1 hour to produce surface-treated magnetic particles.

Further, the mixture was kneaded again with an open kneader for 4 hours according to the following formulation.

The above-mentioned surface-treated magnetic particles 855 g Diacetyl cellulose 25.3 g Methyl ethyl ketone 136.3 g Cyclohexanone 136.3 g Further, the following formulation was finely dispersed in a sand mill (1/4 G sand mill) at 2,000 rpm for 4 hours. did. As the medium, glass beads having a diameter of 1 mm were used.

The above kneading liquid 45 g diacetyl cellulose 23.7 g methyl ethyl ketone 127.7 g cyclohexanone 127.7 g Further, a magnetic substance-containing intermediate liquid was prepared according to the following formulation.

Preparation of Magnetic Substance-Containing Intermediate Solution 674 g of the above magnetic substance fine dispersion liquid 24280 g (solid content: 4.34%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) cyclohexanone 46 g After mixing these, The mixture was stirred with a disper to prepare a "magnetic substance-containing intermediate liquid".

An α-alumina abrasive dispersion of the present invention was prepared according to the following formulation.

(A) Sumicorundum AA-1.5 (average primary particle diameter 1.5 μm, specific surface area 1.3 m ² / g) Preparation of particle dispersion Sumicorundum AA-1.5 152 g Silane coupling agent KBM903 (Shin-Etsu Silicone Co., Ltd.) 0.48 g Diacetylcellulose solution 227.52 g (solid content 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Ceramic-coated sand mill (1/1)
(4G sand mill) at 800 rpm for 4 hours. As the media, zirconia beads having a diameter of 1 mm were used.

(B) Colloidal silica particle dispersion (fine particles) "MEK-ST" manufactured by Nissan Chemical Industries, Ltd. was used.

This is a dispersion liquid of colloidal silica having an average primary particle diameter of 0.015 μm using methyl ethyl ketone as a dispersion medium, and has a solid content of 30%.

Preparation of Coating Solution for Second Layer The above magnetic substance-containing intermediate solution 19053 g Diacetyl cellulose solution 264 g (solid content: 4.5%, solvent: methyl ethyl ketone / cyclohexanone = 1/1) Colloidal silica dispersion “MEK-ST” [Dispersion b] 128 g (solid content 30%) AA-1.5 dispersion [Dispersion a] 12 g Millionate MR-400 (manufactured by Nippon Polyurethane Industries, Ltd.) Diluent 203 g (solid content 20%, diluent solvent: methyl ethyl ketone) / Cyclohexanone = 1/1) 170 g of methyl ethyl ketone 170 g of cyclohexanone The coating solution obtained by mixing and stirring the above was applied with a wire bar so as to have an application amount of 29.3 mL / m ² . Drying is 1
Performed at 10 ° C. The thickness as a magnetic layer after drying is 1.0
μm.

3) Third layer (layer containing a higher fatty acid ester slip agent) Preparation of a stock solution of a slip agent The following solution A was heated and dissolved at 100 ° C, added to the solution A, and dispersed with a high-pressure homogenizer. Was prepared.

Solution A The following compound 399 parts by weight C ₆ H ₁₃ CH (OH) (CH ₂ ) ₁₀ COOC ₅₀ H _{101 The following} compound 171 parts by weight nC ₅₀ H ₁₀₁ O (CH ₂ CH ₂ O) ₁₆ H cyclohexanone 830 Parts by weight.

Solution A Cyclohexanone 8600 parts by weight.

Preparation of Spherical Inorganic Particle Dispersion A spherical inorganic particle dispersion [c1] was prepared according to the following formulation.

Isopropyl alcohol 93.54 parts by weight Silane coupling agent KBM903 (manufactured by Shin-Etsu Silicone Co., Ltd.) Compound 1-1: (CH ₃ O) ₃ Si— (CH ₂ ) ₃ —NH ₂ ) 5.53 parts by weight Compound 2-1 2.93 parts by weight

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Seahoster KEP50 88.00 parts by weight (amorphous spherical silica, average particle size 0.5 μm, manufactured by Nippon Shokubai Co., Ltd.).

After stirring for 10 minutes with the above formulation, the following is further added.

252.93 parts by weight of diacetone alcohol The above liquid was cooled with ice and stirred, while an ultrasonic homogenizer “SONIFIER450 (BRANSON CORPORATION) was used.
)) For 3 hours to obtain a spherical inorganic particle dispersion c1.
Was completed.

Preparation of Spherical Organic Polymer Particle Dispersion A spherical organic polymer particle dispersion [c2] was prepared according to the following formulation.

XC99-A8808 (manufactured by Toshiba Silicone Co., Ltd., spherical crosslinked polysiloxane particles, average particle size 0.9 μm) 60 parts by weight Methyl ethyl ketone 120 parts by weight Cyclohexanone 120 parts by weight (solid content 20%, solvent: methyl ethyl ketone / cyclohexanone) = 1/1) While cooling with ice and stirring, the ultrasonic homogenizer “SONI
The dispersion was performed for 2 hours using FIER450 (manufactured by BRANSON Corporation) to complete a spherical organic polymer particle dispersion c2.

Preparation of Third Layer Coating Solution The following was added to 542 g of the above-mentioned slip agent dispersion stock solution to prepare a third layer coating solution.

Diacetone alcohol 5950 g Cyclohexanone 176 g Ethyl acetate 1700 g The above sea hosta KEP50 dispersion [c1] 53.1 g The above spherical organic polymer particle dispersion [c2] 300 g FC431 2.65 g (3M Corporation) BYK310 5.3 g (manufactured by BYK Chemi Japan KK, solid content 25%).

The above third layer coating solution was applied on the second layer by 10.3
It was applied at a coating amount of 5 mL / m ² , dried at 110 ° C., and further dried at 97 ° C. for 3 minutes.

4) Coating of Photosensitive Layer Next, on the side opposite to the back layer obtained above, each layer having the following composition was applied in a multilayer manner to prepare a color negative film.

(Composition of photosensitive layer) The main materials used in each layer are classified as follows: ExC: cyan coupler UV: ultraviolet absorber ExM: magenta coupler HBS: high boiling point organic solvent ExY: yellow Coupler H: Gelatin hardener (specific compounds are described below with numerical values following symbols and chemical formulas after).

The numbers corresponding to the respective components indicate the coating amounts in g / m ² , and the silver halide indicates the coating amount in terms of silver.

First Layer (First Antihalation Layer) Black Colloidal Silver Silver 0.122 0.07 μm Silver Iodobromide Emulsion Silver 0.01 Gelatin 0.919 ExC-1 0.002 ExC-3 0.002 Cpd -2 0.001 HBS-1 0.005 HBS-2 0.002 Second layer (second antihalation layer) Black colloidal silver Silver 0.055 Gelatin 0.425 ExF-1 0.002 Solid disperse dye ExF-9 0.120 HBS-1 0.074 Third layer (low-sensitivity red-sensitive emulsion layer) Em-D silver 0.577 Em-C silver 0.347 ExC-1 0.188 ExC-2 0.011 ExC-30 0.075 ExC-4 0.121 ExC-5 0.010 ExC-6 0.007 Cpd-2 0.025 Cpd-4 0.025 Cpd-7 0.050 Cpd- 0.050 HBS-1 0.114 HBS-5 0.038 Gelatin 1.474 4th layer (Medium-speed red-sensitive emulsion layer) Em-B silver 0.431 Em-C silver 0.432 ExC-1 0.154 ExC-2 0.068 ExC-3 0.018 ExC-4 0.103 ExC-5 0.023 ExC-6 0.010 Cpd-2 0.036 Cpd-4 0.028 Cpd-7 0.010 Cpd- 8 0.010 HBS-1 0.129 Gelatin 1.086 Fifth layer (high-sensitivity red-sensitive emulsion layer) Em-A Silver 1.108 ExC-1 0.180 ExC-3 0.035 ExC-6 0.029 Cpd-2 0.064 Cpd-4 0.077 Cpd-7 0.040 Cpd-8 0.040 HBS-1 0.329 HBS-2 0.120 Gelatin 1.245 6th layer Intermediate layer) Cpd-1 0.094 Cpd-9 0.369 Solid disperse dye ExF-4 0.030 HBS-1 0.049 Polyethyl acrylate latex 0.088 Gelatin 0.886 7th layer (overlying red sensitive layer) Layer giving effect) Em-J silver 0.293 Em-K silver 0.293 Cpd-4 0.030 ExM-2 0.120 ExM-3 0.016 ExY-1 0.016 ExY-6 0.036 Cpd -6 0.011 HBS-1 0.090 HBS-3 0.003 HBS-5 0.030 Gelatin 0.610 Eighth layer (low-sensitivity green-sensitive emulsion layer) Em-H silver 0.329 Em-G silver 0 .333 Em-I silver 0.088 ExM-2 0.378 ExM-3 0.047 ExY-1 0.017 HBS-1 0.098 HBS-3 0.010 HBS -4 0.077 HBS-5 0.548 Cpd-5 0.010 Gelatin 1.470 9th layer (Medium speed green-sensitive emulsion layer) Em-F Silver 0.457 ExM-2 0.032 ExM-3 0. 029 ExM-4 0.029 ExY-1 0.007 ExC-6 0.010 HBS-1 0.065 HBS-3 0.002 HBS-5 0.020 Cpd-5 0.004 Gelatin 0.446 10th layer (High-sensitivity green-sensitive emulsion layer) Em-E silver 0.794 ExC-6 0.002 ExM-1 0.013 ExM-2 0.011 ExM-3 0.030 ExM-4 0.017 ExY-5 0. 003 Cpd-3 0.004 Cpd-4 0.007 Cpd-5 0.010 HBS-1 0.148 HBS-5 0.037 Polyethyl acrylate latex 0.099 Ratin 0.939 Eleventh layer (yellow filter layer) Cpd-1 0.094 Solid disperse dye ExF-2 0.150 Solid disperse dye ExF-5 0.010 Oil-soluble dye ExF-7 0.010 HBS-1 049 Gelatin 0.630 12th layer (low-sensitivity blue-sensitive emulsion layer) Em-O silver 0.112 Em-M silver 0.320 Em-N silver 0.240 ExC-1 0.027 ExY-1 0.027 ExY -2 0.890 ExY-6 0.120 Cpd-2 0.100 Cpd-3 0.004 HBS-1 0.222 HBS-5 0.074 Gelatin 2.058 13th layer (high-sensitivity blue-sensitive emulsion layer) Em-L silver 0.714 ExY-2 0.211 Cpd-2 0.075 Cpd-3 0.001 HBS-1 0.071 gelatin 0.678 Fourteenth layer (first Protective layer) 0.07 μm silver iodobromide emulsion Silver 0.301 UV-1 0.211 UV-2 0.132 UV-3 0.198 UV-4 0.026 F-18 0.009 S-10 0.086 HBS-1 0.175 HBS-4 0.050 Gelatin 1.984 15th layer (second protective layer) H-1 0.400 B-1 (1.7 μm in diameter) 0.050 B-2 (diameter 1.7 μm) 0.150 B-3 0.050 S-1 0.200 Gelatin 0.750 Furthermore, each layer may be appropriately preserved, processed, pressure-resistant, and mold-proof.
In order to improve antibacterial properties, antistatic properties and coatability, W-
1 to W-6, B-4 to B-6, F-1 to F
-17 and a lead salt, a platinum salt, an iridium salt, and a rhodium salt.

Preparation of Dispersion of Organic Solid Disperse Dye ExF-2 of the eleventh layer was dispersed by the following method.

ExF-2 wet cake (containing 17.6% by weight of water) 2.800 kg Sodium octylphenyldiethoxymethanesulfonate (31% by weight in water) 0.376 kg F-15 (7% in water) 0. 011 kg Water 4.020 kg Total 7.210 kg (adjusted to pH = 7.2 with NaOH) After the slurry having the above composition was coarsely dispersed by stirring with a dissolver, the peripheral speed was 10 m / min using an agitator mill LMK-4.
s, a discharge rate of 0.6 kg / min, a filling rate of zirconia beads having a diameter of 0.3 mm of 80%, and an absorbance ratio of the dispersion of 0.29.
To obtain a solid fine particle dispersion. The average particle size of the fine dye particles was 0.29 μm.

Similarly, ExF-4 and ExF-9
Was obtained. The average particle size of the fine dye particles was 0.28 μm and 0.49 μm, respectively. ExF-5
Was dispersed by a microprecipitation dispersion method described in Example 1 of European Patent No. 549,489A. The average particle size was 0.06 μm.

The compounds used for forming each layer are shown below.

[0195]

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[0196]

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[0197]

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[0198]

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[0199]

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[0200]

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[0201]

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[0202]

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[0203]

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[0204]

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[0205]

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The color negative photosensitive material prepared as described above was used as Sample 101. Samples 102 to 106 were prepared by changing the emulsions of the fifth and tenth layers to those shown in Table 5.

The sample 101 was passed through a continuous wedge through a gelatin filter SC-39 manufactured by Fuji Film Co., Ltd.
It was exposed for 00 seconds.

The development was performed by an automatic processor F manufactured by Fuji Photo Film Co., Ltd.
Performed as follows using P-360B. The remodeling was performed so that the overflow solution of the bleaching bath was not discharged to the post-bath but was entirely discharged to the waste liquid tank. This FP-360B is equipped with the evaporation correction means described in Hatsumei Kyokai Disclosure Technique No. 94-4992.

The processing steps and the composition of the processing solution are shown below.

(Processing Step) Step Processing time Processing temperature Replenishment amount * Tank capacity Color development 3 minutes 5 seconds 37.8 ° C 20 mL 11.5L Bleaching 50 seconds 38.0 ° C 5 mL 5L Fixing (1) 50 seconds 38.0 ° C ─ 5L fixing ( 2) 50 seconds 38.0 ℃ 8 mL 5L water washing 30 seconds 38.0 ℃ 17 mL 3L stable (1) 20 seconds 38.0 ℃ ─ 3L stable (2) 20 seconds 38.0 ℃ 15 mL 3L drying 1 minute 30 seconds 60.0 ℃ * replenishment amount Is per 35 m of photosensitive material and 1.1 m in width (equivalent to 24 Ex. 1 line)

The stabilizing solution and the fixing solution were of a countercurrent type from (2) to (1), and the overflow of the washing water was all introduced into the fixing bath (2). The amount of the developer brought into the bleaching step, the amount of the bleaching liquid brought into the fixing step, and the amount of the fixing liquid brought into the washing step were 35 mm in width of the photosensitive material and 1.1 m in width.
2.5 mL, 2.0 mL, and 2.0 mL, respectively. The crossover time is 6 seconds in each case, and this time is included in the processing time of the previous step.

The opening area of the above processing machine was 10
0cm ² , 120cm ^{2 for} bleaching solution, about 1 other processing solution
00 cm ² .

The composition of the processing liquid is shown below.

(Color developer) Tank solution (g) Replenisher (g) Diethylenetriaminepentaacetic acid 3.0 3.0 Catechol-3,5-disulfonate disodium 0.3 0.3 Sodium sulfite 3.9 3 Potassium carbonate 39.0 39.0 Disodium-N, N-bis (2-sulfonatoethyl) hydroxylamine 1.5 2.0 Potassium bromide 1.3 0.3 Potassium iodide 1.3mg-4-Hydroxy -6-methyl-1,3,3a, 7-tetrazaindene 0.05-hydroxylamine sulfate 2.4 3.3 2-methyl-4- [N-ethyl-N- (β-hydroxyethyl) amino Aniline sulfate 4.5 6.5 Add water 1.0 L 1.0 L pH (adjusted with potassium hydroxide and sulfuric acid) 10.05 10.18.

(Bleaching solution) Tank solution (g) Replenisher solution (g) Ferric ammonium 1,3-diaminopropanetetraacetate monohydrate 113 170 Ammonium bromide 70 105 Ammonium nitrate 14 21 Succinic acid 34 51 Maleic acid 28 42 Water was added and 1.0 L 1.0 L pH [adjusted with aqueous ammonia] 4.6 4.0.

(Fixing (1) tank liquid) A mixture of the bleaching tank liquid and the following fixing tank liquid in a ratio of 5 to 95 (volume ratio).

(PH 6.8) (Fixing (2)) Tank solution (g) Replenisher (g) Ammonium thiosulfate aqueous solution 240 mL 720 mL (750 g / L) Imidazole 721 Ammonium methanethiosulfonate 515 Ammonium methanesulfinate 10 30 Ethylenediaminetetraacetic acid 1339 Water was added to 1.0 L 1.0 L pH [adjusted with aqueous ammonia and acetic acid] 7.4.45.

(Washing water) Tap water was replaced with H-type strongly acidic cation exchange resin (Amberlite IR- manufactured by Rohm and Haas Company).
120B) and a mixed bed column packed with an OH type strongly basic anion exchange resin (Amberlite IR-400) to reduce the calcium and magnesium ion concentration to 3 m.
g / L or less, followed by sodium diisocyanurate 20 mg / L and sodium sulfate 150 mg / L
Was added. The pH of this solution was in the range of 6.5 to 7.5.

(Stabilizing solution) Common to tank solution and replenisher (unit: g) Sodium p-toluenesulfinate 0.03 Polyoxyethylene-p-monononylphenyl ether 0.2 (Average degree of polymerization: 10) 1,2-benzo Isothiazolin-3-one sodium 0.10 Disodium ethylenediaminetetraacetate 0.05 1,2,4-triazole 1.3 1,4-bis (1,2,4-triazol-1-ylmethyl) piperazine 0. 75 Add water to 1.0 L pH 8.5.

The density of the treated sample was measured with green and red filters. The sensitivity was represented by the relative value of the reciprocal of the exposure necessary to give a density of fog plus 0.2. Also, RM
The S granularity is uniformly exposed with a light amount giving a density of 0.2, and after performing the above-mentioned development processing, the “The.
Theory of the Photographic Process "6
It was measured by the method described on page 19. Further, in order to measure the sharpness, each sample was exposed through an MTF pattern, and after performing the above-mentioned developing treatment, the sharpness was evaluated by measuring with a microdensitometer at a value of a spatial frequency of 10 cycles / mm. Note that the above measured values are expressed as relative values when the value of the sample 101 is set to 100.

Table 5 shows the obtained results.

[0222]

[Table 5]

As is clear from Table 5, the light-sensitive material using the emulsion of the present invention has a high sensitivity and the graininess is remarkably improved.
It was also found that the sharpness of the red-sensitive layer of the present invention was superior to that of the light-sensitive layer.

Example 3 The aforementioned Em-A5 and EM-E
Emulsions Em-A6 and Em-E6 in which gelatin added twice during grain growth of Example 5 was used only once after the completion of ripening
Was prepared. Table 6 shows the results of preparing and evaluating the sample 107 by applying it in the same manner as in Example 2. It became clear that the graininess was better when gelatin was added twice.

[0225]

[Table 6]

[Example 4] Sample 101 manufactured in Example 2
Samples 201 to 206 in which the same photosensitive layer composition as in Examples Nos. 106 to 106 was coated on an undercoated cellulose triacetate film support
Was prepared and evaluated, and the same results as in Example 2 were obtained.

Example 5 Sample 101 manufactured in Example 2
A comparison was made between the photographs actually taken by loading Nos. 1 to 106 in a packaging unit having a photographing mechanism, and it was confirmed that the photosensitive material of the present invention had fine and sharp particles and a clear improvement effect.

Continued on the front page (72) Inventor Hiroki Sasaki 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 2H023 BA01 BA04 DB05

Claims (4)

[Claims] In a method for producing a silver halide photographic emulsion containing tabular grains which form grains through respective steps of nucleation, ripening and grain growth in a dispersion medium, the tabular grains have an average aspect ratio of 5 or more. 100 or less, and at least the particle growth is carried out in the presence of at least 40% by weight of the dispersion medium of chemically modified gelatin represented by the following general formula 1 or low molecular weight gelatin having a weight average molecular weight of 1,000 or more and 70,000 or less. A method for producing a silver halide photographic emulsion. General formula 1 Gel-NH-L-COOH Here, Gel represents a gelatin polypeptide. -NH-
Represents a group derived from an amino group in the gelatin polypeptide. L is (i) a substituted or unsubstituted alkylene having 1 to 5 carbon atoms or a substituted or unsubstituted alkenylene group having 2 to 5 carbon atoms, (ii) -C (= O) -R- (where R Represents a divalent linking group selected from the group consisting of substituted or unsubstituted alkylene having 1 to 4 carbon atoms or a substituted or unsubstituted alkenylene group having 2 to 4 carbon atoms). 2. The amino group of the chemically modified gelatin having -L
The method for producing a silver halide photographic emulsion according to claim 1, wherein the chemical modification ratio with -COOH is 15% or more and 100% or less. 3. The method for producing a silver halide photographic emulsion according to claim 1, wherein the chemically modified gelatin or the low molecular weight gelatin is added at least twice from the start of nucleation to the end of grain growth. Method. 4. A silver halide photographic light-sensitive material having at least one photosensitive silver halide emulsion layer on a support, wherein the silver halide emulsion layer has the structure described in any one of claims 1 to 3. A silver halide photographic light-sensitive material comprising a silver halide photographic emulsion produced by the method.