JPH09160159A - Silver halide photographic emulsion and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the silver halide photographic emulsion high in sensitivity and superior in the storage stability of the emulsion by adding a specified compound within a specified time length after the end of chemical ripening following the addition of a sensitizing dye. SOLUTION: The silver halide photographic emulsion spectrally sensitized by adding the sensitizing dye represented by formula I and/or formula II before the end of the chemical ripening has the compound represented by formula III added within 5hrs after the end of chemical ripening. In formulae I-III, each of Z<1> and Z<3> is a nonmetallic atomic group necessary to form an optionally substituted benzothiazole ring or the like; Z<2> is an optionally substituted 5- or 6-membered carbon atom ring; each of R<4> and R<5> is an optionally substituted alkyl group; R<6> is an H atom or the like; Z<4> is a nonmetallic atomic group necessary to form a 5- or 6-membered N-containing hetero ring; X1 <-> is a counter-ion; each of (p), (n), and (m) is 1 or 2; each of R<7> and R<8> is a hydroxy group or the like; and Z<5> is a nonmetallic atomic group necessary to form an optionally substituted a 5- or 6-membered ring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic emulsion and a method for producing the same, and more particularly to a silver halide photographic emulsion having a stable emulsion coating solution and a method for producing the same.

[0002]

2. Description of the Related Art In recent years, in the medical field, silver halide photographic light-sensitive materials have been actively scanned and exposed with a laser beam to record an image. In this laser imager system, it is desired that the information is recorded in a short time and the development processing is performed quickly so that information diagnosis can be obtained urgently.

Various light sources for this laser system are known, but semiconductor lasers are compact, inexpensive, easy to modulate, and have a relatively long life. Is believed to be.

The emission wavelength of the semiconductor laser is 700 to 15
Since it is at 00 nm, it has a photosensitive wavelength range in the near infrared region,
Moreover, a photosensitive material capable of high-sensitivity recording even for a laser beam having a small output is required.

Regarding the spectral sensitization of silver halide grains to the near infrared region, it is known to use di- or tricarbocyanine dyes, for example, the same applicant as the present invention, JP-A-5-224335. The publication discloses improvement in storage stability and pressure resistance by using a specific dicarbocyanine and a specific triazole compound.

However, a silver halide emulsion color-sensitized in the near infrared region is liable to cause a decrease in sensitivity when the coating solution is stagnant for a long time, and a light-sensitive material having a stable sensitivity should be produced over a long time. Was not possible, which was a problem in production. Therefore, further sensitization technology is required to perform rapid recording and / or rapid development processing in the near infrared region which is the emission wavelength of the semiconductor laser.

[0007]

An object of the present invention is to provide a silver halide photographic emulsion having high sensitivity and excellent emulsion storability and a method for producing the same, and to provide silver halide having high sensitivity and excellent stagnation of coating solution. To provide a photographic emulsion and a method for producing the same.

[0008]

The above object of the present invention is achieved by the following constitution.

(1) In a silver halide photographic emulsion spectrally sensitized by adding a sensitizing dye represented by the following general formula [I] and / or general formula [II] before the completion of chemical ripening.
A silver halide photographic emulsion characterized in that a compound represented by the following general formula [III] is added within 5 hours after the completion of chemical ripening after the addition of a sensitizing dye.

[0010]

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In the formula, Z ¹ and Z ³ represent a group of non-metal atoms necessary for forming a benzothiazole, benzoxazole and naphthoxazole ring which may have a substituent. Z ²
Represents a 5- to 6-membered carbon atom ring which may have a substituent,
R ¹ and R ² each represent a substituted or unsubstituted alkyl group. X ₁ ⁻ represents a counter ion, and n represents 1 or 2.

[0012]

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In the formula, Z ⁴ represents a nonmetallic atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and R ⁴ and R ⁵ each represent a substituted or unsubstituted alkyl group. R ⁶ represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a benzyl group, X ₁ ⁻ represents a counter ion, and p, m and n are 1
Or 2 is represented.

[0014]

[Chemical 6]

In the formula, R ⁷ and R ⁸ are each independently a hydroxy group, a mercapto group, or a substituted or unsubstituted amino group,
It represents an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group or an alkylthio group. Z ⁵ is substituted or unsubstituted 5 to 6
Represents the group of atoms necessary to form a member ring.

(2) The compound represented by the general formula [III] is added by the time the preparation of the coating solution is completed, and the general formula [I] and / or the general formula is prepared by the completion of the chemical aging until the preparation of the coating solution is completed. A silver halide photographic emulsion characterized by being spectrally sensitized by adding a sensitizing dye represented by [II].

(3) A step of spectrally sensitizing by adding the sensitizing dye represented by the general formula [I] and / or the general formula [II] before the completion of the chemical ripening, and a chemical process after the sensitizing dye is added. A method for producing a silver halide photographic emulsion, which comprises the step of adding the compound represented by the general formula [III] within 5 hours after the completion of ripening.

(4) A step of adding the compound represented by the above-mentioned general formula [III] until the preparation of the coating solution is completed, and the above-mentioned general formula [I] and /
Alternatively, a method for producing a silver halide photographic emulsion comprising a step of spectrally sensitizing by adding a sensitizing dye represented by the general formula [II].

The inventor has heretofore used the above general formula [I] and / or general formula [I] before the completion of chemical ripening of a silver halide emulsion.
By adding the sensitizing dye represented by
Although it was spectrally sensitized to m or more and 1500 nm or less, there was a defect that the sensitivity was lowered during storage of the emulsion. However, it was discovered that by adding the compound represented by the general formula [III] after the addition of the sensitizing dye and before the completion of the chemical ripening, high sensitivity can be obtained, and further, the sensitivity reduction during emulsion storage is eliminated, and the present invention Done Further, a silver halide spectrally sensitized to 700 nm or more and 1500 nm or less by adding a sensitizing dye represented by the above general formula [I] and / or general formula [II] between the end of chemical ripening and the end of preparation of a coating solution. The emulsion has the drawback that the sensitivity varies greatly when the coating solution is stagnant, and it has been discovered that the sensitivity can be increased by adding the compound represented by the general formula [III], and the variation can be reduced, thereby completing the present invention. .

In the present invention, the term "at the end of chemical ripening" means, for example, 4-hydroxy-6-methyl-1, as a stabilizer.
It refers to the time when 3,3a, 7-tetrazaindene was added.
In the present invention, the coating solution preparation means that the chemical ripening is completed and the temperature of the silver halide emulsion is adjusted to 50 to 60 at the time of chemical ripening.
This is a step of slightly lowering the temperature to 40 to 45 ° C. and adding an additive necessary for the coating solution, such as gelatin. And, when the preparation of the coating solution is completed, the addition of these additives is completed and the temperature of the silver halide emulsion is further lowered to 35 ° C. or lower.

In the silver halide photographic light-sensitive material of the present invention, the light-sensitive silver halide emulsion layer contains 700 nm or more of the dye represented by the above general formula [I] or general formula [II],
It is spectrally sensitized to 1500 nm or less.

Next, the compounds of the general formulas [I] and [II] according to the present invention will be explained.

[0023]

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In the formula, Z ¹ and Z ³ represent a non-metallic atom group necessary for forming a benzothiazole, naphthothiazole, benzoxazole and naphthoxazole ring which may have a substituent. Z ² represents a 5- or 6-membered carbon atom ring which may have a substituent, and R ¹ and R ² each represent an alkyl group or a substituted alkyl group. X ₁ ^- it is n represents a counter ion is 1 or 2. The benzothiazole ring, naphthothiazole ring, benzoxazole ring, and naphthoxazole ring represented by Z ¹ and Z ³ may have a substituent, for example, an alkyl group having 1 to 4 carbon atoms,
And 4 to 4 alkoxy groups, phenyl groups, halogen atoms (eg, chlor atom, bromo atom) and the like may be substituted. R ¹ and R ² are an alkyl group having 1 to 4 carbon atoms,
Examples of the substituted alkyl group having 1 to 4 carbon atoms include methyl, ethyl, hydroxyethyl, 2-methoxyethyl, 2-acetoxyethyl, carboxymethyl, 2-carboxyethyl, 3-carboxypropyl, 4-carboxybutyl,
Examples thereof include 2-sulfopropyl, 3-sulfobutyl, 4-sulfobutyl, vinylmethyl, benzyl, phenethyl, p-sulfophenethyl, n-propyl, isopropyl, and n-butyl groups.

Preferred compounds of the present invention represented by the general formula [I] when Z ² is a 5-membered carbon atom ring are:
Specifically, it can be represented by the following general formula [Ia].

[0026]

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R ¹³ and R ¹⁴ are each a hydrogen atom and have 1 carbon atom.
Represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom (for example, a chlor atom or a bromo atom), and R ¹⁵ and R ¹⁶ each have an alkyl group having 1 to 12 carbon atoms and a substituent. Phenyl group (for example, phenyl group, m-tolyl group, p-tolyl group, m-chlorophenyl group, and p-substituted alkoxy group having 1 to 4 carbon atoms).
A methoxyphenyl group) and an alkoxycarbonylalkyl group having 1 to 4 carbon atoms (such as an ethoxycarbonylmethyl group).

R ¹⁷ represents an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 1 to 4 carbon atoms, or a phenyl group. Z ¹ , Z ³ , R ¹ ,
R ² and X ₁ ⁻ , n have the same meanings as those in formula [I].

Preferred compounds of the present invention represented by the above general formula [I] when Z ² is a 6-membered carbon atom ring are:
Specifically, it can be represented by the following general formula [Ib].

[0030]

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In the formula, R ¹⁸ and R ¹⁹ each represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms or phenyl. Z ¹ ,
Z ^3, R ^1, R ² and X ₁ ^-, n are as defined in formula (I).

Specific examples of the compound of the general formula [I] according to the present invention are shown below, but the present invention is not limited thereto.

[0033]

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[0034]

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[0035]

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[0036]

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Next, the compound of the general formula [II] according to the present invention will be described in detail.

[0038]

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In the formula, R ⁴ and R ⁵ represent an alkyl group or a substituted alkyl group, preferably an alkyl group having 1 to 8 carbon atoms. Examples of the group substituted with the alkyl group include a carboxyl group, a sulfone group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, and a fluorine atom), a hydroxyl group, an alkoxycarbonyl group (preferably having 8 or less carbon atoms), an alkoxy group, Group (preferably having 7 or less carbon atoms),
Examples thereof include an aryloxy group, an acyloxy group (preferably having 3 or less carbon atoms), an acyl group (preferably having 8 or less carbon atoms), a carbamoyl group, a sulfamoyl group, and an aryl group. R ⁶ is a hydrogen atom, an alkyl group,
An alkoxy group, a phenyl group or a benzyl group, preferably an alkyl group having 1 to 4 carbon atoms or a benzyl group. Y represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkoxy group or a halogen atom (eg, chlorine atom, bromine atom, fluorine atom).

Examples of the 5- or 6-membered nitrogen-containing heterocycle represented by Z ⁴ include a thiazole ring, a selenazole ring, an oxazole ring, a 3,3-dialkylindolenine ring, an imidazole ring and the like. Of these, preferred are a thiazole ring and an oxazole ring, and more preferred are a benzothiazole ring, a naphthothiazole ring, a benzoxazole ring and a naphthoxazole ring.

[0041] X ₁ ^- represents a counter ion, m, n and p 1
Or 2 is represented.

Specific examples of the compound of the general formula [II] according to the present invention are shown below, but the present invention is not limited thereto.

[0043]

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[0044]

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The above-mentioned spectral sensitizing dyes of the present invention may be used either individually or in combination of the general formulas [I] and [II]. In the case of a single case, they are selected from the general formula [I]. The dyes mentioned above are particularly preferably used, and the addition amount of the above-mentioned spectral sensitizing dye may be 1 to 100 mg, and more preferably 2 to 40 mg, per mol of silver halide. The dye may be added by a conventional solution addition method using a solvent or a solid dispersion method.

In the general formula [III] of the present invention, R ⁷ , R
Each ⁸ independently includes a hydroxy group, a mercapto group, an amino group (including those having a C1-10 alkyl group such as a methyl group, an ethyl group, an n-butyl group, or a hydroxyethyl group as a substituent). Acylamino group (acetylamino group, benzoylamino group, etc.), alkylsulfonylamino group (methanesulfonylamino group, etc.), arylsulfonylamino group (benzenesulfonylamino group, p-toluenesulfonylamino group, etc.), alkoxycarbonylamino group (methoxy A carbonylamino group) and an alkylthio group (methylthio group, ethylthio group, etc.). Preferred examples of R ⁷ and R ⁸ include a hydroxy group, an amino group, an alkylsulfonylamino group and an arylsulfonylamino group. Z ⁵ is preferably composed of a carbon atom, an oxygen atom or a nitrogen atom, and together with the two vinyl carbons substituted by R ⁷ and R ⁸ and the carbonyl carbon form a 5- or 6-membered ring, particularly a reductone ring preferable. Specific examples of Z ⁵ include -O.
^{-, - C (R 10)} (R 11) -, - C (R 12) =, - C
(= O) -, - N (R 13) -, - formed by combining the N =. However, R ¹⁰ , R ¹¹ , R ¹² , and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms which may be substituted (a hydroxy group, a carboxy group, or a sulfo group can be given as a substituent). Represents an aryl group having 6 to 15 carbon atoms which may be substituted (an alkyl group, a halogen atom, a hydroxy group, a carboxy group or a sulfo group can be mentioned as a substituent), a hydroxy group or a carboxy group. Further, a saturated or unsaturated condensed ring may be formed on the 5- or 6-membered ring. Examples of the 5- to 6-membered ring include a dihydrofuranone ring, a dihydropyrone ring, a pyranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrrolinone ring, a pyrazolinone ring, a pyridone ring, an azacyclohexenone ring, and a uracil ring. Preferred examples of the 5- or 6-membered ring include a dihydrofuranone ring, a cyclopentenone ring, a cyclohexenone ring, a pyrazolinone ring, an azacyclohexenone ring and a uracil ring. Specific examples of the compound represented by the general formula [III] of the present invention are shown below, but the present invention is not limited thereto.

[0047]

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[0048]

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[0049]

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When the compound represented by the general formula [III] of the present invention is an acid, it may be a free acid or a salt form.
Among the above compounds, L-ascorbic acid represented by III-1 or erythorbic acid or a salt thereof is particularly preferable. The addition amount varies depending on factors such as the silver halide composition of the emulsion and the coating amount of silver, but is 5 × per mol of silver halide.
The range of 10 ^-5 to 1 × 10 ^-1 mol is preferable, and 1 × 10 ^-4
The range of up to 1 × 10 ^-2 mol is more preferable.

When the compound represented by the general formula [I] or [II] of the present invention is added before the completion of the chemical ripening, the addition timing is preferably from after the desalting step to the start of the chemical ripening. More preferably, it is from 60 minutes before the start of aging to the start of chemical aging. In this case, the compound represented by the general formula [III] of the present invention is preferably added for 1 hour after the completion of the chemical ripening.

When the compound represented by the general formula [I] or [II] of the present invention is added from the end of chemical ripening to the end of preparation of the coating solution, the addition timing is preferably from the start to completion of the coating solution preparation. . In that case, the compound represented by the general formula [III] of the present invention is preferably within 10 minutes after the addition of the compound represented by the general formula [I] or [II].

[0053]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Example 1 (Preparation of seed particles) 40 ° C., pAg = 9.0, pH = 2.
While controlling it to 0, monodispersed cubic emulsion grains of silver iodobromide containing 2.0 mol% of silver iodide having an average grain size of 0.09 μm were obtained by the double jet method. The obtained emulsion was precipitated at 40 ° C. using Demol N (aldehyde condensate of sodium naphthalenesulfonate) and aqueous magnesium sulfate manufactured by Kao Atlas Co., Ltd., and decanted to remove unnecessary inorganic salts.

(Grain Growth from Seed Emulsion) Of this seed emulsion, an amount corresponding to 4.7% of all silver halide used for growth was used as a seed crystal and grown as follows. That is, 40 ° C
Containing gelatin kept at 0.16% ammonia concentration
This seed crystal was dissolved in a prescribed solution, and the pH was adjusted to 8.5 with glacial acetic acid. Using this solution as a mother liquor, 3.2N ammoniacal silver ion aqueous solution and halide aqueous solution were added by the double jet method and mixed by stirring.

At this time, a core portion having a silver iodide content of 30 mol% was formed, then pAg was adjusted to 8.0 and pH was adjusted to 8.
5 to form a silver bromide shell, and designated as emulsion E-1.

The obtained emulsion had an average grain size of 0.25 μm.
m, average silver iodide content 2.2 mol%, S / r = 0.12
Of monodispersed cubic particles.

Then, in order to remove excess salts, desalting with desmol N and magnesium sulfate as described above was performed. Then, an aqueous gelatin solution containing 9.2 g of ossein gelatin per mole of silver halide was added and stirred and dispersed.

Pure water was added to the obtained E-1 silver halide emulsion so that the volume per mol of silver was 300 ml, and the temperature was raised to 52 ° C.
0.05 g per mol was added, an appropriate amount of chloroauric acid and hypo were added, and further 4.5 mg of triphenyl-phosphine selenide was added for chemical ripening. afterwards,
4-Hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added to complete the chemical ripening.

The dyes listed in Table 1 were added as described to perform spectral sensitization. The compound represented by the general formula [III] was also added as shown in Table 1. In the table, the term "addition time" means that the addition was performed under the following conditions.

(A): Before addition of gelatin aqueous solution after desalting (b): 10 minutes before addition of ammonium thiocyanate salt (c): 4-hydroxy-6-methyl-1,3,3a,
Simultaneous with the addition of 7-tetrazaindene (d): Immediately before the addition of the emulsion coating solution additive The emulsion that had been chemically ripened was cooled to gel and stored at 5 ° C.

Preparation of Support 400 g of gelatin as backing layer, 2 g of polymethylmethacrylate, sodium dodecylbenzenesulfonate 6
g, 20 g of the following antihalation dye, and N, N′-ethylenebis- (vinylsulfonylacetamide) polyethylenesulfonate sodium coating solution were prepared, and glycidyl methacrylate 50 wt%, methyl acrylate 10 wt%, butyl methacrylate 4
Gelatin on one side of a polyethylene terephthalate base coated with an aqueous dispersion of a copolymer obtained by diluting a copolymer consisting of 0 wt% of three kinds of monomers so as to have a concentration of 10 wt% , Matting agent (polymethylmethacrylate: average particle size 3.5 μ), glyoxal, sodium t-octylphenoxyethoxyethane sulfonate, and

[0063]

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A backed support obtained by coating with a protective layer liquid consisting of was prepared. The coating amount is the backing layer,
Each of the protective layers was 2.0 g /
m ² and 1.2 g / m ² .

[0065]

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Preparation of Emulsion Coated Samples Each of the obtained emulsions was heated to 42 ° C. and silver halide 1
The following was added per mol to prepare a coating solution. After the addition, the emulsion temperature was brought to 35 ° C.

Gelatin 78 g 1-Trimethylolpropane 10 g Nitrophenyl-triphenylphosphonium chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 1 g 2-Mercaptobenzimidazole-5-sodium sulfonate 10 mg

[0068]

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1,1-Dimethylol-1-bromo-1-nitromethane 10 mg

[0070]

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The following was prepared as a protective layer liquid. The amount of addition is indicated by the amount per liter of the coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-iso-amyl-n-decylsulfosuccinate 1 g Polymethylmethacrylate (matting agent having an average particle size of 3.5 μ) 1.1 g Silicon dioxide particles (average particle size 1 .2μ matting agent) 0.5 g Ludox AM (Colloidal silica manufactured by DuPont) 30 g 2-4-dichloro-6-hydroxy-1,3,5-triazine sodium salt aqueous solution 2% 10 ml Holimarin 35% 2 ml Glyoxal 40% 1 0.5 ml

[0073]

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On the backed base described above, the respective layers were sequentially coated from the support by the slide hopper method, and two layers of the silver halide emulsion layer and the protective layer were simultaneously coated at a coating speed of 60 m / min to obtain a sample. Amount of silver is 2.5 g / m ^2, gelatin amount emulsion layer 2.0 g / m ^2, the protective layer was 1.1 g / m ^2.

On the day of application, the time from the completion of preparation of the coating solution to the application was all 1 hour. The application was carried out 3 days, 1 week and 2 weeks after the chemical aging. The coated sample thus obtained was left under conditions of 23 ° C. and 55% RH for 3 days to stabilize the hardenability, and then exposed with a semiconductor laser emitting at 780 nm while changing the light amount. Then, it was processed for 45 seconds at 35 ° C. by an automatic processor for X-ray SRX-503 (manufactured by Konica Corporation). Treatment liquid is X
SR-DF (manufactured by Konica Corp.), which is a developing solution and a fixing solution for rays, was used.

<Evaluation of Sensitivity> For each sample after development, Sample No. obtained by the common logarithm of the reciprocal of the exposure amount required to give a density of fog + 1.0 1 (1 from completion of emulsion coating solution preparation)
It is shown as a relative value when the sensitivity of the sample applied after the elapse of time is 100.

[0077]

[Table 1]

As is clear from Table 1, the samples according to the present invention have high sensitivity, and the sensitivity is slightly deteriorated during emulsion storage after chemical ripening, and stable performance is maintained. The spectral sensitizing dye should be added at the time of addition of ammonium thiocyanate at the start of chemical ripening.
Minutes was the best.

Example 2 The samples shown in Table 2 were prepared in the same manner as in Example 1. In addition,
The samples obtained by coating 1 hour, 3 hours and 9 hours after the completion of the preparation of the emulsion coating solution were evaluated in the same manner as in Example 1, and the results are shown in Table 2.

[0080]

[Table 2]

As is clear from Table 2, the samples according to the present invention had high sensitivity, and the deterioration of sensitivity was very slight and stable even when the stagnation time after preparation of the coating solution was long.

[0082]

EFFECT OF THE INVENTION According to the present invention, the sensitivity is high, and the deterioration of the sensitivity is small in the emulsion storage after the chemical ripening.
It was possible to obtain a silver halide photographic emulsion that maintains stable performance and a method for producing the same.

Claims (4)

[Claims] 1. A sensitizing dye in a silver halide photographic emulsion spectrally sensitized by adding a sensitizing dye represented by the following general formula [I] and / or general formula [II] before the completion of chemical ripening. Within 5 hours after the completion of chemical ripening after the addition, the following general formula [II
A silver halide photographic emulsion comprising the addition of a compound represented by the formula [I]. Embedded image In the formula, Z ¹ and Z ³ represent a non-metal atom group necessary for forming a benzothiazole, benzoxazole and naphthoxazole ring which may have a substituent. Z ² represents a 5- to 6-membered carbon atom ring which may have a substituent, and R ¹ and R ² each represent a substituted or unsubstituted alkyl group. X ₁ ⁻ represents a counter ion, and n represents 1 or 2. Embedded image In the formula, Z ⁴ represents a non-metal atom group necessary for forming a 5- or 6-membered nitrogen-containing heterocycle, and R ⁴ and R ⁵ each represent a substituted or unsubstituted alkyl group. R ⁶ represents a hydrogen atom, an alkyl group, an alkoxy group, a phenyl group or a benzyl group, X ₁ ⁻ represents a counter ion, and p, m and n represent 1 or 2. Embedded image In the formula, R ⁷ and R ⁸ each independently represent a hydroxy group, a mercapto group, or a substituted or unsubstituted amino group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkoxycarbonyl group or an alkylthio group. . Z ⁵ represents an atomic group necessary for forming a substituted or unsubstituted 5- or 6-membered ring. 2. The above general formula [II
I] and the spectral sensitization by adding the sensitizing dye represented by the general formula [I] and / or general formula [II] from the end of chemical ripening to the end of preparation of the coating solution. A silver halide photographic emulsion characterized by a feeling. 3. A step of spectrally sensitizing by adding a sensitizing dye represented by the above general formula [I] and / or general formula [II] before completion of chemical ripening, and chemical ripening after addition of the sensitizing dye. A method for producing a silver halide photographic emulsion, which comprises the step of adding the compound represented by the general formula [III] within 5 hours after completion. 4. The above general formula [II
I] and the spectral sensitization by adding the sensitizing dye represented by the general formula [I] and / or the general formula [II] from the completion of the chemical ripening to the preparation of the coating solution. A method for producing a silver halide photographic emulsion, which comprises the step of sensitizing.