JPH11240861A - Iodide ion releasing compound silver halide particle and silver halide photosensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an iodide ion releasing compound useful for silver halide photosensitive materials rapidly releasing iodide ions, high sensitivity and low in fogging. SOLUTION: This compound is expressed by formula I (R1 to R3 are each H, a substituent; EWG is CO2 , OCO, S or the like; L is a bonding group; SOL is a water soluble group; R4 to R9 are each H, a substituent; (n) and (m) are each 1 to 4). The compound of formula I, for example, in the case of a compound of formula II, is obtained by dissolving phenolsulfonic acid in water, adding sodium bicarbonate, cooing, and then dropping chloropropionic acid chloride and adding sodium iodide to the obtained compound of formula III, and heating. The compound is preferably used by adding 1×10<-7> to 30 mol.%, to silver halide to make articles of the silver halide.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an iodide ion releasing compound, silver halide grains, and a silver halide photographic light-sensitive material. More specifically, the present invention relates to an iodide ion releasing compound excellent in sensitivity and fog, silver halide grains, And a silver halide photographic material.

[0002]

2. Description of the Related Art Photographic equipment such as cameras has become increasingly popular in recent years, and opportunities for taking photographs using silver halide photographic materials have been increasing. The demand for higher sensitivity and higher image quality is also increasing.

One of the dominant factors in increasing the sensitivity and image quality of silver halide photographic light-sensitive materials is silver halide grains. Silver halide grains aiming at higher sensitivity and higher image quality. Particle development has traditionally been pursued in the art.

JP-A-5-323487 and JP-A-6-117
No. 81, No. 6-11772, No. 6-27567, No. 6-250309, No. 6-250310, No. 6-2
Nos. 50311, 6-250313, 6-2425
No. 27 and the like realize high sensitivity and improved fog / pressure resistance by using an iodide ion releasing compound in forming silver halide grains.

However, these known iodide ion-releasing compounds have a slow release rate of iodide ions and have a limit in increasing sensitivity, and are insufficient to satisfy recent demands on photosensitive materials. The development of a new technology was desired.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic material having high sensitivity and low fog by using a compound capable of rapidly releasing iodide ions.

[0007]

The above objects of the present invention are as follows. An iodide ion-releasing compound represented by the following general formula [I],

[0008]

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In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom or a substituent, and EWG represents —CO ₂ —, —OCO— or —SO
_{2 -, - SO 2 O -} , - OSO 2 -, - CONR 4 -,
_{-NR 5 CO -, - CSNR 6} -, - NR 7 CS -, -
_{NR 8 -, - O -,} - S -, - CO -, - COCO-,
—NR ₉ SO ₂ —, L represents a linking group, and SOL represents a water-soluble group. R ₄ , R ₅ , R ₆ , R ₇ , R ₈ , and R ₉ represent a hydrogen atom or a substituent. Preferably, the EWG is -CO
_{2 -, - SO 2 -,} - CONHR 4 - ; and particularly preferably, -SO ₂ - is. n and m represent the integer of 1-4.

[0010] 2. An iodide ion releasing compound as described in 1 above, wherein EWG is —SO ₂ —,

3. Silver halide grains formed using at least one of the iodide ion-releasing compounds represented by the above 1 or 2,

4. This has been attained by each of the silver halide photographic light-sensitive materials containing at least one of the silver halide grains shown in the above item 3.

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be specifically described below.

In the general formula [I], R ₁ , R ₂ and R ₃ each represent a hydrogen atom or a substituent, and the substituent is preferably an alkyl group (eg, methyl, ethyl, isopropyl, etc.), a cyano group, a nitro group, an alkoxy group. Groups (eg, methoxy, ethoxy, etc.). Preferably, all of R _{1 to} R ₃ are hydrogen atoms.

The EWG is preferably -CO ₂ -,-
SO ₂ — and —CONHR ₄ —, and particularly preferably —.
SO ₂ —. n and m represent the integer of 1-4. R ₄ ,
R ₅ , R ₆ , R ₇ and R ₈ represent a hydrogen atom or a substituent,
The substituent preferably represents an alkyl group (eg, methyl, ethyl, isopropyl, etc.). The linking group represented by L represents an aromatic group or a heterocyclic group, wherein the aromatic group represents a phenyl group, a naphthyl group, or the like; and the heterocyclic group is a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, Represents a triazine ring, an oxazole ring or the like. Further, they may have a substituent. The substituent is preferably an alkyl group (eg, methyl, ethyl, isopropyl, cyclohexyl, etc.), a cyano group, a nitro group, an amino group, an alkoxy group (eg, methoxy, ethoxy, etc.), a halogen atom (eg, chlorine, bromine, iodine, etc.) And the like. The water-soluble group represented by SOL is specifically -OM,
_-COOM, represents a _{-SO 3 M, -PO 3 M,} 4 quaternary onium salt. M represents a hydrogen atom or an alkali metal. Preferably, -COOM, an -SO ₃ M. Particularly preferably -SO ₃ M. n and m are preferably 1.

Specific examples of the compound of the present invention are shown below.
The compound of the present invention is not limited to this.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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The compound of the present invention can be synthesized by utilizing a known substitution reaction. For example, a method represented by the following equation is used.

[A] -OH + [B] -COCl → base →
[A] -OCO- [B] + H ₂ O: Formula 1 [A] -NH ₂ + [B] -COCl → Base → [A] -N
HCO- [B] + HCl: Formula 2 [A] -OH + [B] -SO ₂ Cl → base → [A] -O
_{SO 2 - [B] + HCl} : Formula 3 [A] is aromatic, [B] represents an aliphatic.

Hereinafter, specific synthetic examples of typical compounds of the present invention will be described.

Synthesis Example 1 (Synthesis of Compound Example 1)

[0026]

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130 g of phenolsulfonic acid was added to 100 parts of water.
The solution was dissolved in 0 ml, and 140 g of sodium hydrogen carbonate was added little by little. After completion of the addition, the mixture was cooled to 10 ° C., and chlorpropionyl chloride (114 g) was slowly added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. Activated carbon 30g
After further stirring, the activated carbon was filtered, and the water in the filtrate was removed under reduced pressure. The compound (1-1) was recrystallized with water to give 1
22 g (62% yield) were obtained. Next, compound (1-1) 10
0 g is dissolved in 800 ml of water, and 400 g of sodium iodide is dissolved.
Was added. Thereafter, the temperature was raised to 60 ° C., and the mixture was stirred for 3 hours. After completion of the reaction, water was removed under reduced pressure and recrystallized from water to obtain 104 g of Compound 1 (yield 73%). Compound 1 is N
Confirmed by MR, MASS.

Synthesis Example 2 (31)

[0029]

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131.8 g of sulfanilic acid was added to 1000 parts of water.
Then, 143.2 g of sodium hydrogen carbonate was added little by little. After completion of the addition, the mixture was cooled to 10 ° C., and 109 g of chloropropionyl chloride was slowly added dropwise. After completion of the dropwise addition, the temperature was raised to room temperature, and the mixture was stirred for 2 hours. Activated carbon 30
g was added and the mixture was further stirred, then the activated carbon was filtered, and the water in the filtrate was removed under reduced pressure. Recrystallized with water to give compound (31-1)
(138 g, yield 60%). Next, the compound (31-
1) 130 g was dissolved in 800 ml of water, and 222 g of sodium iodide was added. Thereafter, the temperature was raised to 60 ° C., and the mixture was stirred for 3 hours. After completion of the reaction, water was removed under reduced pressure and recrystallized with water to obtain 139 g of 31 (yield: 75%). 31 is N
Confirmed by MR, MASS.

Synthesis Example 3 (49)

[0032]

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50 g of the compound (49-1) was dissolved in 250 ml of dichloromethane and cooled to 5 ° C. While maintaining the same temperature, 54.0 g of chlorosulfuric acid was slowly added dropwise. 2
After stirring for an hour, the temperature is raised to room temperature, and 500 ml of a saturated saline solution.
Opened. After stirring for a while while heating, the mixture was filtered.
The collected substance is washed with acetone and dried to give compound (49-2)
62 g (84% yield) were obtained. Next, the compound (49-
The 2) 57 g was dissolved in water _200ml, Na 2 _WO 4 · 2
0.74 g of H ₂ O was added and cooled to 10 ° C. While maintaining the same temperature, 79 g of hydrogen peroxide solution was added dropwise. After the reaction,
Water was removed under reduced pressure. The residue was washed with acetone and dried to obtain 52 g of compound (49-3) (yield: 81%). further,
50 g of the compound (49-3) was dissolved in 400 ml of water, and 109 g of sodium iodide was added. The temperature was raised to 65 ° C. and stirred. After the completion of the reaction, the reaction mixture was cooled, water was removed under reduced pressure, and recrystallized with water to obtain 55 g of 49 (yield: 79%). In addition, 49 was confirmed by NMR and MASS.

The iodide ion releasing compound shown in the present invention means a compound which releases iodide ion under basic conditions. Examples of the base to be used include hydroxide ion, hydroxylamine, ammonium compound and amine. There are compounds and the like, and an alkali hydroxide compound is preferable.

The process for producing a silver halide photographic emulsion and a silver halide photographic light-sensitive material comprises the steps of silver halide grain formation, desalting, spectral sensitization, chemical sensitization, preparation of a coating solution, coating and drying. However, in the present invention, the iodide ion-releasing compound is used in various steps from the start of silver halide grain formation to before the start step, that is, crystal growth and physical ripening, desalting, and spectral sensitization of silver halide grains. , Chemical sensitization, and a coating liquid preparation step.

In the present invention, silver halide grain formation means that after the nuclei of the silver halide grains are formed in the silver halide photographic emulsion according to the present invention, the crystal growth and physical ripening of the silver halide grains are completed. Up to the process. In the present invention, the silver halide emulsion grains are desalted, if necessary, before coating.
Spectral sensitization, chemical sensitization, etc. can be performed, but the coating solution preparation step referred to in the present invention uses the silver halide photographic emulsion according to the present invention after the completion of the last step among the necessary steps. Before the application of the silver halide photographic light-sensitive material is started.

In the present invention, the iodide ion releasing compound can be used in any step of the production of a silver halide emulsion as described above, but is preferably used after the formation near the outermost surface of silver halide grains. Can be That is, it is used after 90% of the amount of silver used up to the formation of silver halide grains is added and before the coating liquid preparation step.

In the present invention, in order to add the iodide ion releasing compound in the step of producing a silver halide photographic emulsion, they may be directly dispersed in the emulsion or may be added to a solvent such as water, methanol or ethanol. A solution dissolved alone or in a mixed solvent may be added, and a method in which an additive is generally added to a silver halide emulsion in the art can be applied.

In the present invention, the amount of the iodide ion releasing compound to be added is 1 × 10 ^{−7 to} 3 × 10 ^{−7 with} respect to silver halide.
0 mol% is preferred, and 1 × 10 ^{−6 to} 5 mol% is more preferred.

In the present invention, the timing and rate of iodide ion release can be controlled by the method of adding the base, the concentration, and the reaction temperature.

In the present invention, the concentration of the base is 1 × 10
^-7 to 50 mol is preferable, 1 * 10 < ^-5 > to 10 mol is more preferable, and 1 * 10 < ^-3 > to 5 mol is particularly preferable.
As for temperature, 20-90 ° C is preferred, 30-85 ° C is more preferred, and 35-80 ° C is still more preferred. In the present invention, when a base is used for releasing a halide ion, p
H may be controlled. The pH at this time is preferably 2 to 12, and more preferably 3 to 11.

The iodide ion released is preferably 0.001 to 30 mol% of the total silver halide amount, and 0.01 to 1 mol%.
0 mol% is more preferred.

In the present invention, the iodide ion releasing compound may release all of the iodine atoms in the compound, or a part thereof may remain without being decomposed.

In the present invention, the iodide ion releasing compounds may be used alone or in combination of two or more.

The silver halide grains in the silver halide photographic emulsion of the present invention preferably have dislocation lines therein. There is no particular limitation on the position where the dislocation line exists, but it is preferable that it exists near the outer peripheral portion, near the ridge line, or near the vertex of the silver halide grain. The introduction position of the dislocation lines in the silver halide grains is preferably 50% or less, more preferably 60% or more and less than 85%, based on the total silver content of the silver halide grains. The number of dislocation lines is preferably 30% or more (number) of silver halide grains having 5 or more dislocation lines.
It is more preferably 0% or more, further preferably 80% or more. In each case, the number of dislocation lines in one particle is preferably 10 or more, more preferably 20 or more, and even more preferably 30 or more.

Dislocation lines of silver halide grains are described, for example, in J. Am. F. Hamilton, Photo. Sci.
Eng. 11 (1967) 57 and T.I. Shiozaw
a. Soc. Photo. Sci. Japan35
(1972) 213 can be observed by a direct method using a transmission electron microscope at a low temperature. That is, silver halide grains taken out from the emulsion without paying enough pressure to generate new dislocation lines on the grains are placed on a mesh of an electron microscope to prevent damage (printout, etc.) by the electron beam. The specimen is observed by a transmission method in a cooled state. At this time, the thicker the silver halide grains, the more difficult it is for an electron beam to pass through. Therefore, a clearer observation can be obtained by using a high-pressure electron microscope. From the particle photograph obtained by such a method,
The position and number of dislocation lines in each silver halide grain can be determined.

The method of introducing dislocation lines into silver halide grains is not particularly limited. For example, a method of adding an aqueous solution of an iodide ion such as potassium iodide and a solution of a water-soluble silver salt by double jet, a method of adding silver iodide A method of adding fine particles, a method of adding only an iodine ion solvent,
A known method such as a method using an iodide ion releasing compound described in No. 81 or the like is used.

The silver halide grains contained in the silver halide photographic emulsion according to the present invention may have a regular crystal structure such as cubic, octahedral or tetradecahedral, or may have a spherical or plate-like shape. It may have such an irregular crystal form. In these particles, the ratio between the (100) plane and the (111) plane can be arbitrarily used. Further, a composite of these crystal forms may be used, and particles of various crystal forms may be mixed.

In the present invention, the average grain size of the silver halide grains is preferably from 0.2 to 10 μm, more preferably from 0.3 to 7.0 μm.
Is more preferable, and 0.4 to 5.0 μm is most preferable.

In the present invention, any silver halide photographic emulsion such as a polydisperse emulsion having a wide particle size distribution and a monodisperse emulsion having a narrow particle size distribution is used, but a monodisperse emulsion is preferable.

In the present invention, the silver halide photographic emulsion may be any silver halide such as silver iodobromide, silver iodochlorobromide, silver iodochloride and the like. However, silver iodobromide and silver iodochlorobromide are particularly preferred.

In the present invention, the average silver iodide content of silver halide grains contained in a silver halide photographic emulsion is from 1 to 4
0 mol%, more preferably 2 to 2 mol%.
0 mol%.

As the silver halide grains contained in the silver halide photographic emulsion of the present invention, core / shell type grains can be preferably used. The core / shell type particles are particles composed of a core and a shell covering the core,
The shell is formed by one or more layers. The silver iodide content of the core and the shell are preferably different from each other.

For producing the silver halide photographic emulsion of the present invention, various methods well known in the art can be used. That is, a single jet method, a double jet method, a triple jet method, a silver halide fine particle supply method, or the like can be used in any combination. Also, the pH in the liquid phase in which silver halide is produced,
A method of controlling pAg according to the growth rate of silver halide can also be used.

For the production of the silver halide photographic emulsion of the present invention, a seed emulsion can also be used. When a seed emulsion is used, the silver halide grains in the seed emulsion may have a regular crystal structure such as cubic, octahedral, or tetradecahedral, or may have a spherical or plate-like shape. It may have an irregular crystal form. In these particles, the (100) plane and the (11) plane
1) Any ratio of planes can be used. Further, a composite of these crystal forms may be used, and particles of various crystal forms may be mixed. In the present invention, when tabular silver halide grains are used, the silver halide grains in the seed emulsion used are preferably twinned silver halide grains having twin planes, and two opposite parallel silver halide grains are used. Particularly preferred are twinned silver halide grains having a twinned plane.

In the present invention, whether a seed emulsion is used or a seed emulsion is not used, the conditions for silver halide nucleation and ripening are those known in the art. Can be.

For the production of the silver halide photographic emulsion of the present invention, a silver halide solvent known in the art can be used. Examples of silver halide solvents include:
(A) US Patent Nos. 3,271,157 and 3,53
Nos. 1,289 and 3,574,628;
No. 1019, No. 54-158917, and Japanese Patent Publication No. 58
Organic thioethers described in No.
(B) JP-A-53-82408 and 55-29829
And thiourea derivatives having a thiocarbonyl group sandwiched between an oxygen or sulfur atom and a nitrogen atom described in JP-A-53-144319 and the like. Silver solvent, (d) JP-A-54-
Imidazoles described in 100717 and the like;
(E) sulfites, (f) thiocyanates, (g) ammonia, (h) ethylenediamines substituted with hydroxylalkyl described in JP-A-57-196228, and (i) JP-A-57-202531. Substituted mercaptotetrazoles described in, for example, (j) water-soluble bromide,
(K) Benzoimidazole derivatives described in JP-A-58-54333 and the like.

For the production of the silver halide photographic emulsion of the present invention, any of an acidic method, a neutral method and an ammonia method can be used.

In the production of the silver halide photographic emulsion of the present invention, halide ions and silver ions are simultaneously mixed,
One may be mixed while the other is present. In consideration of the critical growth rate of silver halide crystals, halide ions and silver ions can be added sequentially or simultaneously while controlling the pAg and pH in the mixing vessel. In any step of silver halide formation, the halogen composition of the silver halide grains may be changed by using a conversion method.

In the production of the silver halide photographic emulsion of the present invention, cadmium salts, zinc salts, lead salts, thallium salts, iridium salts are formed during the process of nucleating silver halide grains and / or growing the generated nuclei. (Including a complex salt), a rhodium salt (including a complex salt), iron or another salt of a Group VIII metal (including a complex salt), and the like. These metals can be contained on the particle surface.

In the present invention, twin silver halide grains having two opposing parallel twin planes can be used, but in this case, tabular silver halide grains are preferred. The twins are silver halide twins having one or more twin planes in one grain, and the classification of twins is based on the report by Klein and Moiser. (Photographhi
she Korrespondentz) Volume 99
Page 100, p. 57. When tabular silver halide grains are used in the present invention, it is preferable that 50% or more of the total projected area of the silver halide grains contained in the silver halide photographic emulsion of the present invention is tabular silver halide grains. , More preferably at least 60%, even more preferably at least 80%.

When tabular silver halide grains are used in the present invention, the ratio of tabular silver halide grains having two twin planes parallel to the main plane is 60% or more in terms of the number of silver halide grains. And more preferably 70
%, More preferably 80% or more.

In the present invention, tabular silver halide grains are silver halide grains having an aspect ratio (ratio of diameter to thickness of silver halide grains) of 1.3 or more. The aspect ratio is preferably 3.0 or more, and more preferably 5.0 or more.

To determine the aspect ratio, first, the diameter and thickness of the silver halide grains are determined by the following method. A latex ball having a known particle size as an internal standard and a sample coated such that the main plane was oriented parallel to the support were prepared on the support, and shadowing was performed by a carbon deposition method from a certain direction. Thereafter, a replica sample is prepared by a normal replica method. An electron micrograph of the sample is taken, and the projected area diameter and thickness of each silver halide grain are determined using an image processing device or the like. In this case, the thickness of the silver halide grains can be calculated from the internal standard and the length of the shadow of the silver halide grains.

The twin plane of the silver halide grains can be observed with a transmission electron microscope. The specific method is as follows. First, a sample is prepared by coating a silver halide emulsion on a support so that the main plane of the tabular silver halide grains is oriented substantially parallel to the support. This is cut using a diamond cutter to a thickness of 0.1 μm
Obtain approximately thin sections. By observing this section with a transmission electron microscope, the presence of twin planes can be confirmed.

In the production of the silver halide photographic emulsion of the present invention, a substance capable of forming a protective colloid can be used as a dispersion medium, but gelatin is preferably used.

In the present invention, when gelatin is used as a dispersion medium, lime-treated gelatin, acid-treated gelatin, ion-exchanged gelatin and the like can be used. For details on the gelatin production method, see Arthur Weiss, "The Macromolecular Chemistry of
Gelatin "(Academic Press, 1964)
And so on.

Examples of substances that can form protective colloids other than gelatin include gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethylcellulose, carboxymethylcellulose, and cellulose sulfate. Cellulose derivatives such as sodium alginate, starch derivatives, etc., polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-n-vinylpyrrolidone, polyacrylic acid, polyacrylamide, polymethacrylic acid, polyvinylimidazole, polyvinylpyrazole, etc. There may be mentioned various kinds of synthetic or semi-synthetic hydrophilic polymer substances such as one or copolymer. In the production of the silver halide photographic emulsion of the present invention, reduction sensitization can be carried out using a method known in the art. Reduction sensitization may be performed during or after silver halide grain formation.

As a more specific method of reduction sensitization, a method of ripening and growing at a low pAg by supplying silver ions to silver halide grains, which is referred to as silver ripening in the art, and using an alkaline compound, etc. It is also possible to use any method or a combination of these methods, such as a method of ripening and growing by increasing the pH and adding a reducing agent. In the present invention, when using a reducing agent, for example, thiourea dioxide or ascorbic acid and its derivatives, stannous salts, borane compounds, hydrazine derivatives, formamidine sulfinic acid, silane compounds, amines and polyamines and sulfites Can be used, but preferably,
Thiourea dioxide, ascorbic acid and its derivatives, and stannous salts are used.

In producing the silver halide photographic emulsion of the present invention, an oxidizing agent known in the art can be used.
Examples of the oxidizing agent include hydrogen peroxide (water) and its adducts: H ₂ O ₂ , NaBO ₂ , H ₂ O ₂ -3H ₂ O,
_{NaCO 3 -3H 2 O 2, Na} 4 P 2 O 7 -2H
Etc. _{2 O 2, 2Na 2 SO 4} -H 2 O 2 -2H 2 O. Peroxy acid salts: K ₂ S ₂ O ₃ , K ₂ C ₂ O ₃ , K ₄ P ₂
O ₃ , K ₂ [Ti (O) ₂ C ₂ O ₄ ] -3H ₂ O, peracetic acid, ozone, thiosulfonic acid compound and the like can be mentioned.

In the production of the silver halide photographic emulsion of the present invention, the above reduction sensitization and the addition of an oxidizing agent can be carried out in combination.

In the present invention, silver halide grains according to the present invention can be formed by supplying fine silver halide grains. The silver halide fine grains may be prepared in advance before preparing the silver halide grains according to the present invention, or may be prepared in parallel with the preparation of the silver halide grains. In the case of preparing by changing the latter, see JP-A-1-11-1.
Nos. 83417, 2-44335, etc. can be used to produce fine silver halide grains by using a separate mixer provided outside the reaction vessel in which the silver halide grains according to the present invention are formed. Although it is possible to provide a preparation container separately from the mixer, the silver halide fine particles once prepared in the mixer can be arbitrarily selected so as to be suitable for a growth environment in a reaction container in which the preparation of the silver halide particles concerned is performed. It is preferable to supply the mixture to the reaction vessel after the preparation.

The method for preparing the silver halide fine grains is preferably an acidic to neutral environment (pH ≦ 7).

To produce the silver halide fine particles, a water-soluble silver salt containing silver ions and an aqueous solution containing halide ions may be mixed while appropriately controlling the supersaturation factor.
Regarding control of the supersaturation factor, see JP-A-63-92942.
And JP-A-63-31244 can be referred to.

PAg for producing the silver halide fine particles
Is preferably at least 3.0, more preferably at least 5.0, even more preferably at least 8.0 in order to suppress the generation of reduced silver nuclei in the silver halide fine grains themselves. .

The temperature for producing the silver halide fine particles is as follows:
The temperature is preferably 50 ° C. or lower, more preferably 40 ° C. or lower, and most preferably 35 ° C. or lower.

As the protective colloid used for producing the silver halide fine particles, the above-mentioned protective colloid-forming substance used for producing the silver halide particles according to the present invention can be used.

When silver halide fine particles are formed at a low temperature, coarsening of the particle size due to Ostwald ripening after the formation of the silver halide fine particles can be suppressed. However, at a low temperature, gelatin is easily coagulated. 2-1664
It is preferable to use low molecular weight gelatin described in No. 22, etc., a synthetic molecular compound having a protective colloid action on silver halide grains, or a natural high molecular compound other than gelatin. The concentration of the protective colloid is preferably 1% by weight
Or more, more preferably 2% by weight or more, still more preferably 3% by weight.

The silver halide fine particles have a particle size of 0.1 μm.
Or less, more preferably 0.05 μm or less.

The silver halide fine grains may optionally contain the above-described reduction sensitization and optionally metal ions and the like.

In the production of the silver halide photographic emulsion of the present invention, desalting can be carried out during or after the formation of silver halide grains for the purpose of suppressing the progress of physical ripening or removing insoluble salts. Desalting is performed, for example, by Research Disclosure (Research Disc).
Hereafter, it is abbreviated as RD. ) No. 17643, paragraph II.

More specifically, in order to remove unnecessary soluble salts from the precipitated product or the emulsion after physical ripening, a Nudel washing method in which gelatin is gelled may be used, and inorganic salts and anionic salts may be used. A precipitation method using a surfactant, an anionic polymer (eg, polystyrene sulfonic acid), or a gelatin derivative (eg, acylated gelatin, carbamoylated gelatin) can be used.

In addition, desalting using membrane separation described in Chemical Engineering Handbook, Revised 5th Edition (edited by The Chemical Industry Association, Maruzen), pages 924 to 954 can also be used.

Regarding the method of membrane separation, RD No. 102, 10208 and 131, 13122, JP-B-59-43727, JP-B-6-27008, and JP-A-6-27008
2-113137, 57-209823, 59
-43727, 62-11137, 61-2
No. 19948, No. 62-23035, No. 63-401
No. 37, 63-400039, JP-A-3-1409
No. 46, No. 2-172816, No. 2-172817
And the methods described in JP-A No. 4-22942 can also be referred to.

In the preparation of the silver halide photographic emulsion of the present invention, conditions other than those described above are described in JP-A-61-66.
No. 43, No. 61-14630, No. 61-112142
No. 62-157024, No. 62-18556,
63-92942, 63-151618, 6
Nos. 3-163451, 63-220238, 63
-311244, RD 365, 36544, 367
Appropriate conditions can be selected with reference to Vol. 36736, Vol.

In constructing a color photographic light-sensitive material using the silver halide emulsion of the present invention, a silver halide emulsion which has been subjected to physical ripening, chemical ripening and spectral sensitization is used. The additive used in such a process is RD176
43, 18716 and 308119. Table 1 shows relevant descriptions.

[0087]

[Table 1]

Known photographic additives that can be used in forming a color photographic light-sensitive material using the silver halide emulsion of the present invention are also described in the above RD. Table 2 shows relevant descriptions.

[0089]

[Table 2]

In constructing a color photographic light-sensitive material using the silver halide emulsion of the present invention, various couplers can be used, and specific examples are described in the above RD. Table 3 shows relevant descriptions.

[0091]

[Table 3]

The additive used for forming a color photographic light-sensitive material using the silver halide emulsion of the present invention is RD3
It can be added by a dispersion method described in 08119XIV or the like. When a color photographic light-sensitive material is formed using the silver halide emulsion of the present invention, the RD1
The supports described in pages 765328, RD18716 647-648 and RD308119 XIX can be used.

The color photographic light-sensitive material using the silver halide emulsion of the present invention includes the aforementioned RD308119VII-K
An auxiliary layer such as a filter layer or an intermediate layer described in the section can be provided.

The color photographic light-sensitive material using the silver halide emulsion of the present invention includes the aforementioned RD308119VII-K
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in the section can be adopted.

The silver halide emulsion of the present invention is preferably used for various color light-sensitive materials represented by general or movie color negative films, slide or television color reversal films, color papers, color positive films and color reversal papers. Can be applied.

The color photographic light-sensitive material using the silver halide emulsion of the present invention is described in RD17643 28-29.
RD18716, page 615 and RD308119, XIX.

[0097]

The present invention will be specifically described below with reference to examples.
The present invention is not limited to these. Example 1 (Preparation of seed emulsion T-1)
A seed emulsion having parallel twin planes was prepared. (E-1 solution) Deionized alkali-treated gelatin (average molecular weight 15,000) 244.0 g Potassium bromide 156.6 g HO (CH₂CH₂O)_m(CH (CH₃) CH₂O)_19.8(CH₂CH ₂ O)_n10% methanol solution of H (m + n = 9.77) 0.48 ml 34.0 liters with water (F-1 solution) 1200 g of silver nitrate 3716 ml with water (G-1 solution) Deionized alkali-treated gelatin (average molecular weight 15,000) 31.6 g Potassium bromide 906.0 g 4.0 L with water (H-1 solution) Ammonia water (28%) 299 ml (I-1 solution) Water 8.0 L (J-1 solution) Ossein gelatin 400 0.032 g of water 4832 ml (K-1 solution) 69.2 g of potassium bromide 386 ml of water (L-1 solution) 56 wt% acetic acid aqueous solution 1000 ml Using a stirrer described in JP-A-62-160218, 3
Solution I-1 was added to solution E-1 which was vigorously stirred at 0 ° C.
After that, the F-1 solution and the G-1 solution are subjected to double jet method 2
Per minute to produce silver halide nuclei.

Thereafter, the solution J-1 was added, the temperature was raised to 68 ° C. over 41 minutes, the solution H-1 was added, and the mixture was aged for 5 minutes. Thereafter, the K-1 solution was further added, and one minute later, the pH was adjusted to 4.7 using the L-1 solution, and immediately desalting was performed by a conventional method. When this seed emulsion was observed with an electron microscope, the average grain size (grain size in terms of projected area circle) having two twin planes parallel to each other was 0.31 μm, and the grain size distribution was 16%.
Was obtained.

(Preparation of Emulsion Em-1) Seed emulsion (T-1)
And using the solution shown below to prepare an emulsion (Em-1)
Was. (H-2 solution) Ossein gelatin 223.6 g HO (CH₂CH₂O)_m(CH (CH₃) CH₂O)_19.8(CH₂CH ₂ O)_nH (m + n = 9.77) 10% methanol solution 3.6 ml Emulsion (T-1) 0.774 mol equivalent 5904 ml with water (I-2 solution) 3.5N silver nitrate aqueous solution 6490 ml (J-2 solution) 5N potassium bromide aqueous solution 7,500 ml (K-2 solution) Fine grain emulsion composed of 3.0% by weight of gelatin and silver iodide fine grains (average grain size: 0.05 μm) (Preparation method is shown below)

<Preparation method of fine grain emulsion> 5000 m of a 6.0% by weight gelatin solution containing 0.06 mol of potassium iodide
To each liter, 2,000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium bromide were added at a constant speed over 10 minutes. During the formation of the fine particles, the pH was adjusted to 2.0 using nitric acid.
And the temperature was controlled at 40 ° C. After the addition was completed, the pH was adjusted to 6.0 using an aqueous sodium carbonate solution. The finished weight was 12.53 kg.

(Liquid L-2) 1.75N Potassium bromide aqueous solution required amount (M-2 liquid) 56% by weight acetic acid aqueous solution Required amount (N-2 liquid) 3.5N Potassium bromide aqueous solution 500ml H in the reaction vessel -2 solution is added and with vigorous stirring,
Solution I-2, Solution J-2 and Solution K-2 were added by the simultaneous mixing method according to the combination shown in Table 4 to grow a seed crystal to prepare a core / shell type silver halide emulsion.

Here, the addition rate of the liquids I-2, J-2, and K-2 was changed in a function-wise manner with respect to the addition time in consideration of the critical growth rate. The generation of small particles and the deterioration of the particle size distribution due to Ostwald ripening between growing particles were prevented.

In the crystal growth, the first addition was performed while controlling the solution temperature in the reaction vessel to 75 ° C. and the pAg to 8.8, and then the solution temperature in the reaction vessel was reduced to 60 ° C. in 15 minutes. Solution 2 was added over 4 minutes, and solution K-2 was added in an amount equivalent to 2% of the total silver used, followed by a second addition. Second
The addition was performed by setting the solution temperature in the reaction vessel to 60 ° C. and the pAg to 9.
8. The pH was controlled at 8.5. For control of pAg and pH, L-2
Solution M-2 was added.

After grain formation, desalting was carried out according to the method described in JP-A-5-72658, and gelatin was added and dispersed to obtain an emulsion having a pAg of 8.06 and a pH of 5.8 at 40 ° C. Was.

When the silver halide grains in this emulsion were observed with an electron microscope, they were hexagonal tabular monodispersed silver halide grains having an average particle size of 1.30 μm and a particle size distribution of 17% and an average aspect ratio of 8.0. The main surface is a (111) plane, and 95% or more of all silver halide grain surfaces are (111) planes.
Was composed of planes. The tabular silver halide grains had dislocation lines.

[0106]

[Table 4]

(Preparation of Emulsions Em-2 to Em-14) The same procedure as in the preparation of Emulsion (Em-1) was carried out except that the compounds described in Table 5 were added in the amounts indicated relative to the total silver halide before desalting. To prepare emulsions (Em-2 to Em-14).

[0108]

[Table 5]

These emulsions Em-1 to Em-14 were used after being optimally subjected to spectral sensitization and chemical sensitization.

On a triacetylcellulose film support provided with an undercoat layer, layers having the following compositions were sequentially formed from the support side to obtain a multilayer color photographic light-sensitive material sample 10.
Nos. 1-114 were created.

[0111] The addition amount is expressed in grams per 1 m ^2.
The sensitizing dye (indicated by SD) was represented by the number of moles per mole of silver, in terms of the amounts of silver halide and colloidal silver. First layer (antihalation layer) Black colloid layer 0.16 UV-1 0.3 CM-1 0.123 CC-1 0.044 OIL-1 0.167 Gelatin 1.33

Second Layer (Intermediate Layer) AS-1 0.160 OIL-1 0.20 Gelatin 0.69

Third layer (low-sensitivity red-sensitive layer) Silver iodobromide a 0.20 Silver iodobromide b 0.29 SD-1 2.37 × 10 ⁻⁵ SD-2 1.2 × 10 ^{− 4} SD-3 2.4 × 10 ^-4 SD-4 2.4 × 10 ^-6 C-1 0.32 CC-1 0.038 OIL-2 0.28 AS-2 0.002 Gelatin 0.73

Fourth layer (medium-speed red-sensitive layer) Silver iodobromide c 0.10 Silver iodobromide d 0.86 SD-1 4.5 × 10 ⁻⁵ SD-2 2.3 × 10 ^{− 4} SD-3 4.5 × 10 ^-4 C-2 0.52 CC-1 0.06 DI-1 0.047 OIL-2 0.46 AS-2 0.004 Gelatin 1.30

Fifth layer (high-sensitivity red-sensitive layer) Silver iodobromide c 0.13 Silver iodobromide d 1.18 SD-1 3.0 × 10 ⁻⁵ SD-2 1.5 × 10 ^{− 4} SD-3 3.0 × 10 ^-4 C-2 0.047 C-3 0.09 CC-1 0.036 DI-1 0.024 OIL-2 0.27 AS-2 0.006 Gelatin 1. 28

Sixth Layer (Intermediate Layer) OIL-1 0.29 AS-1 0.23 Gelatin 1.00

Seventh layer (low-sensitivity green color-sensitive layer) Silver iodobromide a 0.19 Silver iodobromide b 0.062 SD-4 3.6 × 10 ^-4 SD-5 3.6 × 10 ^{− 4} M-1 0.18 CM-1 0.033 OIL-1 0.22 AS-2 0.002 AS-3 0.05 Gelatin 0.61

Eighth Layer (Intermediate Layer) OIL-1 0.26 AS-1 0.054 Gelatin 0.61

Ninth layer (medium-sensitive green color-sensitive layer) Silver iodobromide e 0.54 Silver iodobromide f 0.54 SD-6 3.7 × 10 ⁻⁴ SD-7 7.4 × 10 ^{− 5} SD-8 5.0 × 10 ^-5 M-1 0.17 M-2 0.33 CM-1 0.024 CM-2 0.029 DI-2 0.024 DI-3 0.005 OIL-1 0.73 AS-3 0.035 AS-2 0.003 Gelatin 1.80

Tenth Layer (High Sensitive Green Color Sensitive Layer) Em-1 1.19 SD-6 4.0 × 10 ^-4 SD-7 8.0 × 10 ^-5 SD-8 5.0 × 10 ^{− 5} M-1 0.065 CM-2 0.026 CM-1 0.022 DI-3 0.003 DI-2 0.003 OIL-1 0.19 OIL-2 0.43 AS-3 0.017 AS -2 0.014 gelatin 1.23

Eleventh Layer (Yellow Filter Layer) Yellow Colloidal Silver 0.05 OIL-1 0.18 AS-1 0.16 Gelatin 1.00

Twelfth layer (low-sensitivity blue-sensitive layer) Silver iodobromide b 0.22 Silver iodobromide a 0.08 Silver iodobromide h 0.09 SD-9 6.5 × 10 ^-4 SD -10 2.5 × 10 ^-4 Y-1 0.77 DI-4 0.017 OIL-1 0.31 AS-2 0.002 Gelatin 1.29

Thirteenth layer (high-sensitivity blue-sensitive layer) Silver iodobromide h 0.41 Silver iodobromide i 0.61 SD-9 4.4 × 10 ^-4 SD-10 1.5 × 10 ^{− 4} Y-1 0.23 OIL-1 0.10 AS-2 0.004 Gelatin 1.20

Fourteenth layer (first protective layer) Silver iodobromide j 0.30 UV-1 0.055 UV-2 0.110 OIL-2 0.30 gelatin 1.32

Fifteenth layer (second protective layer) PM-1 0.15 PM-2 0.04 WAX-1 0.02 D-1 0.001 Gelatin 0.55

The characteristics of the silver iodobromide are shown below (the average grain size here is the average of the length of one side of a cube of the same volume). The method for producing the emulsion conforms to the above-described Em-1. Emulsion No. Average particle size (μm) Average AgI amount (mol%) Average diameter / thickness ratio Silver iodobromide a 0.30 2.0 1.0 b 0.40 8.0 1.4 c 0.60 7.0 3 0.1 d 0.74 7.0 5.0 e 0.60 7.0 4.1 f 0.65 8.7 6.5 h 0.65 8.0 1.4 i 1.00 8.0 2 0.0 j 0.05 2.0 1.0

Incidentally, in addition to the above composition, a coating aid SU-
1, SU-2, SU-3, dispersing aid SU-4, viscosity modifier V-1, stabilizers ST-1, ST-2, antifoggant A
F-1, two types of polyvinylpyrrolidone (AF-2) having a weight average molecular weight of 10,000 and a weight average molecular weight of 1,000,000, inhibitors AF-3, AF-4 and AF-
5. Hardeners H-1, H-2 and preservative Ase-1 were added.

The structure of the compound used in the above sample is shown below.

[0129]

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[0130]

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[0131]

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[0135]

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[0136]

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[0137]

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Each of the samples was subjected to the following color development processing. << Reference color development processing >> Processing step Processing time Processing temperature Replenishment amount * Color development 3 minutes 15 seconds 38 ± 0.3 ° C. 780 ml Bleaching 45 seconds 38 ± 2.0 ° C. 150 ml Stable 60 seconds 38 ± 5.0 ° C. 830 ml Drying 1 minute 55 ± 5.0 ° C.-* The replenishment amount is a value per m ² of the photosensitive material.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used. Color developer Water 800 ml Potassium carbonate 30 g Sodium bicarbonate 2.5 g Potassium sulfite 3.0 g Sodium bromide 1.3 g Potassium iodide 1.2 mg Hydroxylamine sulfate 2.5 g Sodium chloride 0.6 g 4-amino-3-methyl -N-ethyl-N- (β-hydroxylethyl) aniline sulfate 4.5 g Diethylenetriaminepentaacetic acid 3.0 g Potassium hydroxide 1.2 g Add water to make 1 liter, and add potassium hydroxide or 20%
Adjust to pH 10.06 with sulfuric acid.

Color developing replenisher Water 800 ml Potassium carbonate 35 g Sodium bicarbonate 3 g Potassium sulfite 5 g Sodium bromide 0.4 g Hydroxylamine sulfate 3.1 g 4-Amino-3-methyl-N-ethyl-N- (β-hydroxyl Ethyl) aniline sulfate 6.3 g potassium hydroxide 2 g diethylenetriaminepentaacetic acid 3.0 g water was added to make 1 liter, and potassium hydroxide or 20%
Adjust to pH 10.18 with sulfuric acid.

Bleaching solution Water 700 ml 1,3-Diaminopropanetetraacetic acid iron (III) ammonium 125 g ethylenediaminetetraacetic acid 2 g sodium nitrate 40 g ammonium bromide 150 g glacial acetic acid 40 g Add water to make 1 liter, and use ammonia water or glacial acetic acid. And adjust to pH 4.4.

Fixing solution Water 800 ml Ammonium thiocyanate 120 g Ammonium thiosulfate 150 g Sodium sulfite 15 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 4.4 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Fixing replenisher Water 800 ml Ammonium thiocyanate 150 g Ammonium thiosulfate 180 g Sodium sulfite 20 g Ethylenediaminetetraacetic acid 2 g After adjusting the pH to 6.5 using aqueous ammonia or glacial acetic acid, add water to make 1 liter.

Stabilizing Solution and Stabilizing Replenisher Water 900 ml Paraoctylphenyl polyoxyethylene ether (n = 10) 2.0 g Dimethylol urea 0.5 g Hexamethylenetetramine 0.2 g 1,2-Benzoisothiazolin-3-one 0.1 g Siloxane (UCC L-77) 0.1 g Ammonia water 0.5 ml After adding water to make 1 liter, add ammonia water or 50
Adjust to pH 8.5 with% sulfuric acid.

[0145] Samples 101 to 114 were prepared using white light.
/ 200 seconds, after step wedge with 3.2CMS,
Immediately perform the above color development processing to obtain a characteristic curve,
The green sensitivity (reciprocal of the exposure amount giving a density of fog density + 0.10, indicated by a relative value with the value of sample 101 being 100) was determined.

Each sample was stored for one week under the conditions of 40 ° C. and 80% RH, and then exposed and treated in the same manner. The fog is shown as a relative value with the value of sample 101 being 100. Table 6 shows the results.

[0147]

[Table 6]

Table 6 shows that emulsions Em-5 to Em-1 of the present invention
Coating Samples 105 to 114 using No. 4 were prepared as Comparative Emulsion Em-
Excellent sensitivity and low fog were exhibited for coating samples 101 to 104 using 1 to Em-4.

Example 2 (Preparation of Emulsions Em-15 to Em-28) In Comparative Emulsion Em-1 of Example 1, the compounds shown in Table 7 were added after spectral sensitization in the amounts described in relation to total silver halide. An emulsion (Em-15 to Em-15) was prepared in the same manner except that chemical sensitization was performed later.
Em-28) was prepared.

[0150]

[Table 7]

The Em-1 of the tenth layer in Example 1 was replaced with the Em
Multilayer color photographic light-sensitive material samples 201 to 214 were prepared and evaluated in the same manner as in Sample 101, except that the temperature was changed to -15 to Em-28. The fog value of the sample 201 was 100
The relative values are shown below. Table 8 shows the results.

[0152]

[Table 8]

Table 8 shows that the emulsions Em-19 to Em-
Coating samples 205 to 214 using No. 28 were emulsion Em-1
Excellent sensitivity was exhibited with respect to coating samples 201 to 204 using 5-Em-18. Also, it can be seen that fog is low.

Example 3 Measurement of Iodide Ion Release Rate O Square Wave V was measured using a BAS 100B / W Electrochemical Workstation.
The release rate was calculated by measuring the oxidation potential of the iodide ion of each compound by the alternatemetry method. As the electrodes, a silver / silver chloride electrode was used as a reference electrode, a fine gold electrode was used as a working electrode, and a platinum electrode was used as a match. The pH of the sodium bicarbonate-sodium carbonate buffer solution was adjusted to 10.5, each compound was dissolved in the aqueous solution, and the oxidation potential at 42 ° C. was measured. The release rate was calculated by taking the ratio of the oxidation potential of the KI solution to the oxidation potential of each compound as the release rate, and changing over time. Table 9 shows the measurement and calculation results.
Shown in Table 9 shows the time to release 90% of iodide ions for each compound.

[0155]

[Table 9]

[0156]

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[0157]

According to the present invention, a novel iodide ion releasing compound and a silver halide photographic light-sensitive material excellent in sensitivity, fog and storage stability can be provided.

Claims (4)

[Claims] 1. An iodide ion releasing compound represented by the following general formula [I]. Embedded image In the formula, R ₁ , R ₂ and R ₃ represent a hydrogen atom or a substituent,
EWG is _{-CO 2 -, - OCO -,} - SO 2 -, - SO
_{2 O -, - OSO 2 -} , - CONR 4 -, - NR 5 CO
_{-, - CSNR 6 -, -} NR 7 CS -, - NR 8 -, -
O -, - S -, - CO -, - COCO -, - NR 9 SO
_2- , L represents a linking group, and SOL represents a water-soluble group. R ₄ , R
₅ , R ₆ , R ₇ , R ₈ and R ₉ represent a hydrogen atom or a substituent. n and m represent the integer of 1-4. 2. The iodide ion releasing compound according to claim 1, wherein the EWG is —SO ₂ —. 3. A silver halide grain formed using at least one of the iodide ion releasing compounds according to claim 1 or 2. 4. A silver halide photographic material comprising at least one of the silver halide grains as defined in claim 3.