JPH08122956A - Silver halide photographic emulsion - Google Patents

Abstract

(57) [Summary] [Objective] To provide a silver halide photographic emulsion with high sensitivity and low fog. A silver halide photographic emulsion characterized in that a metal chelating agent and a saccharide are added to a silver halide photographic emulsion which has been subjected to reduction sensitization and / or chemical ripening.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a silver halide photographic emulsion, and more particularly to a silver halide photographic emulsion having high sensitivity and low fog.

[0002]

2. Description of the Related Art In recent years, the demand for silver halide photographic emulsions has become strict, and it is required to have photographic characteristics such as high sensitivity, low fog and excellent graininess.

A means for increasing the emulsion sensitivity is to improve the quantum efficiency of light absorbed by one grain of silver halide crystal during exposure. Factors that reduce the quantum efficiency include recombination of electrons and holes and latent image dispersion.
In order to solve these problems, a reduction sensitization method in which a silver nucleus having a small developing activity is formed in a silver halide crystal or on the surface thereof is well known.

The reduction sensitization method has been extensively studied for a long time. Reducing substances, that is, those using tin compounds in US Pat. No. 2,487,850, those using polyamine compounds in US Pat. No. 2,512,925, those using thiourea dioxide compounds British Patent No. 78
No. 9,823, and in particular, thiourea dioxide is also effective as a reduction enhancer.
Further, those using ascorbic acid or a derivative thereof are disclosed in JP-B-57-33572, JP-A-58-1410, and JP-A-Hei-2.
-136852, 2-168247, 2-18
9541. Further, various reduction sensitization methods are described in US Pat. Nos. 2,518,698 and 3,201,
No. 254, No. 3,411,917, No. 3,77.
9,777 and 3,930,867.

However, as is known, the silver nuclei produced by reduction sensitization are thermally unstable,
A light-sensitive material using a silver halide photographic emulsion whose sensitivity is increased by reduction sensitization has a big defect that it is easily fogged.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a silver halide photographic emulsion having high sensitivity and low fog.

[0007]

SUMMARY OF THE INVENTION The above objects of the present invention are as follows.
It has been found to be achieved by a silver halide photographic emulsion which is characterized by the addition of a metal chelating agent and a saccharide to a reduction sensitized and / or chemically ripened silver halide photographic emulsion.

[0008] As a particularly preferred embodiment, tartaric acids are ethylenediaminetetraacetic acid, compounds such as nitrilotriacetic acid, Uramiru diacetate, comprises at least one of these compounds, per mol of silver halide 1 × 10 ^{over 7} ~
^Contains 1 × 10 ⁻¹ molar amount. Further, the saccharide is a monosaccharide,
Disaccharides and polysaccharides, at least 1 of these compounds
Including types, 1 × 10 ^-7 to 1 × 1 per mol of silver halide
0 ^{- 1} molar amount to be achieved by a silver halide photographic emulsion comprising been found.

The reduction sensitization carried out in the present invention may be carried out at any step in the process for producing a silver halide photographic emulsion.
That is, the reduction sensitization can be carried out during physical ripening, before or after sulfur sensitization, selenium sensitization, tellurium sensitization, or gold sensitization. As a preferable example of the reducing agent,
Thiourea dioxide, tin (II) chloride, amines and polyamines, hydrazine derivatives, formamidinisulfinic acid,
Examples thereof include silane compounds, borane compounds, ascorbic acid and its derivatives, thiazolidine acid and the like.

The preferred amount of the reducing agent added varies depending on the type of reduction sensitizer, the size and shape of the silver halide grains, the composition ratio, the processing conditions (reaction temperature, pH, pAg) and the like.
For example, thiourea dioxide is preferably used in an amount of about 0.01 to 2 mg per mol of silver halide. Further, in ascorbic acid, about 5 mol per mol of silver halide.
It is preferable to use 0 mg to 2 g. As conditions for reduction sensitization, temperature is about 40 to 70 ° C. and time is about 5 to 5.
180 minutes, pH about 6-1, pAg about 1-9
Is preferred.

The silver halide emulsion of the present invention is chemically sensitized by sulfur or selenium or tellurium compound plus gold sensitization. As the sulfur sensitizer used in the present invention, various sulfur compounds such as thiosulfates, thioureas, thiazoles, and rhodanines can be used in addition to the sulfur compounds contained in gelatin. The gold sensitizer used in the present invention is various gold salts such as chloroauric acid, trichloroauric acid and thiocyanatoauric acid. As conditions for chemical sensitization, temperature is about 40 to 70 ° C. and time is about 5
~ 180 minutes, pH about 6-1, pAg about 1
A range of 9 is preferred.

Examples of tartaric acid which is a metal chelating agent used in the present invention include D, L-tartaric acid, ammonium hydrogen tartrate, ammonium tartrate, sodium hydrogen tartrate,
Sodium tartrate, sodium ammonium tartrate, potassium hydrogen tartrate, potassium tartrate, silver tartrate, anitimonyl potassium tartrate, dimethyl tartrate, diethyl tartrate, etc.Examples of ethylenediaminetetraacetic acid include ethylenediaminetetraacetic acid and disodium ethylenediaminetetraacetic acid. Get Tartaric acid is particularly preferable.

As an example of the monosaccharide used in the present invention,
D, L-glucose, erythrulose, threose, arabinose, xylulose, ribulose, lyxose,
Ribose, arabitol, lyxitol, altrose, allulose, allose, galactose, quinovose, gulose, ketoextose, sorbose, dagatose, fucose, fructose, mannose, rhamnose, glitole, glucitol, mannitol, iduronic acid, glamic acid, galactaric acid, glucaric acid. And examples of disaccharides such as heptose, octose, nonose, agarobiose, allolactose, isomaltose, xylobiose, gentiobiose, kojibiose, chondrosin, sucrose, cellobiose, sophorose, turanose, trehalose, nigerose, maltose, melibiose, lactose, laminose, laminose, laminose. Examples of polysaccharides such as rutinose, gentianose, stachyose, cellotriose Planteose, maltotriose, agarose, amylose, amylopectin, araban, arabinogalactan, alginic acid, inulin, galactan, xylan, chitin, glycogen, glycomannan, chondroitin, dextran, cellulose, hyaluronic acid, pekunanoic acid, mannan, lichenan, Levan etc. are mentioned.

When the above-mentioned metal chelating agent and saccharide are added in the process for producing the silver halide photographic emulsion of the present invention, each may be used alone or in a mixture, and it may be directly dispersed in the emulsion, or water. Alternatively, it may be dissolved in a single solvent such as methanol or ethanol or a mixed solvent and added.

The metal chelate and saccharide used in the present invention may be added at any stage in the emulsion production process, but preferably before or during the chemical ripening or after the chemical ripening. Particularly preferably, it is before chemical ripening.

The metal chelate and saccharide used in the present invention may be added at the same time or separately or at different positions in the emulsion manufacturing process.

The amount of metal chelating agent used in the present invention, it is to choose from per mol of silver halide 1 × 10 ^{over 7} to 1 × 10 ^-1 mols. More preferably, 1 × 1
0 is to select from the molar range of ^over 4 to 1 × 10 ^-2.

The amount of saccharide used in the present invention, it is to choose from per mol of silver halide 1 × 10 ^{over 7} to 1 × 10 ^-1 mols. More preferably, 1 × 10 ^-4 to 1 × 1
It is to select from 0 ^{- 2} mols.

The shape of the silver halide of the silver halide photographic emulsion of the present invention is not particularly limited, but those having a regular crystal band such as cubes and octahedra are preferable, and cubes are particularly preferable.

The silver halide of the silver halide photographic emulsion of the present invention is not particularly limited, and silver chloride, silver bromide, silver chloroiodobromide, silver iodobromide and the like can be used. When silver iodide or silver chloroiodobromide is used, the content of silver iodide is preferably 5 mol% or less.

In the emulsion used in the present invention, a metal salt such as iridium can be used during physical ripening or chemical ripening of silver halide. The photographic emulsion used in the present invention can be sensitized using a quaternary ammonium salt, a thioether compound, a polyethylene oxide derivative, a diketone, or the like. These methods are described in US Pat.
708, 162, 3,046,132, 3,0
46, 133, 3,046,134, 3,04
6,135, British Patent 939,357 and the like.

Various hydrophilic colloids are used in the silver halide photographic emulsion of the present invention, and examples of the hydrophilic colloid used as a vehicle for the photographic emulsion include gelatin, colloidal albumin, casein, carboxymethyl cellulose, hydroxyethyl cellulose and the like. Examples thereof include cellulose derivatives, agar, sodium alginate, sugar derivatives such as starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol, poly N-vinylpyrrolidone, polyacrylamide or their derivatives, and partial hydrolysates.
If desired, compatible mixtures of two or more of these colloids are used. The most commonly used of these is gelatin, but gelatin can be partially or wholly replaced by synthetic polymeric substances, and so-called gelatin derivatives, that is, amino groups as functional groups contained in the molecule, An imino group, a hydroxy group, or a carboxyl group treated with a reagent having one group capable of reacting with them and modified may be replaced with a graft polymer to which the molecular chains of other polymer substances are bonded. .

The silver halide photographic emulsion of the present invention may contain an inorganic or organic hardener. For example, chloric acid (chromium alum, chromium acetate, etc.), aldehydes (formaldehyde, glyoxal, glutaraldehyde, etc.), N-methylol compounds (dimethylol urea,
Methyloldimethylhydantoin etc.), dioxane derivative (2,3-dihydroxydioxane etc.), active vinyl compound (1,3,5-triacryloyl-hexahydro-S-triazine, 1,3-vinylsulfonyl-2)
-Propanol, etc.), active halogen compounds (2,4-
Dichloro-6-hydroxy-S-triazine and the like) mucohalogen acids (mucochloric acid, mucophenoxycycloric acid and the like) and the like can be used alone or in combination.

The silver halide photographic emulsion of the present invention may contain a surface active agent for various purposes such as a coating aid, antistatic property, slip property improvement, emulsion dispersion, and adhesion prevention.

For example, saponins (steroids), alkylene oxide derivatives (eg polyethylene glycol, polyethylene glycol / polypropylene glycol condensates, polyethylene glycol alkyl ethers or polyethylene glycol alkyl alule ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, Polyalkylene glycol alkyl amines or amides, polyethylene oxide adducts of silicones), glyoxidolyl derivatives (for example, alkenyl succinic acid polyglyceride, alkylsoenol polyglyceride), fatty acid esters of polyhydric alcohols, alkyl esters of sugars Nonionic surfactants such as class, alkyl carboxylates, alkyl sulfonates, Le Kill benzene sulfonate, alkyl naphthalene sulfonate, alkyl sulfates, alkyl phosphate esters, N- acyl -
N-alkyl taurines, sulfosuccinates,
Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfate group, a phosphate group, such as sulfoalkyl polyoxyethylene alkyl phosphates: amino acids, aminoalkyl sulfonic acids, Aminoalkyl sulfates or phosphates,
Amphoteric surfactants such as alkyl betaines and amine oxides: alkylamine salts, aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridium and imidazolium, and aliphatic or heterocyclic salts Cationic surfactants such as phosphonium or sulfonium salts can be used. It is also possible to add latex polymer or the like to modify the physical properties of the gelatin film, or to add silica, starch powder, colloidal silica, glass powder or the like to form a mat.

The silver halide photographic emulsion of the present invention contains various compounds for the purpose of preventing fog during the production process of the silver halide photographic emulsion, storage or photographic processing, or stabilizing photographic performance. Can be included. That is, azoles such as benzothiazolium salts, nitroindazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted compounds): heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzthiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (particularly 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines: the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group: a thioketo compound , For example oxazoline thione: azaindenes, for example tetraazaindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes):
Many compounds known as antifoggants or stabilizers can be added, such as benzenethiosulfonic acids: benzenesulfinic acid :, and the like.

The silver halide photographic emulsion of the present invention uses various compounds other than those mentioned above, for example, antistatic agents, antihalation dyes, plasticizers, developing agents, ultraviolet absorbers, fluorescent dyes, development accelerators, couplers and the like. can do.

[0028]

EXAMPLES Examples will be shown below to more specifically describe the present invention, but the present invention is not limited to these examples, and various applications can be made within the scope of the claims.

Example 1 Preparation of emulsion: An aqueous solution containing 5 g of sodium chloride and 40 g of gelatin in 600 ml of water was added to a silver nitrate aqueous solution and a water-soluble iridium salt (to 1 mol of silver) by a double jet method in which pAg 8.6 was controlled at 40 ° C. 3.25 × 10 ^-6 mol) and hexachlororhodate potassium (per 1 mol of silver halide solution was mixed an average particle size 0.34μm silver chlorobromide containing 3.78 × 10 ^-7 mol) against ( A silver bromide (30 mol%) emulsion was prepared, a potassium iodide (0.1 mol% based on silver) solution was added, and then the precipitate was washed with water and redissolved. The emulsion thus obtained was divided.

(A-1) The above emulsion was treated at 55 ° C. with optimum sulfur +
Gold sensitization was applied.

[0031] (A-2) 55 (1 × 10 ^-3 mol 1 mol of silver) of sodium potassium tartrate at ° C., after addition of glucose (1 × 10 ^-3 mol 1 mol of silver), 55
Sulfur + gold sensitization was performed to obtain high sensitivity and low fog at ℃.

(A-3) After adding potassium sodium tartrate (1 × 10 ⁻³ mol to 1 mol of silver) at 55 ° C.,
Sulfur + gold sensitization was performed at 55 ° C. to obtain high sensitivity and low fog.

(A-4) D-glucose (silver 1
After the addition of 1 × 10 ⁻³ mol), the mixture was subjected to sulfur + gold sensitization at 55 ° C. so as to have high sensitivity and low fog.

Thereafter, 1-phenyl-5-mercaptotetrazole, 2,4-dichloro-6-hydroxytriazine, a phenoxypolyethylene glycol surfactant, hydroquinone and a water-soluble latex were added respectively. These emulsions were adjusted to pH 5.5 to give finished emulsions.

These emulsions were provided with a protective layer (1.5 g of gelatin).
/ M ^-2 ) and 4.1 g of silver on a polyester film
Samples were prepared by applying multiple layers so as to have m ^-2 . The emulsion was kept for 12 hours at 37 ° C. and then coated in the same manner. These samples were subjected to sensitometric exposure for 10 to ⁴ seconds through a blue colored glass filter, developed with a PQ developing solution, fixed, washed with water and dried to obtain characteristics. The results are shown in Table 1. Sensitivity was 3.2 when the (A-1) emulsion was coated at pH 5.5 and the density was 3.2 immediately after completion.
The sensitivity was set to 100.

[0036]

[Table 1]

Example 2 Preparation of emulsion: An aqueous solution containing 5 g of sodium chloride and 40 g of gelatin in 600 ml of water was added to the aqueous solution of silver nitrate by the double jet method at a pAg of 8.6 at 40 ° C. and a water-soluble iridium salt (to 1 mol of silver). 3.25 × 10 ^-6 mol) and hexachlororhodate potassium (per 1 mol of silver halide solution was mixed an average particle size 0.34μm silver chlorobromide containing 3.78 × 10 ^-7 mol) against ( A silver bromide (30 mol%) emulsion was prepared, a potassium iodide (0.1 mol% based on silver) solution was added, and then the precipitate was washed with water and redissolved. The emulsion thus obtained was divided.

(B-1) Thiourea dioxide (silver 1) at 55 ° C.
After reduction sensitization was carried out using 1 × 10 ⁻⁵ mol), the sulfur + gold sensitization was carried out at 55 ° C. so as to obtain high sensitivity and low fog.

(B-2) Thiourea dioxide (silver 1
Reduction sensitization was performed using 1 × 10 ⁻⁵ mol)
Sodium potassium tartrate (per 1 mol of silver 1 × 10 ^-3
Mol), and then sulfur + gold sensitization was performed at 55 ° C. so as to obtain high sensitivity and low fog.

(B-3) Thiourea dioxide (silver 1
Reduction sensitization was performed using 1 × 10 ⁻⁵ mol)
After adding D-glucose (1 × 10 ⁻³ mol per mol of silver), it was subjected to sulfur + gold sensitization at 55 ° C. so as to have high sensitivity and low fog.

(B-4) Thiourea dioxide (silver 1
Reduction sensitization was performed using 1 × 10 ⁻⁵ mol)
Sodium potassium tartrate (per 1 mol of silver 1 × 10 ^-3
Mol) and D-glucose (1 × 10 ⁻³ mol per 1 mol of silver) were added, and then sulfur + gold sensitization was performed at 55 ° C. so as to obtain high sensitivity and low fog.

(B-5) Thiourea dioxide (silver 1
Reduction sensitization was performed using 1 × 10 ⁻⁵ mol)
After high-sensitivity and low fog sensitization at 55 ° C, after sensitizing with sulfur and gold, potassium sodium tartrate (1 x 10 ^-3 mol per 1 mol of silver) and D-glucose (1 mol per 1 mol of silver).
× ^10-3 mol) was added.

Thereafter, 1-phenyl-5-mercaptotetrazole, 2,4-dichloro-6-hydroxytriazine, phenoxypolyethylene glycol surfactant, hydroquinone and water-soluble latex were added respectively. These emulsions were adjusted to pH 5.5 to give finished emulsions.

These emulsions were treated with a protective layer (gelatin 1.5 g).
/ M ^-2 ) and 4.1 g of silver on a polyester film
Samples were prepared by applying multiple layers so as to have m ^-2 . The emulsion was kept for 12 hours at 37 ° C. and then coated in the same manner. These samples were subjected to sensitometric exposure for 10 to ⁴ seconds through a blue colored glass filter, developed with a PQ developing solution, fixed, washed with water and dried to obtain characteristics. Table 2 shows the results. The sensitivity was 3.2 when the (B-1) emulsion was coated at pH 5.5, and the density was 3.2 immediately after completion.
The sensitivity was set to 100.

[0045]

[Table 2]

Example 3 Preparation of emulsion: An aqueous solution containing 5 g of sodium chloride and 40 g of gelatin in 600 ml of water was added to the aqueous solution of silver nitrate by the double jet method in which pAg 8.6 was controlled at 40 ° C. and a water-soluble iridium salt (to 1 mol of silver). 3.25 × 10 ^-6 mol) and hexachlororhodate potassium (per 1 mol of silver halide solution was mixed an average particle size 0.34μm silver chlorobromide containing 3.78 × 10 ^-7 mol) against ( A silver bromide (30 mol%) emulsion was prepared, a potassium iodide (0.1 mol% based on silver) solution was added, and then the precipitate was washed with water and redissolved. The emulsion thus obtained was divided.

(A-1) The above emulsion was treated at 55 ° C. with optimum sulfur +
Gold sensitization was applied.

(C-1) Ethylenediaminetetraacetic acid (1 × 10 ⁻³ mol per 1 mol of silver) and glucose (1 × 10 ⁻³ mol per 1 mol of silver) were added at 55 ° C., and then at 55 ° C. Sulfur + gold sensitization was applied to obtain high sensitivity and low fog.

(C-2) Ethylenediaminetetraacetic acid (1 × 10 ⁻³ mol per mol of silver) was added at 55 ° C., and then 5
Sulfur + gold sensitization was performed at 5 ° C. to obtain high sensitivity and low fog.

(C-3) D-glucose (silver 1
After the addition of 1 × 10 ⁻³ mol), the mixture was subjected to sulfur + gold sensitization at 55 ° C. so as to have high sensitivity and low fog.

Thereafter, 1-phenyl-5-mercaptotetrazole, 2,4-dichloro-6-hydroxytriazine, phenoxypolyethylene glycol surfactant, hydroquinone and water-soluble latex were added respectively. These emulsions were adjusted to pH 5.5 to give finished emulsions.

These emulsions were provided with a protective layer (gelatin 1.5 g).
/ M ^-2 ) and 4.1 g of silver on a polyester film
Samples were prepared by applying multiple layers so as to have m ^-2 . The emulsion was kept for 12 hours at 37 ° C. and then coated in the same manner. These samples were subjected to sensitometric exposure for 10 to ⁴ seconds through a blue colored glass filter, developed with a PQ developing solution, fixed, washed with water and dried to obtain characteristics. The results are shown in Table 3. Sensitivity was 3.2 when the (A-1) emulsion was coated at pH 5.5 and the density was 3.2 immediately after completion.
The sensitivity was set to 100.

[0053]

[Table 3]

Example 4 Preparation of emulsion: An aqueous solution containing 5 g of sodium chloride and 40 g of gelatin in 600 ml of water was added to a silver nitrate aqueous solution by a double jet method in which pAg 8.6 was controlled at 40 ° C. and a water-soluble iridium salt (to 1 mol of silver). 3.25 × 10 ^-6 mol) and hexachlororhodate potassium (per 1 mol of silver halide solution was mixed an average particle size 0.34μm silver chlorobromide containing 3.78 × 10 ^-7 mol) against ( A silver bromide (30 mol%) emulsion was prepared, a potassium iodide (0.1 mol% based on silver) solution was added, and then the precipitate was washed with water and redissolved. The emulsion thus obtained was divided.

(B-1) Thiourea dioxide (silver 1
After reduction sensitization was carried out using 1 × 10 ⁻⁵ mol), the sulfur + gold sensitization was carried out at 55 ° C. so as to obtain high sensitivity and low fog.

(D-1) Thiourea dioxide (silver 1
Reduction sensitization was performed using 1 × 10 ⁻⁵ mol)
After adding ethylenediaminetetraacetic acid (1 × 10 ⁻³ mol to 1 mol of silver), sulfur + gold sensitization was performed at 55 ° C. so as to obtain high sensitivity and low fog.

(D-2) Thiourea dioxide (silver 1
Reduction sensitization was performed using 1 × 10 ⁻⁵ mol)
After adding D-glucose (1 × 10 ⁻³ mol per mol of silver), it was subjected to sulfur + gold sensitization at 55 ° C. so as to have high sensitivity and low fog.

(D-3) Thiourea dioxide (silver 1
Reduction sensitization was performed using 1 × 10 ⁻⁵ mol)
After adding ethylenediaminetetraacetic acid (1 × 10 ⁻³ mol to 1 mol of silver) and D-glucose (1 × 10 ⁻³ mol to 1 mol of silver), to obtain high sensitivity and low fog at 55 ° C. Sulfur + gold sensitization was applied.

(D-4) Thiourea dioxide (silver 1
Reduction sensitization was performed using 1 × 10 ⁻⁵ mol)
After high sensitivity and low fog sensitization at 55 ° C with sulfur + gold sensitization, ethylenediaminetetraacetic acid (1 mol per 1 mol silver)
X ^10-3 mol), D-glucose (1 x per mol of silver)
^10-3 mol) was added.

Thereafter, 1-phenyl-5-mercaptotetrazole, 2,4-dichloro-6-hydroxytriazine, a phenoxypolyethylene glycol surfactant, hydroquinone and a water-soluble latex were added. These emulsions were adjusted to pH 5.5 to give finished emulsions.

These emulsions were treated with a protective layer (1.5 g of gelatin).
/ M ^-2 ) and 4.1 g of silver on a polyester film
Samples were prepared by applying multiple layers so as to have m ^-2 . The emulsion was kept for 12 hours at 37 ° C. and then coated in the same manner. These samples were subjected to sensitometric exposure for 10 to ⁴ seconds through a blue colored glass filter, developed with a PQ developing solution, fixed, washed with water and dried to obtain characteristics. The results are shown in Table 4. The sensitivity was 3.2 when the (B-1) emulsion was coated at pH 5.5, and the density was 3.2 immediately after completion.
The sensitivity was set to 100.

[0062]

[Table 4]

Example 5 Preparation of emulsion: An aqueous solution containing 5 g of sodium chloride and 40 g of gelatin in 600 ml of water was added to a silver nitrate aqueous solution and a water-soluble iridium salt (to 1 mole of silver) by a double jet method in which pAg 8.6 was controlled at 40 ° C. 3.25 × 10 ^-6 mol) and hexachlororhodate potassium (per 1 mol of silver halide solution was mixed an average particle size 0.34μm silver chlorobromide containing 3.78 × 10 ^-7 mol) against ( A silver bromide (30 mol%) emulsion was prepared, a potassium iodide (0.1 mol% based on silver) solution was added, and then the precipitate was washed with water and redissolved. The emulsion thus obtained was divided.

(A-1) Optimum sulfur +
Gold sensitization was applied.

(E-1) Nitrilotriacetic acid (silver 1
1 × 10 ^-3 mol mol), was added glucose (1 × 10 ^-3 mol 1 mol of silver), high sensitivity 55 ° C.,
Sulfur + gold sensitization was applied to achieve low fog.

(E-2) Nitrilotriacetic acid (NT
A) (1 × 10 ⁻³ mol per mol of silver) was added,
Sulfur + gold sensitization was performed at 55 ° C. to obtain high sensitivity and low fog.

(E-3) D-glucose (silver 1
After the addition of 1 × 10 ⁻³ mol), the mixture was subjected to sulfur + gold sensitization at 55 ° C. so as to have high sensitivity and low fog.

Thereafter, 1-phenyl-5-mercaptotetrazole, 2,4-dichloro-6-hydroxytriazine, a phenoxypolyethylene glycol surfactant, hydroquinone and a water-soluble latex were added respectively. These emulsions were adjusted to pH 5.5 to give finished emulsions.

These emulsions were coated with a protective layer (gelatin 1.5 g).
/ M ^-2 ) and 4.1 g of silver on a polyester film
Samples were prepared by applying multiple layers so as to have m ^-2 . The emulsion was kept for 12 hours at 37 ° C. and then coated in the same manner. These samples were subjected to sensitometric exposure for 10 to ⁴ seconds through a blue colored glass filter, developed with a PQ developing solution, fixed, washed with water and dried to obtain characteristics. The results are shown in Table 5. Sensitivity was 3.2 when the (A-1) emulsion was coated at pH 5.5 and the density was 3.2 immediately after completion.
The sensitivity was set to 100.

[0070]

[Table 5]

Example 6 Preparation of emulsion: An aqueous solution containing 5 g of sodium chloride and 40 g of gelatin in 600 ml of water was added to the aqueous solution of silver nitrate by a double jet method at a pAg of 8.6 at 40 ° C. and a water-soluble iridium salt (1 mol of silver). 3.25 × 10 ^-6 mol) and hexachlororhodate potassium (per 1 mol of silver halide solution was mixed an average particle size 0.34μm silver chlorobromide containing 3.78 × 10 ^-7 mol) against ( A silver bromide (30 mol%) emulsion was prepared, a potassium iodide (0.1 mol% based on silver) solution was added, and then the precipitate was washed with water and redissolved. The emulsion thus obtained was divided.

(B-1) Thiourea dioxide (silver 1
After reduction sensitization was carried out using 1 × 10 ⁻⁵ mol), the sulfur + gold sensitization was carried out at 55 ° C. so as to obtain high sensitivity and low fog.

(F-1) Thiourea dioxide (silver 1
Reduction sensitization was performed using 1 × 10 ⁻⁵ mol)
After adding nitrilotriacetic acid (1 × 10 ⁻³ mol to 1 mol of silver), sulfur + gold sensitization was performed at 55 ° C. so as to obtain high sensitivity and low fog.

(F-2) Thiourea dioxide (silver 1
Reduction sensitization was performed using 1 × 10 ⁻⁵ mol)
After adding D-glucose (1 × 10 ⁻³ mol per mol of silver), it was subjected to sulfur + gold sensitization at 55 ° C. so as to have high sensitivity and low fog.

(F-3) Thiourea dioxide (silver 1
Reduction sensitization was performed using 1 × 10 ⁻⁵ mol)
Nitrilotriacetic acid (1 × 10 ⁻³ mol per mol of silver), D
-After adding glucose (1 x ^10-3 mol per mol of silver), sulfur at 55 ° C for high sensitivity and low fog +
Gold sensitization was applied.

(F-4) Thiourea dioxide (silver 1
Reduction sensitization was performed using 1 × 10 ⁻⁵ mol)
High sensitivity 55 ° C., was subjected to sulfur + gold sensitization so that low fog, nitrilotriacetic acid (1 mol of silver to 1 × 10 ^-3
Mol) and D-glucose (1 × 10 ⁻³ mol per mol of silver) were added.

Thereafter, 1-phenyl-5-mercaptotetrazole, 2,4-dichloro-6-hydroxytriazine, a phenoxypolyethylene glycol type surfactant, hydroquinone and a water-soluble latex were added respectively. These emulsions were adjusted to pH 5.5 to give finished emulsions.

These emulsions were treated with a protective layer (gelatin 1.5 g).
/ M ^-2 ) and 4.1 g of silver on a polyester film
Samples were prepared by applying multiple layers so as to have m ^-2 . The emulsion was kept for 12 hours at 37 ° C. and then coated in the same manner. These samples were subjected to sensitometric exposure for 10 to ⁴ seconds through a blue colored glass filter, developed with a PQ developing solution, fixed, washed with water and dried to obtain characteristics. The results are shown in Table 6. The sensitivity was 3.2 when the (B-1) emulsion was coated at pH 5.5, and the density was 3.2 immediately after completion.
The sensitivity was set to 100.

[0079]

[Table 6]

As is clear from Tables 1 to 6, by adding a metal chelating agent and a saccharide, a silver halide photographic emulsion having high sensitivity and low fog can be obtained.

[0081]

As will be understood from the examples, a silver halide photographic emulsion with high sensitivity and low fog can be obtained.

Claims (3)

[Claims] 1. A silver halide photographic emulsion characterized by containing a metal chelating agent and a saccharide in a silver halide photographic emulsion which has been subjected to reduction sensitization and / or chemical ripening. 2. The silver halide photographic emulsion according to claim 1, wherein the metal chelating agent is at least one of tartaric acid, ethylenediaminetetraacetic acid, nitrilotriacetic acid and uramildiacetic acid. 3. The silver halide photographic emulsion according to claim 1, wherein the saccharide is at least one kind of monosaccharide, disaccharide and polysaccharide.