JPH1195354A - Silver halide photographic sensitive material and coating liquid for silver halide emulsion layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material having high sensitivity, low fog and excellent graininess, and to provide a coating liquid for a silver halide emulsion layer having excellent residence stability. SOLUTION: This silver halide photographic material contains a gelatin of 500 to 50000 weight average mol.wt. by 0.15 to 20 g per 1 m<2> . The coating liquid contains a gelatin of 500 to 50000 weight average mol.wt. by 3 to 300 g per 1 mol of silver.

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 light-sensitive material and a silver halide emulsion layer coating solution, and more particularly, to a silver halide photographic light-sensitive material having high sensitivity, low fog and excellent graininess, and stagnant stability. And a silver halide emulsion layer coating solution excellent in the following.

[0002]

2. Description of the Related Art In recent years, photographic performance of silver halide photographic materials has been required to have higher sensitivity and higher image quality than ever before. In addition to conventional sensitization techniques such as sulfur sensitization and gold sensitization as chemical sensitization of silver halide emulsions, sensitization techniques using chalcogen compounds such as selenium sensitization and tellurium sensitization as new high sensitivity techniques in recent years Came to be used. In the production of silver halide grains, sensitization techniques such as reduction sensitization using thiourea dioxide, ascorbic acid, dimethylaminoborane or the like have come to be used. However, these techniques have the disadvantage that fog increases with increasing sensitivity. As a compound that suppresses fog, a fog-suppressing compound such as a water-soluble mercapto compound or tetrazaindene is known.However, these compounds have a disadvantage that they reduce fog and also cause desensitization. The improvement is desired.

When the above-mentioned sensitization technique is used, the time required for the silver halide emulsion to be chemically sensitized and before it is coated on a support (stagnation time) increases, resulting in a significant decrease in sensitivity and an increase in fog. There is a demand for a silver halide emulsion layer coating solution having stable stagnation performance.

[0004]

An object of the present invention is to provide a silver halide photographic light-sensitive material having high sensitivity, low fog, and excellent graininess, and a silver halide emulsion layer coating solution having excellent stagnation stability. It is in.

[0005]

The above objects of the present invention have been attained by the following constitutions.

(1) A silver halide photographic light-sensitive material characterized in that the silver halide light-sensitive material contains gelatin having a weight average molecular weight of 500 or more and 50,000 or less per square meter of 0.15 g or more and 20 g or less.

(2) A coating solution for a silver halide emulsion layer, wherein the coating solution for a silver halide emulsion layer contains gelatin having a weight average molecular weight of 500 to 50,000 or less per mol of silver in a range of 3 g to 300 g.

The present invention will be described in more detail. The silver halide photographic light-sensitive material of the present invention (hereinafter also referred to as light-sensitive material)
It can be obtained by incorporating the gelatin of the present invention into a layer constituting a photographic material described below.

The silver halide emulsion layer coating solution of the present invention can be obtained by adding the gelatin of the present invention to the silver halide emulsion layer coating solution. Here, the coating solution is a gelatin crosslinking agent (a so-called hardener). ) Refers to a liquid to which no) has been added.

Regarding the properties and manufacturing method of gelatin used for photography, see "Basics of photographic engineering: silver salt photography" (Corona) 1
Details are described on pages 16 to 150. Photographic gelatin is often used as a dispersion medium and binder in photographic emulsions. Gelatin is extracted from collagen, which is a constituent protein of animal connective tissue, and its raw materials include cow bone, cow skin, pig skin, and fish skin. By subjecting these gelatins to acid treatment or alkali treatment, they are extracted from collagen in the raw material. As photographic gelatin, usually extracted by alkaline treatment of cow bone and cow hide,
Those having a weight average molecular weight of about 70,000 to 130,000 are often used. The gelatin of the present invention is a gelatin having a weight-average molecular weight of about 100,000, which is further subjected to enzymatic degradation by adding a gelatin-degrading enzyme, hydrolysis by adding an acid or alkali, and heating under atmospheric pressure or under pressure. It can be obtained by thermally decomposing by heating, decomposing by ultrasonic irradiation, or by using those methods in combination.

Japanese Patent Application Laid-Open Nos. Hei 6-214331 and No. 6 describe an example in which a relatively low molecular weight gelatin having a weight average molecular weight in the range of 500 to 50,000 is used at the time of preparing a silver halide photographic emulsion and further coated. No. 230493, 8-
29904 and 6-230493. However, these amounts are much smaller than those used in the present invention, and do not indicate the effects of the present invention.

The effect of the present invention, which is exhibited by using gelatin having a weight-average molecular weight of 500 or more and 50,000 or less for a silver halide photosensitive material, is as follows. And the properties of the silver halide photographic light-sensitive material and the coating solution of the silver halide emulsion layer may be changed by the presence of a specific molecular weight component.

The silver halide photographic material of the present invention comprises at least one layer containing photosensitive silver halide grains (hereinafter also referred to as a photosensitive layer). If necessary, a light-insensitive layer containing no light-sensitive silver halide grains may be formed in the light-sensitive material. The photosensitive layer can have sensitivity in any wavelength region of visible light and invisible light by spectral sensitization described below.

When the gelatin of the present invention comprises at least one photosensitive layer and two or more non-photosensitive layers, any of these layers can be used, but it is preferably used in the photosensitive layer. When the gelatin of the present invention has two or more photosensitive layers, it can be contained in any photosensitive layer. When the photosensitive material is composed of a plurality of photosensitive layers having different sensitivities such as a high-sensitivity layer, a medium-sensitivity layer, and a low-sensitivity layer,
It is preferable to use at least the layer having the highest sensitivity.

The gelatin of the present invention has a weight average molecular weight of 5
From 00 to 50,000, preferably from 2000 to 50,000
40,000, more preferably 5,000 to 25,000. The weight average molecular weight of gelatin can be determined by gel filtration chromatography.

The gelatin of the present invention may be added at any time as long as it is present in the silver halide photographic material.
When used in a photosensitive layer, the gelatin is preferably added at a time after the completion of crystal growth of silver halide grains contained in the silver halide emulsion, and more preferably a spectral sensitizer or a chemical sensitizer is added. More preferably, after the chemical sensitization is started, and more preferably, after the temperature is lowered after the chemical sensitization or when the chemical sensitization is completed by adding a stabilizer or the like, and before the coating on the support.

When the gelatin of the present invention is used in a coating solution for a silver halide emulsion layer, it is preferable to add the gelatin before adding a hardener.

The gelatin of the present invention may be used in place of at least a part of the above-mentioned gelatin usually used for photography. When constructing a color light-sensitive material, the gelatin of the present invention may be contained in a coupler dispersion or the like.

The coupler dispersion referred to in the present invention is a mixture of a high boiling solvent such as dibutyl phthalate and tricresyl phosphate and a low boiling solvent such as ethyl acetate or a low boiling solvent alone. After dissolving the coupler alone or in combination of two or more in a solvent, mixed with an aqueous gelatin solution containing a surfactant, and then emulsified and dispersed using a high-speed rotary mixer or a colloid mill or an ultrasonic disperser. . In the coupler dispersion, gelatin having a weight average molecular weight of about 100,000 is usually used.

The gelatin of the present invention may be added as it is in a solid state, or may be a method in which water or an organic solvent such as methanol or ethanol is dissolved alone or in a mixed solvent.

The gelatin of the present invention is used in the silver halide light-sensitive material in an amount of 0.15 g to 20 g per square meter, preferably 0.25 g to 15 g,
More preferably, it is 0.35 g or more and 10 g or less.

The gelatin of the present invention is used in the silver halide emulsion coating solution at a concentration of 3 g / mol Ag to 300 g / mol Ag, preferably 5 g / mol Ag to 250 g / mol Ag, more preferably 10 g / mol Ag. More than 20
0 g / mol Ag or less.

The amount and position of the gelatin of the present invention are as described above. For the method of preparing the coating solution, see "Basics of Photographic Engineering: Silver halide photography" (Corona) 253-255.
It is described in detail on the page. Although methods such as a batch method and a continuous production method are known, the gelatin of the present invention can be applied to any method. The temperature of the coating solution of the present invention is from 30 ° C.
50 ° C., pH 4.0-8.0, viscosity 10-200c
It is preferably p.

The silver halide composition of the silver halide emulsion used in the present invention is arbitrary, and examples thereof include silver bromide, silver iodobromide, silver iodochlorobromide, silver chlorobromide and silver chloride, and the like. Any of the mixtures may be used.

When silver iodobromide is used, the content of silver iodide in one grain is preferably from 0.1 mol% to 5 mol%.

The shape of the silver halide grains contained in the silver halide emulsion used in the present invention may be spherical, cubic, octahedral, or tetradecahedral. Particularly, tabular silver halide grains are used. It is desirable.

Tabular silver halide grains are silver halide grains having two parallel main planes and having an aspect ratio of 2 or more. Here, the aspect ratio means a circle-equivalent diameter of the main plane (the It refers to the ratio between the diameter of a circle having the same projected area as the main plane (the diameter of a circle) and the distance between the main planes (ie, the thickness of the particles). The average aspect ratio refers to an average value when the aspect ratio is measured for 1000 or more particles indiscriminately.

When a tabular silver halide emulsion is used in the present invention, the average aspect ratio is preferably from 2.0 to 50, more preferably from 5.0 to 20.

The silver halide emulsion used in the present invention is preferably an emulsion having a coefficient of variation of 20% or less, more preferably 1% or less.
Emulsions of 6% or less are preferred. Here, the coefficient of variation is 100, which is a value obtained by dividing the standard deviation of the particle diameter distribution by the average particle diameter.
Defined as double.

The silver halide emulsion used in the present invention is preferably subjected to reduction sensitization. Reduction sensitization is performed by adding a reducing agent to a silver halide emulsion or a mixed solution for grain growth. Alternatively, a silver halide emulsion or a mixed solution for grain growth is prepared with a low pAg of 7 or less.
g or under high pH conditions of pH 7 or higher. These methods may be performed in combination.

In addition, JP-A-7-219093 and 7-19093
As described in JP-A-225438, reduction sensitization may be performed before or after the chemical sensitization step. Further, reduction sensitization may be performed in the presence of an oxidizing agent.

Preferred examples of the reducing agent include thiourea dioxide, ascorbic acid and its derivatives, and stannous salts. Other suitable reducing agents include borane compounds,
Examples include hydrazine derivatives, formamidinesulfinic acid, silane compounds, amines and polyamines, and sulfites. The addition amount is 10 ^-2 per mol of silver halide.
Preferred is from 10 to 10 ^-8 mol.

For low pAg ripening, a silver salt can be added, but a water-soluble silver salt is preferred. Silver nitrate is preferred as the water-soluble silver salt. The pAg at ripening is suitably 7 or less, preferably 6 or less, more preferably 1 or less.
３3 (where pAg = −log [Ag ⁺ ]).

The high pH ripening is carried out, for example, by adding an alkaline compound to a silver halide emulsion or a mixed solution for grain growth. As the alkaline compound,
For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, ammonia and the like can be used. In the method of adding ammoniacal silver nitrate to silver halide formation, an alkaline compound other than ammonia is preferably used because the effect of ammonia is reduced.

As a method for adding a silver salt or an alkaline compound for reduction sensitization, rush addition or addition over a certain period of time may be used. In this case, the addition may be performed at a constant flow rate, or may be performed by changing the flow rate like a function. Further, the required amount may be added several times. Prior to the addition of the soluble silver salt and / or the soluble halide to the reaction vessel, it may be present in the reaction vessel, or may be mixed in a soluble halide solution and added together with the halide. Further, it may be added separately from the soluble silver salt and the soluble halide.

The silver halide emulsion used in the present invention is:
An oxidizing agent for silver may be added during the manufacturing process. The oxidizing agent for silver refers to a compound having an effect of acting on metallic silver to convert it into silver ions. In particular, a compound which converts silver atoms by-produced in the process of forming silver halide grains into silver ions is effective. The silver ion generated here may form a silver salt which is hardly soluble in water such as silver halide, silver sulfide, silver selenide, or a silver salt which is easily soluble in water such as silver nitrate. Is also good.

The oxidizing agent for silver is inorganic,
It may be an organic substance. As the inorganic oxidizing agent, ozone, hydrogen peroxide and its adduct (for example, NaBO _{2.
H 2 O 2 · 3H 2 O} , 2NaCO 3 · 3H 2 O 2, Na 4 P 2 O
_{7 · 2H 2 O 2, 2Na} 2 SO 4 · H 2 O 2 · H 2 O), peroxy acid salt _{(e.g., K 2 S 2 O 8,} K 2 C 2 O 6, K 4 P
₂ O ₈ ), peroxy complex compounds (for example, K ₂ [Ti
(O ₂₎ C ₂ O _{4] · 3H 2 O, 4K 2 SO} 4 · Ti (O 2)
_{OH · SO 4 · 2H 2 O} , Na 3 _{[VO (O 2) (C 2} O 4)
₂ · 6H ₂ O]), permanganate (e.g. KMn
O ₄ ), oxyacid salts such as chromate (eg, K ₂ Cr ₂ O ₇ ), halogen elements such as iodine and bromine, perhalates (eg, potassium periodate), and salts of high-valent metals (For example, potassium hexacyanoferrate) and thiosulfonate. Examples of the organic oxidizing agent include quinones such as p-quinone, organic peroxides such as peracetic acid and perbenzoic acid, and the like.
Compounds that release an active halogen (for example, N-bromosuccinimide, chloramine T, chloramine B) are mentioned.

In the present invention, the silver halide emulsion is preferably subjected to chemical sensitization and spectral sensitization.

In the present invention, a sulfur sensitizer, a selenium sensitizer, a tellurium sensitizer, or the like can be used as a chemical sensitizer.

Examples of the sulfur sensitizer applicable to the present invention include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine compounds, Preferred examples include dithiocarbamic acids, polysulfide organic compounds, sodium thiosulfate, and sulfur alone. In addition, as an elemental sulfur, α-sulfur belonging to the orthorhombic group is preferable.

Other sulfur sensitizers include US Pat. Nos. 1,574,944, 2,410,689, 2,278,947, 2,728,668, and 3,501. , 313 and 3,656,955, etc. can also be used.

In the present invention, selenium sensitizers that can be used include a wide variety of selenium compounds. For example, US Pat. Nos. 1,574,944 and 1,60
No. 2,592, No. 1,623,499;
150046, JP-A-4-25832, 4-10
No. 9240, No. 4-147250, and the like. Useful selenium sensitizers include colloidal selenium metal, isoselenocyanates (eg, allyl isocyanate, etc.), selenoureas (eg, N, N-dimethylselenourea, N, N, N′-triethylselenourea,
N, N, N'-trimethyl-N'-heptafluoroselenourea, N, N, N'-trimethyl-N'-heptafluoropropylcarbonylselenourea, N, N, N'-trimethyl-N'-4- Nitrophenylcarbonylselenourea, etc.), selenoketones (eg, selenoacetone, selenoacetophenone, etc.), selenoamides (eg, selenoacetamide, N, N-dimethylselenobenzamide, etc.), selenocarboxylic acids and selenoesters (eg, 2-selenopropion) , Methyl-3-selenobutyrates, etc.), selenophosphates (eg, tri-p
-Triselenophosphate, etc.) and selenides (eg, dimethyl selenide, triphenylphosphine selenide, etc.). Particularly preferred selenium sensitizers are selenoureas, selenamides, and selenides.

For tellurium sensitizers and sensitization methods usable in the present invention, see US Pat. No. 1,623,499.
Nos. 3,320,069 and 3,772,031
Nos. 3,531,289 and 3,655,349
No., British Patent Nos. 235,211 and 1,121,46.
No. 9, No. 1, 295, 462, No. 1, 396, 696
No., Canadian Patent No. 800,958, JP-A-4-204
No. 64, etc. Examples of useful tellurium sensitizers include telluroreas, telluramides, and the like.

The addition amount of the sulfur sensitizer, selenium sensitizer, and tellurium sensitizer is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, and the like. It is preferably from 1 × 10 ⁻⁴ mol to 1 × 10 ⁻⁹ mol per mol. More preferably, it is 1 × 10 ⁻⁵ mol to 1 × 10 ⁻⁸ mol.

In the chemical sensitization of the present invention, the sensitivity can be further increased by using a gold sensitizer in combination. Useful gold sensitizers include, in addition to chloroauric acid, gold thiosulfate, gold thiocyanate, and the like, U.S. Pat.
Nos. 49,484 and 5,049,485
No. 15748, JP-A No. 1-147537, 4-7
And gold complexes of organic compounds disclosed in No. 0650 and the like.

Depending on the properties of the compound to be used, the above-mentioned various sensitizers can be added either by adding water or an organic solvent such as methanol or ethanol alone or by dissolving in a mixed solvent, or by adding gelatin. A method in which the mixture is added with a solution in advance and a method disclosed in JP-A-4-140739, that is, a method in which the mixture is added in the form of an emulsified dispersion of a mixed solution with an organic solvent-soluble polymer may be used.

In the present invention, when the chemical sensitization is performed in the presence of a silver halide-adsorbing compound, the effect of the present invention is further enhanced. As the silver halide-adsorbing compound, a sensitizing dye,
Antifoggants and stabilizers can be used.

The silver halide emulsion of the present invention can be sensitized to a desired wavelength region by using a dye known as a sensitizing dye in the photographic industry. The sensitizing dye may be used alone or in combination of two or more. Along with sensitizing dye,
The emulsion itself may be a dye having no spectral sensitizing effect or a compound which does not substantially absorb visible light and which enhances the sensitizing effect of the sensitizing dye.

Examples of the spectral sensitizing dye include polymethine dyes including cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, hemioxonol dyes, oxonol, merostyryl and streptocyanin. Can be mentioned.

Examples of antifoggants and stabilizers include tetrazaindenes, azoles, benzothiazolium salts, nitroindazoles, nitrobenzimidazoles, chlorobenzimidazoles, bromobenzimidazoles, mercaptothiazoles, Mercaptobenzimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (especially 1-phenyl-5-tetrazole)
Also, mercaptopyrimidines, mercaptotriazines, for example, thioketo compounds such as oxazolythion, further benzenethiosulfinic acid, benzenesulfinic acid, benzenesulfonamide, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives,
Ascorbic acid derivatives can be mentioned.

Specific examples of known photographic additives which can be used in forming a photographic material using the silver halide photographic emulsion of the present invention, and various couplers which can be used in forming a color photographic material. Are described below.

In the present invention, the silver halide emulsion is prepared by using Research Disclosure 308119 (hereinafter referred to as RD308).
119). The places to be described are shown below.

[Items] [Page of RD308119] Iodine composition 993 IA Section Production method 993 IA and 994 E Crystal habit (normal crystal) 993 IA Crystal habit (twin crystal) 993 IA Item Epitaxial 993 IA Item Halogen composition (uniform) 993 IB Item Halogen composition (not uniform) 999 IB Item Halogen conversion 994 IC Item Halogen substitution 994 IC Item Metal-containing 994 ID Item Monodispersion 995 I-F Solvent addition 995 I-F Latent image forming position (surface) 995 I-G Latent image forming position (internal) 995 I-G Applicable photosensitive material (negative) 995 I-H Applicable light-sensitive material (positive) Section 995 IH Use the emulsion as a mixture Section 995 IJ Desalting Section 995 II-A The silver halide emulsion of the present invention has physical ripening, chemical ripening and spectral sensitization. Can be used. Additives used in such a process are described in Research Disclosure No. 17643, no. 18716 and no.
308119 (hereinafter referred to as RD17643, RD1
8716 and RD308119).

The following shows the places to be described.

[0055]

[Table 1]

Known photographic additives which can be used in the present invention are also described in the above-mentioned Research Disclosure. The relevant sections are shown below.

[0057]

[Table 2]

Various couplers can be used in the present invention, and specific examples are described in the above-mentioned Research Disclosure. The relevant locations are shown below.

[0059]

[Table 3]

The additive used in the present invention is RD3081
It can be added by the dispersion method described in 19XIV.

In the present invention, the aforementioned RD17643
28 pages, RD18716 pages 647-8 and RD308
The support described in XIX 119 can be used.

The light-sensitive material of the present invention includes the aforementioned RD3081
An auxiliary layer such as a filter layer or an intermediate layer described in the item 19VII-K can be provided.

The light-sensitive material of the present invention can be obtained by using the above-mentioned RD30811
Various layer configurations such as a normal layer, a reverse layer, and a unit configuration described in section 9VII-K can be employed.

The present invention can be applied to various color photosensitive materials typified by color negative films for general use or movies, color reversal films for slides or televisions, color papers, color positive films, and color reversal papers. .

The light-sensitive material of the present invention is the same as the RD17643 described above.
Pages 28-29, RD18716 647 and RD30
The development can be performed by the usual method described in XIX of No. 8119.

[0066]

EXAMPLES The present invention will be described in detail below with reference to examples, but embodiments of the present invention are not particularly limited thereto.

Example 1 <Preparation of Silver Halide Emulsion Em-1> (Preparation of Twin Seed Emulsion 1) Seed Emulsion 1 having two parallel twin planes was prepared by the following method.

A. Ossein gelatin 80.0 g Potassium bromide 47.4 g 20 of HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H (m + n = 9.77) Weight% methanol solution 0.24 ml Make up to 8000.0 ml with distilled water.

B. Silver nitrate 1200.0 g Make up to 1600.0 ml with distilled water.

C. Ossein gelatin 32.2 g Potassium bromide 790.0 g Potassium iodide 70.34 g Make up to 1600.0 ml with distilled water.

D. Aqueous ammonia 470.0 ml To solution A vigorously stirred at 40 ° C., solution B and solution C were added for 7.7 minutes by a double jet method to generate nuclei. During this time, pBr was kept at 1.60.

Thereafter, the temperature was lowered to 20 ° C. over 30 minutes. Further, the solution D was added for 1 minute, followed by aging for 5 minutes. KBr concentration at aging is 0.03mo
l / l and the ammonia concentration were 0.66 mol / l.

After completion of the ripening, the pH was adjusted to 6.0 and desalting was carried out according to a conventional method. 10% by weight of the emulsion after desalting
Was added thereto, and the mixture was stirred and dispersed at 60 ° C. for 30 minutes, and then distilled water was added to prepare 5360 g of an emulsion. When the seed emulsion grains were observed with an electron microscope, the grains had two twin planes parallel to each other. The average grain size of the seed emulsion grains was 0.217 μm, and grains having two parallel twin planes were 75% (number ratio) of all grains.

(Preparation of Silver Halide Emulsion Em-1) A comparative silver halide emulsion (Em-1) was prepared using the following eight kinds of solutions.

(Solution A-1) 67.0 g of ossein gelatin 3176.0 ml of distilled water HO (CH ₂ CH ₂ O) _m [CH (CH ₃ ) CH ₂ O] _19.8 (CH ₂ CH ₂ O) _n H ( m + n = 9.77) in 20% by weight methanol solution 1.25 ml Seed emulsion (1) 98.51 g Make up to 3500.0 ml with distilled water.

(Solution B-1) 332 ml of 0.5N silver nitrate aqueous solution (solution C-1) 18.51 g of potassium bromide 12.44 g of ossein gelatin The solution is made up to 948 ml with distilled water.

(Solution D-1) 3.5N aqueous silver nitrate solution 1565 ml (Solution E-1) Potassium bromide 651.7 g Ossein gelatin 70 g Finished to 1565 ml with distilled water.

(Solution F-1) 862.9 g of a fine grain emulsion (*) consisting of 3% by weight of gelatin and silver iodide grains (average grain size: 0.05 μm) * The preparation method is described below.

6.0 containing 0.06 mol of potassium iodide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium iodide was added to 5000 ml of a weight% gelatin solution over 10 minutes. During the fine particle formation, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate. 12.53k finished weight
g.

(Solution G-1) 1.75 N aqueous solution of potassium bromide Solution A-1 was added to a reaction vessel, and while stirring vigorously,
Solutions B-1 to F-1 were added by a double jet method in accordance with the combinations shown in Table 4 to grow seed crystals to prepare core / shell type silver halide emulsions.

Here, (1) solution B-1, solution C-1 and solution F-1 addition rates, (2) solution D-1, solution E-1
The addition rates of solution 1 and solution F-1 and (3) the addition rates of solution D-1 and solution E-1 were changed in a function-wise manner with respect to time so as to correspond to the critical growth rate of silver halide grains. The addition rate was controlled to an appropriate rate so that the generation of small particles other than the growing seed crystal and the polydispersion due to Ostwald ripening did not occur.

The solution temperature in the reaction vessel was controlled at 75 ° C. and the pAg was controlled at 8.8 over the entire area of crystal growth. Solution p-1 was added as needed for pAg control.

Table 4 shows the grain size at that time with respect to the addition time of the reaction vessel, and the silver iodide content of the silver halide phase forming the surface.

[0084]

[Table 4]

After grain growth, desalting was carried out according to the method described in JP-A-5-72658, 1.19 l of a 20% by weight aqueous gelatin solution was added, and the mixture was dispersed at 50 ° C. for 15 minutes. With 3.5N aqueous potassium bromide solution
The Br was adjusted to 1.5, and while stirring at 50 ° C., the following solution H-2 was added at a constant speed for 10 minutes, followed by stirring for 20 minutes, and then at 40 ° C., a pH of 5.80 and pBr. 3.
Adjusted to 55.

(Solution H-2) Fine particle emulsion (*) consisting of 3% by weight of gelatin and silver bromide particles (average particle size 0.04 μm) 1.02 mol * The preparation method is described below.

6.0 containing 0.06 mol of potassium bromide
2000 ml of an aqueous solution containing 7.06 mol of silver nitrate and 7.06 mol of potassium bromide were added to 5000 ml of the gelatin solution of weight% over 10 minutes. During the formation of fine particles, the pH was adjusted to 2.0 using nitric acid, and the temperature was set to 30 ° C.
Was controlled. After the formation of the particles, the pH was adjusted to 6.0 using an aqueous solution of sodium carbonate.

The resulting emulsion has an average particle size (equivalent circle diameter).
The emulsion was 0.90 μm in average aspect ratio 2.0.

<Preparation of silver halide emulsion Em-2> (Preparation of seed emulsion 2) Seed emulsion 2 was prepared as follows.

Japanese Patent Publication Nos. 58-58288 and 58-58
No. 289, a silver nitrate aqueous solution (1.161 mol) was added to the following solution A1 adjusted to 35 ° C.
And a mixed aqueous solution of potassium bromide and potassium iodide (potassium iodide 2 mol%) while maintaining the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) at 0 mV. For 2 minutes to form nuclei. Subsequently, the temperature of the solution was raised to 60 ° C. over a period of 60 minutes, the pH was adjusted to 5.0 with an aqueous solution of sodium carbonate, and then an aqueous solution of silver nitrate (5.902 mol), potassium bromide and iodide were added. A mixed aqueous solution of potassium (2 mol% of potassium iodide) was added over 42 minutes by a double jet method while keeping the silver potential at 9 mV. After the addition was completed, the temperature was lowered to 40 ° C., and desalting and washing were immediately performed using a normal flocculation method.

The resulting seed crystal emulsion had an average sphere-equivalent diameter of 0.24 μm, an average aspect ratio of 4.8, and a maximum side ratio of 1.0% or more of 90% or more of the total projected area of silver halide grains.
~ 2.0 hexagonal tabular grains. This emulsion is referred to as seed emulsion 2.

[Solution A1] Ossein gelatin 24.2 g Potassium bromide 10.8 g HO (CH ₂ CH ₂ O) m (CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) nH (m + n = 9.77) (10% ethanol solution) 6.78 ml 10% nitric acid 114 ml H ₂ O 9657 ml Preparation of silver iodide fine grain emulsion SMC-1 5 l of 6.0% by weight gelatin aqueous solution containing 0.06 mol of potassium iodide While stirring vigorously, 2 l of a 7.06 mol aqueous solution of silver nitrate and 2 l of a 7.06 mol aqueous solution of potassium iodide were added over 10 minutes. During this time, the pH was controlled at 2.0 using nitric acid, and the temperature was controlled at 40 ° C. After the preparation of the particles, the pH was adjusted to 5.0 using an aqueous sodium carbonate solution. The average particle size of the obtained silver iodide fine particles is 0.05 μm.
Met. This emulsion is designated as SMC-1.

(Preparation of Silver Halide Emulsion Em-2)
178 mol of seed emulsion 2 and HO (CH ₂ CH ₂ O) m
(CH (CH ₃ ) CH ₂ O) _19.8 (CH ₂ CH ₂ O) nH
0.5 m of a 10% ethanol solution of (m + n = 9.77)
700% aqueous 4.5% by weight inert gelatin solution containing
The mixture was maintained at 75 ° C., the pAg was adjusted to 8.9 and the pH was adjusted to 5.0, and then particles were formed by the simultaneous mixing method with vigorous stirring by the following procedure.

1) 2.1 mol silver nitrate aqueous solution and 0.19
5 mol of SMC-1 and an aqueous solution of potassium bromide were added to pA
g was maintained at 8.9 and the pH was maintained at 5.0.

2) Subsequently, a 1.028 mol aqueous silver nitrate solution, 0.032 mol of SMC-1 and an aqueous potassium bromide solution were added while maintaining the pAg at 8.9 and the pH at 5.0.

Each solution was added at an optimum rate throughout the particle formation so as to prevent formation of new nuclei and Ostwald ripening between particles. After completion of the addition, the resultant was subjected to a water washing treatment at 40 ° C. using a normal flocculation method, and then gelatin was added and redispersed to adjust the pAg to 8.1 and the pH to 5.8.

The obtained emulsion has an average particle diameter (equivalent circle diameter).
The emulsion was composed of tabular grains having an average aspect ratio of 7.2 and an average aspect ratio of 7.2.

At this time, the gelatin contained in Em-1 and Em-2 had a weight-average molecular weight of 100,000 and 19.8 g per mol of silver halide.

<Preparation of silver halide emulsion layer coating solution> (Preparation of coating solution a) Using Em-1 prepared as described above, color sensitization and chemical sensitization were performed as follows, and the coating solution was prepared. Prepared. Em-1 was divided, a part of the solution was heated to 52 ° C., and sensitizing dyes SD-1, SD-2, and SD shown below were used.
-3 is 4.5 × 10 ^-4 mol per mol of silver halide,
6.0 × 10 ^-5 mol and 1.0 × 10 ^-4 mol were added. After another 20 minutes, sodium thiosulfate pentahydrate was added 2.0 ×
10 ⁻⁵ mol, 4.0 × 10 ⁻⁶ mol of triphenylphosphine selenide, 4.0 g of tetrachloroauric acid tetrahydrate
× 10 ^-6 mol and potassium thiocyanate 3.0 × 10 ^-4 mol were added, and the mixture was aged for 140 minutes. Thereafter, 6.5 × 10 ^-3 mol of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 1-phenyl-5-mercapto-
8.0 × 10 ^-5 mol of 1,2,3,4-tetrazole was added, and the temperature was lowered to 42 ° C. Then, a weight average molecular weight of 100
An appropriate amount of 000 gelatin and the following CP-1 were added to prepare a coating solution. This is referred to as a coating liquid a.

(Preparation of coating solution b) In the preparation of coating solution a, immediately after adding sodium thiosulfate pentahydrate, triphenylphosphine selenide, tetrachloroauric acid tetrahydrate and potassium thiocyanate, Weight average molecular weight 15
Except that 000 gelatin was added at 70 g / mol Ag.
A coating solution b was prepared in the same manner as the coating solution a. The gelatin having a weight average molecular weight of 15,000 was dissolved in water and added. (Hereinafter, all gelatins having a weight average molecular weight of 15,000 were dissolved in water and added.) (Preparation of Coating Solution c) In the preparation of coating solution a, sodium thiosulfate pentahydrate, triphenylphosphine selenide, Coating solution c was prepared in the same manner as coating solution a, except that immediately after adding tetrachloroauric acid tetrahydrate and potassium thiocyanate, 140 g / mol Ag of gelatin having a weight average molecular weight of 15,000 was added.

(Preparation of Coating Solution d) In the preparation of the coating solution a, 4-hydroxy-6-methyl-1,
3,3a, 7-tetrazaindene, 1-phenyl-5-
Mercapto-1,2,3,4-tetrazole is added,
Coating solution a except that 140 g / mol Ag of gelatin having a weight average molecular weight of 15,000 was added immediately after cooling to 42 ° C.
A coating solution d was prepared in the same manner as described above.

(Preparation of Coating Solution e) A coating solution e was prepared in the same manner as in the case of the coating solution d using Em-2.

(Preparation of Coating Solution f) Coating Solution f was prepared in the same manner as Coating Solution d, except that 140 g / mol Ag of gelatin having a weight average molecular weight of 100,000 was added.

(Preparation of coating solution g) Coating solution g was prepared in the same manner as coating solution d except that gelatin having a weight average molecular weight of 15,000 was added at 7 g / mol Ag.

(Preparation of Coating Solution h) In preparing Coating Solution d, 420 g of gelatin having a weight average molecular weight of 15,000 was added.
A coating solution h was prepared in the same manner as the coating solution d except that mole Ag was added.

(Preparation of Coating Solution i) In preparing Coating Solution d, gelatin having a weight average molecular weight of 15,000 was added at 1.4 g /
A coating solution i was prepared in the same manner as the coating solution d except that mole Ag was added.

(Preparation of Coating Solution j) In preparing Coating Solution d, gelatin having a weight average molecular weight of 15,000 was added to 840 g / g
Coating solution j was prepared in the same manner as coating solution d except that mole Ag was added.

In the examples, the gelatin of the present invention was obtained by enzymatically decomposing gelatin generally used for photography. The weight-average molecular weight of the obtained enzyme-decomposed gelatin and raw material gelatin was measured by the following apparatus and conditions. Weight average molecular weight before enzymatic decomposition is 1000
On the other hand, the weight average molecular weight after enzymatic decomposition was 15,000.

Pump: Shimadzu LC-6A Detector: Hitachi L-4250 Data processor: Shimadzu C-R4A Column oven: GL Science column oven Column: Showa Denko Asahipak GS-620
Two-link eluent: 0.05M potassium dihydrogen phosphate, 0.05M
Sodium dihydrogen phosphate aqueous solution Flow rate: 1.0 ml / min Injection amount: 100 μl Measurement gelatin concentration: 0.2% Detection wavelength: 230 nm Standard sample: Showa Denko standard sample STANDARD
P-82

[0110]

Embedded image

<Preparation of Single Emulsion Layer Sample> A surfactant, a hardener and the like were further added to each coating solution, and immediately applied onto a triacetyl cellulose transparent support to prepare a sample.
The sample coated with the coating liquid a was referred to as Sample 1, and the samples coated with the coating liquids b to j were referred to as Samples 2 to 10. The amount of gelatin added is shown in the table.

<Evaluation of Each Sample> The samples prepared as described above were subjected to a wedge exposure for 1/200 second through a Y-48 filter, and were subjected to development processing according to the following development processing.

(Processing Step) Processing Step Processing Time Processing Temperature Replenishment Color Developing 3 min 15 sec 38 ± 0.3 ° C. 780 ml Bleaching 45 sec 38 ± 2.0 ° C. 150 ml Fixing 1 min 30 sec 38 ± 2.0 ° C. 830 ml Stabilizing 60 seconds 38 ± 5.0 ° C. 830 ml drying 1 min 55 ± 5.0 ℃ - * the replenishing amount is a value per photosensitive material 1 m ^2.

The following color developing solutions, bleaching solutions, fixing solutions, stabilizing solutions and replenishers were used.

Color developer and color replenisher Developer replenisher Water 800 ml 800 ml potassium carbonate 30 g 35 g sodium hydrogen carbonate 2.5 g 3.0 g potassium sulfite 3.0 g 5.0 g sodium bromide 1.3 g 0.4 g potassium iodide 1.2 mg-hydroxylamine sulfate 2.5 g 3.1 g sodium chloride 0.6 g-4-amino-3-methyl-N-ethyl-N-([beta] -hydroxylethyl) aniline sulfate 4.5 g 6.3 g diethylenetriamine Pentaacetic acid 3.0 g 3.0 g Potassium hydroxide 1.2 g 2.0 g Add water to make 1 liter, and use potassium hydroxide or 20% sulfuric acid to adjust the color developing solution to pH 10.06 and the replenisher to pH 10.18. Adjust to

Bleach and Bleach Replenisher Bleach Replenisher Water 700 ml 700 ml Ammonium 1,3-diaminopropanetetraacetate (III) ammonium 125 g 175 g ethylenediaminetetraacetic acid 2 g 2 g sodium nitrate 40 g 50 g ammonium bromide 150 g 200 g glacial acetic acid 40 g 56 g water To 1 liter, and the pH of the bleaching solution is adjusted to pH 4 using aqueous ammonia or glacial acetic acid. In 4, adjust the replenisher to pH 4.0.

Fixer and Fixer Replenisher Fixer Replenisher Water 800 ml 800 ml Ammonium thiocyanate 120 g 150 g Ammonium thiosulfate 150 g 180 g Sodium sulfite 15 g 20 g Ethylenediaminetetraacetic acid 2 g 2 g The fixer is adjusted to pH 6.2 using aqueous ammonia or glacial acetic acid. After adjusting the pH of the replenisher to 6.5, add water to make 1 liter.

Stabilizing Solution and Stabilizing Replenisher Water 900 ml p-octylphenol ethylene oxide 10 mol adduct 2.0 g dimethylolurea 0.5 g hexamethylenetetramine 0.2 g 1,2-benzoisothiazolin-3-one 0.1 g siloxane (UCC 0.1 g ammonia water 0.5 ml Water was added to make up to 1 liter, and then the pH was adjusted to 8.0 using ammonia water or 50% sulfuric acid. Adjust to 5.

The processed sample was evaluated for relative sensitivity and granularity. The fog density indicated the value of the green light transmission density using a Konica PD transmission densitometer. Relative sensitivity is fog density +
The relative value of the reciprocal of the exposure that gives a density of 0.15;
The sensitivity was set to a value where the sensitivity of Sample 1 was 100. The graininess was determined by changing the density of fog density + 0.15 to the aperture scanning area of 250 μm ^2.
Are shown as relative values of the standard deviation (RMS value) of the fluctuation of the density value caused when scanning with a microdensitometer.
The smaller the RMS value, the better the granularity. Sample 1
The RMS value of was set to 100.

[0120]

[Table 5]

As is clear from the above results, the silver halide photographic light-sensitive material obtained according to the present invention shows excellent performance in all of fog, relative sensitivity and graininess as compared with the comparative photographic light-sensitive material.

Example 2 <Preparation of Silver Halide Emulsion Em-3> (Preparation of Silver Halide Emulsion Em-3) At the time of grain growth of Em-2 prepared in Example 1, thiourea dioxide and ethyl thiosulfonic acid were used during grain growth. After reduction sensitization, the average particle size is 1.35μ.
m, and reduction sensitized tabular grains having an average aspect ratio of 7.2 were prepared.

At this time, the gelatin contained in Em-3 was
19. weight-average molecular weight of 100,000, and per mole of silver halide
8 g.

(Preparation of Coating Solution k) In the preparation of the coating solution a of Example 1, except that Em-3 was used instead of Em-1, the same preparation as that of the coating solution a was performed. Prepared.

(Preparation of Coating Solution 1) In preparing Coating Solution d of Example 1, except that Em-3 was used instead of Em-1, the same preparation as Coating Solution d was carried out. Prepared.

<Preparation of Single Emulsion Layer Sample> A sample was prepared in the same manner as in Example 1. Samples to which the coating liquids k and l were applied were used as sample 11 and sample 12, respectively.

<Evaluation of Each Sample> The prepared sample was subjected to the same exposure and development processing as in Example 1, and the same evaluation was performed. The sensitivity and RMS value of Sample 11 were shown as values with 100 being used.

[0128]

[Table 6]

As is evident from the above results, the silver halide photographic light-sensitive material obtained according to the present invention, even when a reduction sensitized emulsion was used, had fog, relative sensitivity, and graininess as compared with comparative photographic light-sensitive materials. Both show excellent performance.

Example 3 (Stagnation stability test of coating solution) A part of the coating solution a and the coating solution d of Example 1 was continuously stirred at 40 ° C. for 12 hours. The obtained coating liquids are referred to as coating liquid m and coating liquid n, respectively.

<Preparation of Single Emulsion Layer Sample> Samples of the prepared coating solution a and coating solution d were prepared in the same manner as in Example 1, and were designated as Sample 1 and Sample 4, respectively. After the stagnation was completed, a hardener was added to the coating solution m and the coating solution n, and the solution was applied onto a triacetyl cellulose transparent support to obtain a sample having a stagnation time of 12 hours. The samples coated with the coating liquid m and the coating liquid n were referred to as Sample 101 and Sample 104, respectively.

<Evaluation of Each Sample>
Exposure and development were carried out in the same manner as described above, and the relative sensitivity and fog were evaluated. Assuming that the sensitivity of Sample 1 was 100, Δ relative sensitivity and Δ fog were evaluated as follows.

ΔRelative sensitivity = (Relative sensitivity at stagnation time 12 hours) − (Relative sensitivity at stagnation time 0 hours) ΔFog = (Fog at stagnation time 12 hours) − (Fog at stagnation time 0 hours) In the evaluation, the values of Δ relative sensitivity and Δ fog were 0
The closer to, the better.

[0134]

[Table 7]

As is apparent from the above results, the light-sensitive material using the silver halide emulsion coating solution obtained according to the present invention shows performance superior in stagnation stability as compared with the comparative coating solution.

[0136]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity, low fog and excellent graininess, and a coating solution for a silver halide emulsion layer having excellent stagnation stability are obtained.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material characterized in that the silver halide light-sensitive material contains gelatin having a weight average molecular weight of 500 or more and 50,000 or less per square meter of 0.15 g or more and 20 g or less. 2. A silver halide emulsion layer coating solution characterized in that the silver halide emulsion layer coating solution contains gelatin having a weight average molecular weight of 500 or more and 50,000 or less per mol of silver of 3 g or more and 300 g or less.