JPH08286308A - Silver halide photosensitive material - Google Patents

Abstract

PURPOSE: To provide a silver halide photosensitive material with high sensitivity which is free from deterioration of desensitizing pressure. CONSTITUTION: In a silver halide photo material having a silver halide emulsion applied onto a support body, the average iodine content of the silver halide particle in the emulsion is 1.5mol% or more, the silver halide particle consists of a silver halide particle having no parallel twin surface, and has a high iodine phase with an average iodine content of 20mol% or more in the particle inner part, a selenium compound is contained in the emulsion, and the difference in sensitivity of this photosensitive material between the exposure with an exposure time of 1/12.5sec. and the exposure with 8sec. is within 0.3 when expressed by the logarithm of inverse of the exposure.

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 more particularly to a silver halide photographic light sensitive material having high sensitivity and improved desensitizing pressure due to bending and the like.

[0002]

2. Description of the Related Art In recent years, along with the prolongation of life, the number of medical X-ray examinations has increased with the development of various diagnostic devices, and there has been a strong demand from the medical society and public opinion to reduce the exposure dose. Therefore, the development of a medical silver halide photographic light sensitive material having higher sensitivity has been awaited.

On the other hand, a high-sensitivity silver halide photographic light-sensitive material (hereinafter referred to as a light-sensitive material) has a relatively high sensitivity to not only light but also various external factors.
Failure is likely to occur. For example, mechanical pressure applied before exposure may cause desensitization pressure (the mechanical pressure applied to the film before exposure causes a desensitization phenomenon during development).

Since a medical film has a large size, it is bent from the supported portion by its own weight,
So-called nail breakage is likely to occur. Recently, medical X
As a line system, automatic exposure and automatic development using mechanical transportation are widely used, but mechanical pressure may be applied to the film even during transportation of such an apparatus.

The desensitizing pressure generated when such a pressure is applied may seriously hinder medical diagnosis.

As a technique for improving the desensitizing pressure, US Pat. Nos. 2628167, 2759822 and 34
55235, 2296204, and French Patent 2296204,
JP-A-51-107129 and JP-A-50-116025 are known,
In all cases, the degree thereof was insufficient, and further improvement was required especially for a light-sensitive material using a selenium (hereinafter referred to as Se) compound for chemical ripening.

[0007]

In order to solve the above problems, an object of the present invention is to solve the above-mentioned drawbacks and provide a silver halide photographic light-sensitive material having high sensitivity and without deterioration of desensitizing pressure. There is something to do.

[0008]

The above object of the present invention is to provide a light-sensitive material in which a silver halide emulsion layer is coated on a support, and the average iodine of the silver halide grains in the silver halide emulsion. The content of the silver halide grains is 1.5 mol% or more, and the silver halide grains are silver halide grains having no parallel twin planes. Further, the grains have a high iodine phase having an average iodine content of 20 mol% or more. And the silver halide emulsion contains a Se compound, and the difference between the sensitivity when the photosensitive material is exposed for an exposure time of 1 / 12.5 seconds and the sensitivity when exposed for 8 seconds is It is achieved by a light-sensitive material characterized by being within 0.3 when expressed by the logarithm of the reciprocal of the exposure dose.

When the above silver halide emulsion is chemically sensitized with a sulfur compound and a Se compound, the above-mentioned general formula (1) is used.
It is a preferred embodiment that the compound represented by

The present invention will be specifically described below.

When an emulsion in which grains having an average iodine content of 1 mol% or more are chemically ripened with a Se compound for the purpose of increasing sensitivity, desensitizing pressure is deteriorated. In the present invention, the average iodine content is per mol of silver.
It is 1.5 mol% or more, preferably 2 mol% or more. Further, the emulsion grains of the present invention have a high iodine phase of 20 mol% or more in the inside, and Se sensitization has been performed. The sensitivity when the material is exposed with an exposure time of 1 / 12.5 seconds, and 8
It was found that the desensitization pressure can be reduced while adjusting the chemical aging conditions so that the difference in sensitivity when exposed in seconds is within 0.3 when expressed by the logarithm of the reciprocal of the exposure amount. Of.

A method of calculating the sensitivity when the exposure time is 1 / 12.5 seconds and 8 seconds according to the present invention will be described. As the exposure conditions, a wedge sphere having a color temperature of 2800 to 2900 ° K and a light amount of 640 to 650 cd is used as a light source, and wedge exposure is performed using a step wedge with an optical density of 0.1. At this time, the distance from the light source to the film is adjusted at each exposure amount so that the light amount on the film surface becomes 3.2 cms. The film thus exposed is developed with the following treating agents.

Developer Part-A Potassium hydroxide 310g Potassium sulfite (50% solution) 1950g Diethylenetetraamine pentaacetic acid 90g Sodium bicarbonate 108g 5-Methylbenzotriazole 1.6g 1-Phenyl-5-mercaptotetrazole 160mg Hydroquinone 290g Water In addition, finish to 3000 ml.

Part-B Glacial acetic acid 158 g Triethylene glycol 150 g 1-Phenyl-3-pyrazolidone 19.5 g 5-Nitroindazole 0.32 g n-Acetyl-D, L-penicillamine 1.1 g Add water to make 350 ml Part-A Part-B was mixed and made up to 10.8 l with water.

Starter (for finishing 1.0 l) Glacial acetic acid 138 g Potassium bromide 325 g 5-Methylbenzotriazole 1.5 g CH ₃ N (C ₃ H ₆ NHCONHC ₂ H ₄ SC ₂ H ₅ ) ₂ 20 mg Add water to 1.0 l Finishing The starter was added in an amount of 20 ml per developer.

Fixer Part-A Ammonium thiosulfate (70wt / vol%) 4600g Sodium sulfite 150g Sodium acetate trihydrate 340g Sodium citrate 40g Gluconic acid 60g Boric acid 28g Glacial acetic acid 120g Add water to finish to 4000m Part-B Aluminum sulfate 56g Sulfuric acid (50wt%) 90g Add water to make 700ml Part-A and Part-B were mixed and made to 16.4l with water.

A film is processed using the above developing solution and fixing solution under the following processing conditions.

Processing Step Processing Temperature (° C) Processing Time (sec) Insert --- 2.4 Development + Crossover 35 29.4 Fixing + Crossover 33 21.8 Washing + Crossover 18 13.0 Squeeze 40 9.0 Dry 50 14.4 Total --90.0 The density is measured with a PDA-65 (manufactured by Konica Corporation) densitometer, and the reciprocal of the light amount at which the optical density becomes the fog density +0.1 is displayed in logarithm and calculated.

The chemical aging conditions are set so that the difference between the sensitivity when exposed for an exposure time of 1 / 12.5 seconds calculated in this way and the sensitivity when exposed for 8 seconds is 0.3 or less, preferably 0.2 or less. To adjust.

Specific examples of the compound of the present invention represented by the general formula (1) include the following compounds, but not limited to these compounds.

1-1 Ga (NO ₃ ) ₃ , 1-2 In (NO ₃ ) ₃ , 1-
3 Tl (NO ₃ ) ₃ , 1-4 GaBr ₃ , 1-5 InBr ₃ , 1-6
TlBr ₃ , 1-7 GaI ₃ , 1-8 InI ₃ , 1-9 Tl
I ₃ , 1-10 Ga ₂ SO ₄ , 1-11 In ₂ SO ₄ , 1-1
2 Tl ₂ SO ₄ , 1-13 Ga ₂ C ₃ , 1-14 In ₂ CO ₃ , 1-15
The addition amount of Tl ₂ CO ₃ and the compound of the present invention represented by the general formula (1) [hereinafter referred to as compound (1)] is preferably 10 mmol or more and 80 mmol or less, and more preferably 20 mmol per mol of silver.
It is not less than mmol and not more than 60 mmol.

The compound (1) should be added before the chemical sensitization, but preferably after the addition of Ag ions and halide ions and the completion of grain formation. It is preferable to add it during the time until the completion of the chemical sensitization.

The silver halide grain in the present invention is a grain having no parallel twin plane. The average particle size of the particles is 0.1
˜2.0 μm is preferable, and 0.4 to 1.4 μm is particularly preferable. Its grain size is defined as the diameter of a sphere having a volume equal to that of the grain from the observation of electron micrographs of silver halide grains.

The size of the silver halide grain can be controlled by the temperature at the time of grain formation and the addition rate of the silver salt and halide aqueous solution. The grain growth may be carried out by supplying an aqueous solution containing silver ions and an aqueous solution containing halogen ions, or may be supplied as fine particles of silver halide. In this case, a combination of silver iodide, silver iodobromide, silver bromide, silver chlorobromide, silver chloride, a halogen ion-containing solution, a silver ion-containing solution and the like can be supplied.

As the silver halide emulsion of the present invention, those which are monodisperse are preferably used, and the variation coefficient of the average grain size is 25%.
It is preferably 20% or less, more preferably 20% or less.

Silver iodobromide and silver chloroiodobromide are used in the silver halide emulsion of the present invention, and the silver iodide content is 1.5 mol% or more, preferably the silver iodide content is 2 mol. % Or more 3
Silver iodobromide of not more than mol% is preferable.

The silver halide grain of the present invention is a so-called core-shell type grain having a high iodine phase inside the grain, and the iodine content of the internal high iodine phase is preferably 25 mol% or more, more preferably It is a high iodine phase having a content of 30 mol% or more.

The phase outside the high iodine phase may be of any silver halide composition as long as it has a lower iodine content than the high iodine phase, but the iodine content is preferably 0.5 mol% or less. Silver iodobromide, more preferably pure silver bromide, is preferred.

Regarding the core / shell type particles, JP-A-59-1
Particles can be prepared by the method described in JP-A-77535, JP-A-59-178447, JP-A-60-35726, JP-A-60-147727 and the like.

The silver halide emulsion may be subjected to a water washing method such as a Noudel water washing method and a flocculation sedimentation method in order to remove soluble salts. As a preferred washing method,
For example, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in JP-B-35-16086, or JP-A-63-1
As a particularly preferable desalting method, a method using G3, G8, etc. exemplified by the aggregation polymer agent described in No. 58644 can be mentioned.

As the chemical sensitization method, selenium sensitization and sulfur sensitization are used, and gold sensitization, sensitization with a noble metal of Group VIII of the periodic table (for example, Pd, Pt, Id, etc.), and a combination thereof are used. A sensitizing method can be used.

The selenium compounds used in the chemical sensitization of the present invention include a wide variety of selenium compounds. For example US patent
1,574,944, 1,602,592, 1,623,499, JP 6
0-150046, JP-A-4-25832, 4-109240, 4-147
Those described in No. 250 can be used. Useful selenium compounds include colloidal selenium metal, isoselenocyanates (eg, allyl isoselenocyanate, 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- Nitrophenylcarbonyl selenourea etc.), selenoketones (eg selenoacetone, selenoacetophenone etc.), selenoamides (eg selenoacetamide, N, N-dimethylselenobenzamide etc.), selenocarboxylic acids and selenoesters (eg 2 -Selenopropionic acid, methyl-3-selenobutylate, etc.), selenophosphates (eg,
Tri-p-triselenophosphate and the like) and selenides (diethyl selenide, diethyl diselenide, triphenylphosphine selenide, etc.). Particularly preferred selenium compounds are selenoureas, selenoamides, and selenium ketones.

Specific examples of techniques for using these selenium compounds are disclosed in the following patent specifications. US Patent 1,574,
944, 1,602,592, 1,623,499, 3,297.446
Issue 3,297,447, 3,320,069, 3,408,196,
3,408,197, 3,442,653, 3,420,670, 3,5
91,385, French Patents 2,693,038, 2,093,209
No. 52-34491, 52-34492, 53-295, 53-295
57-22090, JP-A-59-180536, 59-185330, 59
-181337, 59-187338, 59-192241, 60-1500
46, 60-151637, 61-246738, JP 3-4221
No. 3, No. 3-24537, No. 3-111838, No. 3-116132, No. 3-1
48648, 3-237450, 4-16838, 4-25832,
4-32831, 4-96059, 4-109240, 4-140738
No. 4-140739, 4-147250, 4-149437, 4-
184331, 4-190225, 4-191729, 4-195035
No., British Patent Nos. 255,846, 861,984, etc. HESpen
cer et al., Journal of Photographic Science magazine, Vol. 31, 15
It is also disclosed in scientific literature such as pages 8 to 169 (1983).

The amount of the selenium compound used varies depending on the selenium compound used, silver halide grains, chemical ripening conditions and the like, but it is generally preferable to use about 10 ^-8 to 10 ^-4 mol per mol of silver halide. The addition method is, depending on the properties of the selenium compound to be used, a method of adding by dissolving in water or an organic solvent of methanol, ethanol, ethyl acetate or the like alone or a mixed solvent, or a method of pre-mixing with a gelatin solution and adding. Any method such as the method disclosed in JP-A-4-140739, that is, the method of adding in the form of an emulsion dispersion mixed with an organic solvent-soluble polymer may be used.

The emulsion layer degree of chemical ripening using a selenium compound is preferably in the range of 40 to 90 ° C. More preferably, it is 45 ° C or higher and 80 ° C or lower. The pH is preferably aged in the range of 6.0 to 10.0.

In the present invention, it is possible to sensitize with a selenium compound, but it is also possible to sensitize with a noble metal salt such as a sulfur compound or a gold salt. Further, reduction sensitization can be performed, and these methods can be combined to perform sensitization.

Sulfur sensitizers applicable in the present invention include US Pat. Nos. 1,574,944, 2,410,689 and 2,278,
947, 2,728,668, 3,501,313, 3,656,955
Issue, West German application publication (OLS) 1422,869, JP-A-56-24937
The sulfur sensitizers described in JP-A No. 55-45016 and the like can be used. Specific examples include thiourea derivatives such as 1,3-diphenylthiourea, triethylthiourea, and 1-ethyl-3- (2-thiazolyl) thiourea, rhodanine derivatives, dithiacarbamic acids, polysulfide organic compounds, simple sulfur, etc. Are preferred examples. As the simple substance of sulfur, α-sulfur belonging to the orthorhombic system is preferable.

As the gold sensitizer, chloroauric acid, gold thiosulfate,
In addition to gold thiocyanate, there can be mentioned gold complexes of thioureas, rhodanines, and various other compounds.

The amount of sulfur sensitizer and gold sensitizer used is not uniform depending on the type of silver halide emulsion, the type of compound used, the ripening conditions, etc., but is usually 1 × 10 6 per mol of silver halide. It may be ^-6 mol to 1 x 10 ^-2 mol. Similarly, thiocyanates such as potassium thiocyanate and ammonium thiocyanate are added at 1 × 10 ⁻⁶ per mol of silver halide.
Moles to 1 × 10 ^-2 mol may be used.

In the present invention, the sulfur sensitizer in the chemical ripening, such as sodium thiosulfate and the selenium compound, may have a molar ratio of 100: 1 to 1:10, and further 20: 1 to.
1: 1 is preferred.

It is also preferable to carry out the chemical sensitization in the presence of a compound having adsorptivity to silver halide. Particularly preferred compounds are azoles, diazoles, triazoles, tetrazoles, indazoles, thiazoles, pyrimidines, azaindenes, particularly compounds having a mercapto group and compounds having a benzene ring.

It is also preferable to use a cyanine dye of monomethine or trimethine.

The light-sensitive material of the present invention is subjected to a reduction treatment, that is, a so-called reduction sensitization method, in which a reducing compound is added,
A method of passing a silver ion excess state of pH Ag = 1 to 7 called silver ripening, a high pH of pH = 8 to 11 called high pH ripening
You may apply to a silver halide emulsion by the method of making a state pass. Further, these two or more methods can be used in combination.

The method of adding a reducing compound is preferable because the degree of reduction sensitization can be finely adjusted. The reducing compound may be an inorganic or organic compound, such as thiourea dioxide, stannous salt, amines and polyamines, hydrazine derivatives, formamidinesulfinic acid, silane compounds, borane compounds, ascorbic acid and its derivatives, sulfite. Examples thereof include salts, and particularly preferable examples include thiourea dioxide, stannous chloride and dimethylamine borane. The addition amount of these reducing compounds varies depending on the reducing property of the compound, the type of silver halide, the emulsion production conditions such as the dissolution conditions, and is 1 × 10 ⁻⁸ per mol of silver halide.
A range of up to 1 × 10 ^-2 mol is suitable. These reducing compounds are dissolved in water or an organic solvent such as alcohols and added during the growth of silver halide grains.

Gelatin is preferably used as the hydrophilic colloid or binder used in the light-sensitive material of the present invention, but other hydrophilic colloids can also be used.

For example, gelatin derivatives, graft polymers of gelatin and other polymers, proteins such as albumin and casein, hydroxyethyl cellulose, carboxymethyl cellulose, cellulose derivatives such as cellulose sulfates, sugar derivatives such as sodium alginate, dextran and starch derivatives. Polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylimidazole, polyvinylpyrazole, etc. Can be used. In particular, it is preferable to use dextran or polyacrylamide having a number average molecular weight of 5000 to 100,000 together with gelatin. Examples of these are, for example, JP-A-1-307738, 2-62532, 2-24748,
2-44445, 1-66031, JP-A-64-65540, JP-A-63
-101841 and 153538.

The gelatin includes lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin as described in Bull. Soc. Sci. Phot, Japan. No. 16, page 30 (1966), as well as gelatin derivatives ( For example, those obtained by reacting various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkylene oxides and epoxy compounds ) Is included.

The emulsion according to the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening. Known additives include, for example, Research Disclosure (RD) No. 17643 (December 1978).
No. 18716 (November 1979) and No. 308119 (198)
The compound described in December, 9) is mentioned. The types of compounds and the places where they are described in these three Research Disclosures are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Classification Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 B Dye 25-26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant Agent 26-7 XI 650 Right 1005-6 XI Antistatic agent 27 XII 650 Right 1006-7 XIII Plasticizer 27 XII 650 Right 1006 XII Sliding agent 27 XII Matting agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX The photographic processing of the light-sensitive material of the present invention can be carried out, for example, in RD-17643, XX to XXI, pages 29 to 30 or 308119, XX.
~ XXI, treatment with a treatment solution as described on pages 1011 to 1012 can be performed. This process may be a black and white photographic process that forms a silver image. Processing temperature is usually 18
It is processed in the range of ~ 50 ° C.

Developers for black and white photographic processing include dihydroxybenzenes (eg hydroquinone), 3-pyrazolidones (eg 1-phenyl-3-pyrazolidone), aminophenols (eg N-methyl-p-aminophenol).
Etc. can be used alone or in combination.
It should be noted that the developer may be any known one such as preservative, alkaline agent, pH.
If necessary, a buffering agent, an antifoggant, a development accelerator, a surfactant, an antifoaming agent, a toning agent, a water softener, a solubilizing agent, a viscosity imparting agent and the like can be used.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution and may further contain water-soluble aluminum such as aluminum sulfate or potassium alum as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0052]

EXAMPLES Examples of the present invention will be described below. Naturally, the present invention is not limited to the examples described below.

Example 1 (Preparation of seed particles) While maintaining 60 ° C., pAg = 8 and pH = 2, an Ag ionic liquid and a halide ionic liquid (the ratio of Br ion to I ion is 98: 2) by the double jet method. Was added to obtain a monodispersed silver iodobromide emulsion having an average grain size of 0.3 μm and a silver iodide content of 2 mol%. The pH of the obtained emulsion was adjusted to 6 with sodium carbonate, followed by precipitation using a demol aqueous solution and a magnesium sulfate aqueous solution manufactured by Kao Atlas Co., and decantation was performed to remove unnecessary inorganic salts.

When the grains of the resulting emulsion were observed with an electron microscope, no twins having parallel twin planes were found, but the rate of occurrence of other twins was 1% or less.

(Preparation of growing grains) 0.03 in terms of silver mole number
Three moles of the seed emulsion prepared above was added to the following A1 solution kept at 70 ° C., and 5 minutes after the addition, the following B1 and C1 solutions were added by the double jet method. The speed of addition is B1 and C
An equal amount of each solution was added to each solution, and the operation was performed within the range where no new nuclei were generated.

At this time, a 56% acetic acid solution, which was separately prepared, was added as necessary so as to keep the pH at 7. Potential is 70
A 25% potassium bromide aqueous solution separately prepared was appropriately added as necessary so as to keep the pH at mV.

Immediately after adding the B1 and C1 solutions, B2 and C were added.
Two solutions were added in the same manner as B1 and C1. However, the addition rate of B2 was 1.26 times that of C2. PH during addition
Was kept at 7 and the potential was kept at 70 mV.

When 70% of the added amount of B2 was added,
The whole liquid D1 was added. After that, the potential was not controlled and the particles were grown without any control.

A1 ossein gelatin 15.9g DF-1 0.14ml polypropyleneoxy / polyethyleneoxy copolymer (block polymer) MW = 1500 (10% methanol solution) 1.1ml 28% ammonia water 17.5ml 56% acetic acid 26.0ml water 142.0 ml B1 silver nitrate 16.6 g 28% ammonia water 13.0 ml water 57.4 ml C1 ossein gelatin 0.28 g potassium bromide 8.1 g potassium iodide 4.87 g water 57.4 ml B2 silver nitrate 147.7 g 28% ammonia Water 115.7 ml Water to 248.5 ml C2 ossein gelatin 1.00 g Potassium bromide 100.3 g Water to 198.3 ml D1 Potassium bromide 44.2 g Water to 70 ml After adding B2 and C2, add a 56% acetic acid solution. Was used to adjust the pH to 6.

The emulsion thus obtained was precipitated using an aqueous demol solution manufactured by Kao Atlas and an aqueous magnesium sulfate solution, decanted to remove unnecessary inorganic salts, and gelatin was added to the emulsion to redisperse it. The potential of this silver halide emulsion at 50 ° C. was 50 mV, and its pH was 5.85. When 200 particles thus obtained were arbitrarily selected and the particle diameter was measured by an electron microscope, the average particle diameter was 1.06μ. The coefficient of variation of particle size distribution was 0.15.

1 mol per mol of silver was added to the emulsion prepared above.
% NH ₄ SCN 5.2 ml, 0.2% HAuCl ₄ 0.78 ml, 0.25% Na ₂ S
Immediately before the chemical sensitizer consisting of 5.6 ml of ₂ O ₃ and 3.5 ml of 0.4% triphenylphosphine selenide, 40 mg and 8 mg of the following spectral sensitizing dyes (A) and (B) were added respectively. Chemically aged at 48 ° C.

[0062]

Embedded image

The aging condition was applied so that the fog was 0.02,
2.4 g of 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added per mol of silver halide, and the temperature was lowered to stop the chemical ripening.

Similarly, particles having an average particle size of 0.7 μ and 1.3 μ were prepared and chemically sensitized. The chemical sensitizer, sensitizing dye, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added in amounts proportional to the surface area of the particles.

The average particle size thus obtained is 1.3
μ, 1.06μ, 0.7μ of each silver halide emulsion 8:50:42
A silver halide emulsion was prepared by mixing in the proportion of 1.

The following compounds were added per 1 mol of silver to the emulsion 1 prepared above to prepare a coating solution for emulsion 1.

1-phenyl-5-mercaptotetrazole 10 mg 1-trimethylolpropane 14 g t-butyl-catechol 68 mg polyvinylpyrrolidone (molecular weight 10,000) 850 mg styrene-maleic anhydride copolymer 2.0 g nitrophenyl-triphenyl-phosphonium chloride 50 mg Ammonium 1,3-dihydroxybenzene-4-sulfonate 1.7 g 1,1 Dimethylol-1-bromo-1-nitromethane 6.2 mg nC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 700 mg

[0068]

Embedded image

The additives used in the emulsion protective layer liquid are as follows. The added amount is shown as an amount per 1 g of gelatin.

Matting agent composed of polymethylmethacrylate having an average particle size of 5 μm 21 mg Matting agent composed of polymethylmethacrylate having an average particle size of 3 μm
28 mg

[0071]

Embedded image

When chemical sensitization was performed, emulsions obtained by chemically sensitizing and mixing emulsions of respective grain sizes to prepare a coating solution were prepared as emulsion 2 except that the Se compound was omitted from the sensitizer formulation. To do.

Emulsions prepared in the same manner as Emulsion 1 except that the amount of the sensitizing dye added when preparing Emulsion 1 was 1/2, 1/4, and 1/8, respectively, were Emulsion 3 and Emulsion 4, respectively. , Emulsion 5

This is to control the chemical sensitization by changing the amount of dye and to see the effect on the desensitizing pressure.

When preparing Emulsion 1, C1 at the time of grain formation was used.
Emulsion 6 was prepared in the same manner as Emulsion 1 except that the amounts of potassium bromide and potassium iodide were adjusted to change the iodide composition having high internal iodine from 30 mol% to 10 mol%. To do.

The emulsion coating solution and emulsion protective film solution prepared above were simultaneously coated on the undercoated base. The amount of silver on the emulsion layer side was 2.8 g / m ² per side, the amount of gelatin was 2.4 g / m ^{2 on the} emulsion layer, and the protective film was 1.3 g / m ² .

The chemical sensitization time for each emulsion was adjusted so that the difference between the sensitivity when the light-sensitive material was exposed for 1 / 12.5 seconds and the sensitivity when it was exposed for 8 seconds was the value (ΔS) shown in Table 1. It was adjusted and applied.

The obtained sample was placed in an environment of 30 ° C. and 40% RH for 12 hours.
After leaving for a while, fog, sensitivity difference between exposure for 12.5 seconds and 8 seconds, sensitivity when exposed for 1 / 12.5 seconds, and desensitizing pressure due to bending were evaluated.

The desensitizing pressure was evaluated by using 23 samples.
After leaving it for 1 hour in the environment of ℃ and 40% RH, the radius of curvature is 5mm
Immediately after bending to the
NR-160 (manufactured by Konica Corporation) so that the sample becomes 1.0
X-ray exposure was carried out by sandwiching the intensifying screen, and the treatment according to the above-mentioned prescription and conditions was performed to reduce the density of the bent portion (ΔD /
D) was evaluated.

The results are shown in Table 1.

[0081]

[Table 1]

The results in Table 1 show that the samples of the present invention have high sensitivity and little desensitizing pressure.

Example 2 Addition of chemical sensitizer in preparing Emulsion 1 of Example 1
An emulsion was prepared in the same manner as in Example 1 except that the compound (1) shown in Table 2 was added before the chemical sensitization.
Coating was performed to prepare a sample. The difference between the sensitivity of 12.5 second exposure and the sensitivity of 8 second exposure of the sample prepared in Example 2 (ΔS)
Was 0.35 for all samples.

The results are shown in Table 2.

[0085]

[Table 2]

From the results shown in Table 2, it can be seen that the samples of the present invention containing the compound (1) have less desensitizing pressure.

Example 3 When preparing Emulsion 1, the addition amount of B1 and C1 and B
2, the amount of C2 added liquid is appropriately adjusted so that the internal high iodine phase has an iodine content of 30 mol% and the average iodide content of the grains is 1.0 mol%, 1.5
Silver halide grains were prepared by changing the mol percentage to 2.0 mol%. The silver halide grains were mixed with silver halide grains having different average particle sizes as in Example 1 and chemically sensitized to prepare a sample, which was evaluated in the same manner as in Example 1.

The results obtained are shown in Table 3.

[0089]

[Table 3]

The results shown in Table 3 show that the samples having the average iodine content of the present invention have good sensitivity.

[0091]

According to the present invention, a silver halide photographic light-sensitive material having high sensitivity and no deterioration of desensitizing pressure can be provided.

Claims (2)

[Claims] 1. A silver halide photographic light-sensitive material in which a silver halide emulsion layer is coated on a support, wherein the silver halide emulsion has an average iodide content of 1.
5 mol% or more, and the silver halide grains are silver halide grains having no parallel twin planes, and further have a high iodine phase having an average iodine content of 20 mol% or more inside the grain,
The silver halide emulsion contains a selenium compound, and the difference between the sensitivity when the silver halide photographic light-sensitive material is exposed for an exposure time of 1 / 12.5 seconds and the sensitivity when it is exposed for 8 seconds is A silver halide photographic light-sensitive material characterized by being within 0.3 when expressed by the logarithm of the reciprocal of the quantity. 2. The silver halide according to claim 1, wherein a compound represented by the following formula (1) is present when the silver halide emulsion is chemically sensitized with a sulfur compound and a selenium compound. Photographic material. General formula (1) MXn [In the formula, M represents an element selected from Ga, In, and Tl, and X
Represents a monovalent, divalent, or trivalent anion. n represents an integer. ]