JP2995363B2 - Silver halide photographic material - Google Patents

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 material having high sensitivity and excellent covering power (covering power).

[0002]

Improvement of the covering power of the silver halide emulsion Background of the Invention is a very important technology because it can save silver amount necessary to obtain a constant optical density.

For this reason, many proposals have hitherto been made. For example, US Pat. Nos. 4,411,986 and 4,434,226 disclose that the development silver covering power is remarkably improved by using a tabular emulsion having a high aspect ratio and a small grain thickness. 4,41
No. 3,053 or Japanese Patent Publication No. 2-297539 are disclosed.

Further, as a covering power improver, for example, polyacrylamide, dextran, polyacrylic acid and the like are known.

However, many silver halide photographic light-sensitive materials to which the above-mentioned technology is applied have a short development time when a super-rapid processing such as a processing time of about 45 seconds is performed in all steps. A sufficient developed silver concentration could not be obtained.

Further, when the film physical properties (mainly hardening properties) of the photosensitive material are enhanced in order to cope with rapid development processing, the developability has been further delayed. Therefore, development of a new technique has been desired for further improvement and improvement of sensitivity and covering power.

[0007]

OBJECTS OF THE INVENTION Accordingly, an object of the present invention is to provide a total processing time of 45 minutes.
An object of the present invention is to provide a silver halide photographic light-sensitive material having high physical properties, high covering power and high sensitivity even in ultra-rapid processing in about 2 seconds.

[0008]

The above objects have been found to be achieved by the present invention described below.

(1) On at least one side of the support,
In a silver halide photographic light-sensitive material having a photographic component layer containing at least one silver halide emulsion layer, the total projected area of the silver halide grains contained in at least one of the silver halide emulsion layers is 50. % Or more are tabular silver halide grains having an average aspect ratio (grain diameter / grain thickness) of 3 or more, and at least one erythol compound is contained in the emulsion layer and / or another hydrophilic colloid layer. And (2) a silver halide photographic material as described in the above item (1), which contains at least one of the compounds represented by the following general formula [I]. Was.

[0010]

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In the formula, R ¹ and R ² may be the same or different and each represents a lower alkyl group having 1 to 3 carbon atoms, an aryl group (this aryl group is unsubstituted or an alkyl group having 1 to 2 carbon atoms or a halogen atom) And an aralkyl group (unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms or a halogen atom). R ¹ and R ² may combine with each other to form a piperidine ring or a morpholine ring, and these rings are unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms or a halogen atom (for example, chlorine or bromine). It may be.
R ³ represents a hydrogen atom, a methyl group or an ethyl group, and R ⁴ represents an ethylene group or a simple chemical bond. Me ⁺ represents an alkali metal cation (for example, Li ⁺ , Na ⁺ , K ⁺ ), and X ⁻ represents a chloride ion or a bromide ion.

Hereinafter, the present invention will be described in detail.

[0013] Erythritol in the present invention
The compound is also called erythritol or erythritol,
Three isomers belonging to tetrahydric alcohols, namely D-type, L-type and meso-type, are known (C ₄ H ₁₀ O ₄ ; Mol. Wt 122.12).

[0014] erythritol of the present invention, by Mitsubishi Kasei and Nikken Chemicals, has been established as mass production techniques (chemical industry during the report 1992.6.25), easily be commercially available from Tokyo Kasei and Kanto Chemical Co., Inc. Can be.

These erythritol compounds used in the present invention are added to the photosensitive tabular silver halide emulsion layer and / or another hydrophilic colloid layer according to the present invention.

The term "other hydrophilic colloid layer" used herein refers to a hydrophilic colloid layer having a photosensitive tabular silver halide emulsion layer, and specifically includes a protective layer, an intermediate layer, an antistatic layer, These are constituent layers used for silver halide photographic materials, such as filter layers, antihalation layers, and undercoat layers.

The erythritol compound used in the present invention is preferably added to the silver halide emulsion layer, and the addition amount is 3 g to 30 g, preferably 5 g to 20 g, per mol of silver halide. Further, in the case of a hydrophilic colloid layer other than the emulsion layer, the amount may be 0.03 g to 0.20 g, preferably 0.05 g to 0.15 g, per 1 g of the binder in the addition layer.
It is.

The addition method is used by dissolving in water or a hydrophilic solvent such as methanol or ethanol. In the case of an emulsion, it may be added in any step, but preferably after the growth of silver halide grains or It is preferable before or after chemical ripening or during preparation of a coating solution.

In the present invention, other polyhydric alcohols may be used in combination with the above erythritol compound. The polyhydric alcohol compound referred to herein has at least two hydroxyl groups in the molecule, and preferably has a molecular weight of 150 or less.

Examples of the polyhydric alcohol compound preferably used in the present invention include the following, but the present invention is not limited thereto.

(Compound name) (Molecular weight) 2. Diethylene glycol 62 2. 2,3-dihydroxybutane 90 Glycerin 92 4.2,2-dimethyl-1,3-propanediol 104 5.2 2-butyne-1,4-diol 86 6.2,5-hexanediol 118 7.1 1,6-hexanediol 118 8.2 1,4-hexadiyne-1,6-diol 110 9.2,3,4-hexanetriol 134 10.2-Methyl-2-oxymethyl-1,3-propanediol 120 11. Trimethylolpropane 134 12. Pentaerythritol 136 13.2,3,4,5-hexane tetrol 136 14.1,2,3,4-pentane tetrol 136 15.3-hexyne-1,2,5,6-tetrol 146 16.2 , 6-Octadin-1,8-diol 138 17.2-Methyl-2,3,4-butanetriol 119 18.2,4-Dimethyl-2,3,4-pentanetriol 148 19.2,2-dimethyl -1,3-pentanediol 104 20.1,8-octanediol 146 21.3-hexene-1,2,5,6-tetrol 148 The above polyhydric alcohol compounds are well-known as polyol organic solvents. Is a compound that can be easily obtained as a commercial product.

Among the above, those preferably used in the present invention include diethylene glycol, trimethylolpropane or glycerin.

The above exemplified compounds may be used alone or in combination of two or more. When two or more kinds are used in combination, the molecular weight may be larger than 150 when at least one kind has a molecular weight of 150 or less.

When the amount of erythritol is used in combination with the above-mentioned erythritol, it may be used in a weight ratio of 1: 9 to 9: 1 based on the amount of erythritol.

Next, the hardener represented by the general formula [I] used in the present invention will be described.

The silver halide photographic light-sensitive material of the present invention contains tabular silver halide grains having an average aspect ratio of 3 or more, and is used as a hardening agent in the above erythritol-containing silver halide photographic light-sensitive material. It has not been expected that the carbamoylpyridinium compound represented by the general formula [I] can obtain the hardening property without inhibiting the effect of the present invention.

Hereinafter, specific examples of the compound represented by the general formula [I] described in the present invention are shown, but the present invention is not limited thereto.

[0028]

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[0029]

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[0030]

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[0031]

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The above compounds are described, for example, in Chem. Ber.
Volume, 1831 (1970) and J. Phys. Chem. 68, 3149
Page (1964) or JP-B-58-32699.

These compounds are dissolved in an aqueous solution or a hydrophilic solvent such as methanol or ethanol and then added to the coating solution of the silver halide photographic light-sensitive material according to the present invention.

The hardener of the above general formula [I] of the present invention is preferably added to the hydrophilic colloid layer on the side of the silver halide photographic light-sensitive material constituting layer according to the present invention, which has the emulsion layer.
For example, it can be added to a hydrophilic colloid layer such as an emulsion protective layer, an intermediate layer, an undercoat layer, and an antihalation layer. The hydrophilic colloid layer is intended for a usual coating solution containing a photographic binder such as gelatin, polyvinylpyrrolidone, polyvinyl alcohol, polyacrylamide, dextran and polystyrenesulfonic acid.

When the compound represented by the general formula [I] of the present invention is added to an aqueous gelatin solution as a fast-acting hardener,
There is a tendency for the viscosity to increase significantly. PH of gelatin solution is 5.9
If it is less than 0, the viscosity is further increased, which makes application difficult. When the pH is 6.0 or more and 8.50 or less, the curing reaction is slow and the viscosity increase is small, and when the pH is 8.50 or more, the viscosity tends to increase again. Preferably, the coating solution pH is within 5.90 to 8.50 at 35 ° C,
It is preferable that the mixing be performed within 1 second to 120 seconds applied to the support.

The amount of addition is not uniform depending on the type of the compound or the coating solution, but is usually 0.1 to 10% by weight based on the dry weight of the binder used, and is more preferably.
0.2 to 6% by weight.

The hardener of the general formula [I] of the present invention may be used in combination with other known hardeners. Specific examples of known hardeners that can be used in combination include formalin, glyoxal, and the like. Aldehyde type compounds such as succinaldehyde,
Examples thereof include acid releasing triazine compounds such as dichloro-s-triazine sodium salt described in JP-B-47-6151, and vinylsulfone compounds shown below. _{V-1 (CH 2 = CH} -SO 2 -CH 2 -CONHCH 2) 2 V-2 CH 2 = CH-SO 2 -CH 2 -CH (OH) CH 2 SO 2 -CH = CH 2 V-3 CH _{2 = CH-S0 2 CH 2} -O-CH 2 SO 2 -CH = CH 2 V-4 CH 2 = CH-SO 2 CH 2 CH 2 S0 2 CH = CH 2 V-5 (CH 2 = CH-SO _2- CH ₂ ) ₄ C The above compounds are described, for example, in JP-A-52-21059 and JP-A-53-41221.
No. 49-73122, JP-B-49-13563, JP-A-51-44164
Hardening agents described in No.

Next, the aspect ratio used in the present invention is 3
The above tabular silver halide grains will be described.

The average grain size of the tabular silver halide grains according to the present invention is preferably from 0.2 to 3.0 μm, particularly preferably from 0.5 to 3.0 μm.
2.0 μm.

The tabular silver halide emulsion of the present invention has an average value (referred to as average aspect ratio) of grain diameter / thickness (referred to as aspect ratio) of 3 or more, and preferably 3.5 to 12
And particularly preferably 4 to 8.

The average thickness of the tabular silver halide emulsion of the present invention is preferably 0.5 μm or less, more preferably 0.4 μm or less, and particularly preferably 0.05 to 0.35 μm.

In the present invention, the diameter of a silver halide grain is defined as a sphere-equivalent diameter of the silver halide grain from observation of an electron micrograph of the silver halide grain.

In the present invention, the thickness of a silver halide grain is defined as the minimum of the distance between two parallel planes constituting a tabular silver halide grain.

The thickness of the tabular silver halide grains can be determined from an electron micrograph with a shadow of the silver halide grains or an electron micrograph of a sample tomographic image obtained by coating a silver halide emulsion on a support and drying. .

To determine the average aspect ratio,
Measure 100 samples.

In the silver halide emulsion of the present invention, the ratio of tabular silver halide grains to all silver halide grains is at least 50%, preferably at least 60%, particularly preferably at least 70%.

The tabular silver halide emulsions of the present invention are preferably monodisperse emulsions, and are preferably ±
50% by weight of silver halide grains contained in the 20% particle size range
The above are particularly preferably used.

The tabular silver halide emulsion of the present invention may have any halogen composition such as silver chloride, silver bromide, silver iodide, silver chlorobromide, silver iodobromide, etc. Silver halide is preferred, and the average silver iodide content is 0.1 to 4.0 mol%, particularly preferably 0.5 to 3.0 mol%.

The tabular silver halide emulsion of the present invention comprises:
The halogen composition may be uniform in the grains or silver iodide may be localized, but those localized in the center are preferably used.

The method for producing tabular silver halide emulsions is described in JP-A-58-113926, JP-A-58-113927, JP-A-58-113934 and JP-A-58-113934.
2-1855, European Patents 219,849 and 219,850 can also be referred to.

As a method for producing a monodisperse tabular silver halide emulsion, JP-A-61-6643 can be referred to.

As a method for producing a tabular silver iodobromide emulsion having a high aspect ratio, an aqueous silver nitrate solution or an aqueous silver nitrate solution and an aqueous halide solution are simultaneously added to an aqueous gelatin solution having a pBr of 2 or less to form seed crystals. And then grown by the double jet method.

The size of the tabular silver halide grains can be controlled by the temperature during grain formation and the rate of addition of the silver salt and the aqueous halide solution.

The average silver iodide content of the tabular silver halide emulsion can be controlled by changing the composition of the aqueous halide solution to be added, that is, the ratio of bromide to iodide.

[0055] In addition, at the time of manufacture of the flat plate-shaped silver halide grains,
If necessary, silver halide solvents such as ammonia, thioether, and thiourea can be used.

The emulsion may be subjected to a water washing method such as a noodle washing method or a flocculation sedimentation method in order to remove soluble salts. As a preferred washing method, for example,
As a particularly preferred desalting method, a method using an aromatic hydrocarbon aldehyde resin containing a sulfo group described in 35-16086, or a method using G3, G8 or the like as an aggregating polymer agent described in JP-A-63-158644 is particularly preferred. No.

In the emulsion according to the present invention, various photographic additives can be used before and after physical ripening or chemical ripening. Known additives include, for example, Research
Disclosure No.17643 (December 1978), No.187
16 (November 1979) and No. 308119 (December 1989). These three research
The types of compounds shown in the disclosure and the locations of the compounds 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 Brightener 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 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 support 28 XVII 1009 XVII Examples of the support that can be used in the light-sensitive material according to the present invention include the aforementioned RD-17643, page 28 and RD-308119,
What is described on page 9 is mentioned.

A suitable support is a plastic film or the like, and the surface of these supports may be provided with an undercoat layer, or subjected to corona discharge, ultraviolet irradiation, etc. in order to improve the adhesion of the coating layer.

[0059]

Embodiments of the present invention will be described below. However, needless to say, the present invention is not limited to the embodiments described below.

Example 1 Monodispersed silver iodobromide grains containing 2.0 mol% of silver iodide having an average grain size of 0.2 μm were used as nuclei, and silver iodobromide containing 30 mol% of silver iodide was adjusted to pH 9.1. , Grown on pAg7.7, then pH8.0, pAg9.
In step 1, potassium bromide and silver nitrate are added in an equimolar amount, and the average particle size of a regular tetradecahedron having a mean silver iodide content of 2.1 mol% is 1.05 μm (A) and 0.52 μm (B ), 0.37μm
Monodisperse emulsion particles of (C) were prepared.

[0061] Also, to prepare the following 3 types, such as flat plate-like emulsion grains.

That is, 30 g of gelatin, 10.5 g of potassium bromide, and thioether [HO (CH ₂ ) ₂ S (CH ₂ ) ₂ S (CH ₂ ) ₂ S (C
H ₂ ) ₂ OH] 0.5 wt% aqueous solution (10 ml) was added and dissolved, and the mixture was stirred and stirred at 63 ° C. in a solution (pAg = 9.1, pH = 6.5).
30 ml of a 90 mol silver nitrate solution and 30 ml of a mixed solution of 0.90 mol of potassium iodide and potassium bromide (molar ratio 1:99) were simultaneously added over 15 seconds, and then 600 ml of a 1 mol silver nitrate solution and a molar ratio of 96.5: 3.5 were added. A tabular silver iodobromide emulsion was prepared by simultaneously adding 600 ml of a 1 mol mixed solution of potassium bromide and potassium iodide over 56 minutes.

The resulting tabular silver halide grains had an average grain size of 1.16 μm, a thickness of 0.19 μm, and a silver iodide content of 3.0 mol%. The obtained emulsion was designated as (D).

The emulsion (E) had an average particle size of 0.83 μm prepared in the same manner as (D) except that pAg was changed to 7.0.
Silver halide grains having a thickness of 0.30 μm, an aspect ratio of 2.77, and a silver iodide content of 3.0 mol% were prepared. Emulsion (F) was prepared in the same manner as (D) except that pAg was changed to pAg = 6.8, the average grain size was 0.95 μm, the thickness was 0.27 μm, and the aspect ratio was
3.52, silver halide grains having a silver iodide content of 3.0 mol% were prepared.

Each of the obtained emulsions (A) to (F) was subjected to removal of excess salts by a usual aggregation method.

That is, while maintaining the temperature at 40 ° C., an aqueous solution of sodium formalin condensate of sodium naphthalene sulfonate and an aqueous solution of magnesium sulfate were added to cause aggregation. After removing the supernatant, pure water up to 40 ° C. was further added, and an aqueous solution of magnesium sulfate was added again to cause aggregation, and the supernatant was removed. Each of these particles was prepared by adding ammonium thiocyanate to 1.9 × 10 ⁻³ per mol of silver.
Moles and an appropriate amount of chloroauric acid, hypo, and the following spectral sensitizing dyes (A) and (B) in a weight ratio of 200: 1, and a total amount of 800 mg per mole of silver halide was added for chemical ripening. 15 minutes before completion, add 200 mg of potassium iodide per mole of silver
After addition, 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was stabilized at 3 × 10 ^-2 mol.

Using the obtained six kinds of emulsions, the following Table 1 was used.
The monodisperse emulsion and a flat plate-like emulsions shown in prepared. The monodisperse emulsion was prepared by adding the above particles (A), (B) and (C) to 12
%, 68%, in a mixing ratio of 20%, a flat plate-like emulsion particles (D), (E), those with (F). This emulsion was divided and erythritol and polyhydric alcohols according to the present invention were added as shown in Table 1. The emulsion was adjusted to pH 6.45 at 35 ° C. after addition of the additives described below to prepare a coating solution.

The protective layer solution was prepared with the following composition.

Spectral sensitizing dye (A) Anhydride of sodium 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine Spectral sensitizing dye (B) 5 , 5'-di- (butoxycarbonyl) -1,1'-diethyl-3,
Anhydrous 3'-di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt Additives used in the emulsion are as follows. In addition,
The amount of addition was shown as an amount per mole of silver halide.

Lime-treated ossein gelatin 90 g t-butylcatechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-dihydroxybenzene-4-sulfone ammonium 4g 2-mercaptobenzimidazole-5-sulfonate, sodium 15 mg 1-phenyl-5-mercaptotetrazole _{1mg C 4 H 9 OCH 2 CH} (OH) CH 2 N (CH 2 COOH) 2 1g

[0071]

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1,1-Dimethylol-1-bromo-1-nitromethane 10 mg The following compound was added to the protective layer solution. The amount of addition is shown per 1 liter of the coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 1 g

[0074]

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Polymethyl methacrylate having an average particle size of 5 μm (matting agent) 1.1 g Colloidal silica (average particle size 0.013 μm) 30 g The protective layer solution containing the hardener according to the present invention and the protective layer solution are shown in Table 1. The film was hardened by the hardening method shown. (A) to (D) in the table are as follows.

Addition amount of hardener per liter of protective layer liquid (a) (CH ₂ = CHSO ₂ CH ₂ ) ₂ O 800 mg (b) Glyoxal aqueous solution 40% 3 ml + formalin aqueous solution 38% 1.5 ml (c) (CH ₂ = CHSO ₂ CH ₂ ) ₂ O 400 mg + Exemplified No. 10 400 mg (d) Glyoxal aqueous solution 40% 2 ml + Formalin aqueous solution 38% 0.5 ml + Exemplified No. 10 400 mg The emulsion layer is 1.45 g / m ² in terms of silver per side, and protected. The layers were coated with two slide hopper type coaters at a speed of 90 m / min so that the gelatin weight was 0.99 g / m ² .
Glycidyl methacrylate 50wt%, methyl acrylate
175 μm polyethylene coated with an aqueous dispersion of a copolymer obtained by diluting a copolymer consisting of three types of monomers of 10 wt% and butyl methacrylate 40 wt% to a concentration of 10 wt% as a subbing liquid A sample was obtained by simultaneously coating both surfaces on a terephthalate film base and drying for 2 minutes and 15 seconds.

In the present invention, the solution of the hardener was applied to the protective layer solution immediately before the slide hopper type coater. At this time, the hardener liquid and the protective layer liquid are mixed,
The time until coating on the polyethylene terephthalate support was 9 seconds.

The sample thus obtained was tested under the following conditions.

Development Processing Conditions Processing was performed in a processing mode of 45 seconds using an automatic developing machine SRX-502 (manufactured by Konica Corporation). The development was performed at a developing solution temperature of 35 ° C. and a fixing temperature of 33 ° C.
The washing water was supplied at a temperature of 18 ° C. at a rate of 4 l / min. The drying temperature was 45 ° C. The environment of the room with the automatic processor is 25
° C, 60%.

Formulation of developer Part-A (for finishing 38 l) Potassium hydroxide 1140 g Potassium sulfite 2280 g Sodium bicarbonate 266 g Boric acid 38 g Diethylene glycol 418 g Ethylenediaminetetraacetic acid 61 g 5-Methylbenzotriazole 1.9 g Hydroquinone 1064 g Add water to 9.3 L Finish Part-B (for finishing 38l) Glacial acetic acid 418g Triethylene glycol 418g 1-phenyl-3-pyrazolidone 100g 5-nitroindazole 9.5g Add water to finish 1.0l Part-C (for finishing 38l) Sodium metabisulfite 389g Add water to make up to 770ml Starter Glacial acetic acid 230g Potassium bromide 200g Add water to make up to 1.5l Developing solution preparation method Add 20l of 18 ° C water to the replenisher stock tank, and stir the above Part-A, Add Part-B and Part-C sequentially, and finally add water and aqueous potassium hydroxide solution.
Was adjusted to 10.53 at 25 ° C. Apply this replenisher for 24 hours 25
After the mixture was allowed to stand at 0 ° C., the above starter was added at a rate of 20 ml per liter, and then filled in a developing tank of an automatic developing machine manufactured by Konica Corporation. The pH of the developer at this time was 10.26 at 25 ° C.

The developing replenisher was 250 m / m ² of the sample of the present invention.
l refilled.

Fixer Formulation Part-A (for finishing 38 l) Ammonium thiosulfate 6080 g disodium ethylenediaminetetraacetate dihydrate 0.76 g sodium sulfite 456 g boric acid 266 g sodium hydroxide 190 g glacial acetic acid 380 g Add water to finish 9.5 l B (for finishing 38 l) Aluminum sulfate (in terms of anhydrous salt) 570 g sulfuric acid (50 wt%) 228 g Add water to finish 1.9 l Fixer preparation method Add 20 l of water at 18 ° C to the replenisher stock tank and stir as described above. Part-A and Part-B were sequentially added, and finally, water and acetic acid were added. The pH was adjusted to 4.80 at 38 ° C with 38 l. The fixing replenisher was allowed to stand at 25 ° C. for 24 hours, and then filled in a fixing tank of an automatic developing machine manufactured by Konica Corporation. Fixing replenishment was carried out with 310 ml replenishment per m ² of the sample of the present invention.

The sample obtained by coating was treated at room temperature for 15 minutes.
After standing for days, the following tests were performed.

(Sensitometry) An intensifying screen SRO-250 (sold by Konica Corporation) was used for the front side (X-ray source side) and the back side (back side) of each sample using a medical X-ray photography cassette. And was exposed under the following conditions. The intensifying screen was used for the front side and the back side for the back side. Exposure is performed at a tube voltage of 100 KVP, 50 msec, and the distance method. The relative sensitivity at the time of double-sided exposure is indicated by the relative sensitivity when the reciprocal of the exposure amount that gives a fog of sample No. 1 and a blackening density of 1.0 is set to 100. Was.

(Measurement of Covering Power) The covering power was applied to the sample at the maximum density, and then processed in the above-described developing condition in a 45-second mode. The amount of silver (mg / dm ² ) of the obtained sample was measured by X-ray fluorescence analysis, and the covering power was determined by dividing the concentration by the amount of silver. The higher the value, the better.

(Evaluation of Hardness of Film) A rectangular film of 5 mm × 35 mm was immersed in a 1.5% by weight aqueous solution of sodium hydroxide at 60 ° C., and the time required for the emulsion layer to start dissolving in the solution was measured. The film was durable.

Table 1 also shows the measurement results of the sensitivity, covering power and hardening degree 15 days after application.

[0088]

[Table 1]

As is clear from the table, even if the erythritol of the present invention is added to comparative monodisperse particles or particles having an aspect ratio of less than 3 outside the present invention, the sensitivity and covering power are not improved. Sample N obtained by adding erythritol to tabular grains according to the present invention having an aspect ratio of 3 or more.
In Nos. 14 to 16 and No. 29, high covering power was obtained by rapid development, and the sensitivity was also improved.

In the sample containing the erythritol of the present invention in the emulsion layer and the hardener represented by the general formula [I] of the present invention in the protective layer, the sensitivity and the covering power were not deteriorated. Sufficient hardening properties were obtained.

[0091]

According to the present invention, even in rapid development processing,
A silver halide photographic light-sensitive material having high covering power and high sensitivity was obtained. Even if the physical properties of the film (hardness) were further enhanced, there was no deterioration in these properties.

Claims (2)

(57) [Claims] 1. A silver halide photographic material having a photographic component layer containing at least one silver halide emulsion layer on at least one side of a support, wherein at least one of the silver halide emulsion layers Are tabular silver halide grains having an average aspect ratio (grain diameter / grain thickness) of 3 or more, and 50% or more of the total projected area of the silver halide grains contained in the emulsion layer and / or A silver halide photographic material comprising at least one erythritol compound in another hydrophilic colloid layer. 2. The silver halide photographic material according to claim 1, which contains at least one compound represented by the following general formula [I]. Embedded image In the formula, R ¹ and R ² may be the same or different and represent a lower alkyl group, an aryl group, or an aralkyl group, wherein the aryl group and the aralkyl group are unsubstituted or an alkyl group having 1 to 2 carbon atoms or a halogen atom. It may be replaced. Also, R ¹ and R ²
May combine with each other to form a piperidine ring or a morpholine ring, and these rings may be unsubstituted or substituted with an alkyl group having 1 to 2 carbon atoms or a halogen atom.
R ³ represents a hydrogen atom, an alkyl group having 1 to 2 carbon atoms, R ⁴
Represents an ethylene group or a simple chemical bond. Me ⁺ represents an alkali metal cation, and X ⁻ represents a chloride ion or a bromide ion.