JPH09244176A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject material having increased γ and not causing problem such as pressure blackening in rapid processing under slight replenishment by specifying the relation between the sensitivities of emulsion layers and incorporating a mercapto compd. into nonphotosensitive hydrophilic colloidal layers. SOLUTION: This sensitive material has silver halide emulsion layers and nonphotosensitive hydrophilic colloidal layers on both faces of the substrate. At the time of exposure from one side, the ratio (SA/SB) of the sensitivity SA of the emulsion layer on the exposure side to the sensitivity SB of the emulsion layer on the opposite side is <=4. The colloidal layers contain a mercapto compd. represented by the formula Z-SM (where Z is an N-contg. 5- or 6-membered heterocyclic group and M is H, an alkali metal atom or quat. ammonium).

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 specifically, a high-γ silver halide photographic light-sensitive material free from problems such as pressure blackening in rapid and low replenishment processing. It is about.

[0002]

2. Description of the Related Art In recent years, the processing time has been greatly shortened due to the rapid progress of high temperature in the field of X-ray photographic light-sensitive materials. In addition, low replenishment of processing liquid is being promoted for the purpose of environmental protection. For faster processing and low replenishment,
Overcoming the reduction in contrast (γ) of sensitive materials has become a major issue.

It has been conventionally known that the amount of silver attached to a light-sensitive material is increased and the amount of binder such as gelatin is reduced to obtain a high γ. However, when the amount of silver attached is increased or the amount of binder such as gelatin is decreased, there is a problem that pressure blackening (bending blackening and scratch blackening) on the light-sensitive material is deteriorated.

On the other hand, in recent years, in medical light-sensitive materials, in order to improve the sharpness of images (improvement of MTF value), a dye layer (crossover cut layer) is provided between the emulsion layer and the support to prevent light from crossing over. A technique for reducing "spreading blur" (for example, Japanese Patent Laid-Open No. 7-319093) is disclosed. However, in rapid processing, even if the MTF value is high, γ decreases, and thus the visual sharpness deteriorates.

The inventor of the present invention has found a method in which sharpness in visual observation does not deteriorate even in rapid processing, and has focused on increasing γ rather than the MTF value to complete the present invention.

[0006]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material which has a high .gamma. And is free from problems such as pressure blackening in rapid and low replenishment processing.

[0007]

The above object of the present invention is achieved by the following constitution.

(1) In a silver halide photographic light-sensitive material having a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on both sides of a support, both emulsion layers are exposed on one side when exposed. When the sensitivity of the emulsion layer is SA and the sensitivity of the emulsion layer on the opposite side is SB, SA / SB is 4 or less, and the non-photosensitive hydrophilic colloid layer contains a mercapto compound. Silver photographic light-sensitive material.

(2) An emulsion layer containing a silver halide emulsion chemically added with an azaindene compound and a non-photosensitive hydrophilic colloid layer containing a mercapto compound are separately prepared before and after the addition of the chemical sensitizer. A silver halide photographic light-sensitive material, which is provided on a support.

(3) The silver halide photographic light-sensitive material described in (2) above, wherein the azaindene compound is added before the addition of the chemical sensitizer after addition of the sensitizing dye.

(4) The silver halide photographic light-sensitive material as described in 1, 2 or 3 above, wherein the mercapto compound is represented by the following general formula (1).

General Formula (1) Z-SM In the formula, Z represents a nitrogen-containing 5- or 6-membered heterocyclic group, and M represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group.

(5) The silver halide photographic light-sensitive material as described in 2 or 3 above, wherein the azaindene compound is represented by the following general formula (T).

[0014]

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In the formula, R ¹¹ represents a hydrogen atom, a carboxylic acid group and its ester group, a mercapto group, an alkyl group, an aryl group, a heterocyclic group, an alkylthio group or an alicyclic group, and R ¹² represents hydrogen. Atom, a halogen atom, a carboxylic acid group and an ester group thereof, an alkyl group, an aryl group, a heterocyclic group, and an alicyclic group, R ¹³ is a hydrogen atom, a hydroxyl group, a carboxylic acid group and an ester group thereof, an amino group Represents an alkyl group, an aryl group, a heterocyclic group, or an alicyclic group, and R ¹² and R ¹³ may combine with each other to form a heterocycle or a carbocycle.

The present invention will be described in more detail. The silver halide photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material having a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on both sides of a support, both emulsion layers being from one side. When the sensitivity of the emulsion layer on the exposed side when exposed is SA and the sensitivity of the emulsion layer on the opposite side is SB, SA / SB is 4 or less, and more preferably 2.5 to 4.

As the silver halide composition of the silver halide photographic light-sensitive material of the present invention, silver bromide, silver iodobromide, silver chlorobromide, salt having an average silver iodide content of 1 to 0 mol% are contained. Silver iodobromide is preferred.

If the halogenated particles have the constitution of the present invention,
It may be of any crystal type, for example, a single crystal such as a cube, octahedron, or tetrahedron, or may be polytwinned grains having various shapes. Tabular grains having a (particle diameter / particle thickness ratio) of 3 or more are preferred. The advantage of such tabular grains is that they can improve spectral sensitization efficiency and image graininess and sharpness. For example, British Patent 2,112,157.
Nos. 4,414,310 and 4,434,2
No. 26, etc., and the emulsion can be prepared with reference to the methods described in these publications.

The silver halide emulsion of the present invention is spectrally sensitized, but the type of spectral sensitizing dye used is not particularly limited, and any spectral sensitizing dye for photographic use may be used. it can. However, preferred spectral sensitizing dyes include compounds represented by the following general formula (A) or general formula (B). In the present invention, the spectral sensitizing dye is
It is preferable to add it to the photosensitive silver halide emulsion after dispersing it in the form of solid fine particles of 1 μm or less, preferably 0.01 μm to 1 μm. Addition amount of spectral sensitizing dye is 0.5g
/ AgX is preferably 1 mol or less, more preferably 0.3 to 0.
A range of 48 g / Ag X 1 mol is preferred. The spectral sensitizing dye is a combination of the general formulas (A) and (B), and the weight ratio is 1:
The range of 5 to 1: 200 is preferable.

[0020]

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In the formula, R ¹ and R ³ each represent a substituted or unsubstituted alkyl group, at least one of R ¹ and R ³ is a group other than an ethyl group, and R ² and R 3 ⁴ represents a lower alkyl group, and at least one of R ² and R ⁴ represents an alkyl group substituted with a hydrophilic group. V ¹ ,
V ² , V ³ and V ⁴ each represent a hydrogen atom or a substitutable group in which the sum of the added Hammett σp values is less than 1.7, and V ¹ , V ² , V ³ and V ⁴ are hydrogen at the same time. It cannot be an atom or a chlorine atom.

X ¹ represents an ion necessary for neutralizing the charge in the molecule, and n represents 1 or 2. However, when an inner salt is formed, n is 1.

In the general formula (B), R ⁵ and R ⁶ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, and R 5
^At least one of ⁵ and R ⁶ is a sulfoalkyl group or a carboxyalkyl group.

R ⁷ represents a hydrogen atom, an alkyl group or an aryl group. Z ¹ and Z ² each represent a nonmetallic atom group necessary for completing a benzene ring or a naphtho ring which may have a substituent. X ² represents an ion necessary for neutralizing the charge in the molecule, and m represents 1 or 2. However, m is 1 when forming an intramolecular salt.

The silver halide emulsion of the present invention is chemically sensitized, but can be sensitized with a noble metal salt such as a sulfur compound or a gold salt, or with a selenium compound or a tellurium compound. Further, reduction sensitization can be performed, and sensitization can be performed by combining these methods.

In the second aspect of the present invention, the silver halide emulsion is chemically ripened by adding an azaindene compound before and after the addition of the chemical sensitizer.
Preferred azaindene compounds include compounds represented by general formula (T).

In the general formula (T), R ¹¹ is a hydrogen atom, a carboxylic acid group and its ester group, a mercapto group,
Alkyl group (including those having a substituent), aryl group (including those having a substituent), heterocyclic group (including those having a substituent), alkylthio group (including those having a substituent), ari Represents a cyclic group (including those having a substituent), R ¹² represents a hydrogen atom, a halogen atom, a carboxylic acid group and its ester group, an alkyl group (including those having a substituent), an aryl group (a substituent group) A heterocyclic group (including a substituent), an alicyclic group (including a substituent), R ¹³ represents a hydrogen atom, a hydroxyl group, a carboxylic acid group and The ester group, amino group (including those having a substituent), alkyl group (including those having a substituent), aryl group (including those having a substituent), heterocyclic group (including those having a substituent) Free), represents the alicyclic group (including those having a substituent), R ¹² and R ¹³ may form a heterocyclic ring or carbon ring. Specific examples of tetrazaindene represented by formula (T) are shown below.

[0028]

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[0029]

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[0030]

[Chemical 6]

The addition amount is 5 to 500 m before the addition of the chemical sensitizer.
g / AgX mol, 100 to 2500 mg / Ag after addition
X moles are preferred. The addition timing is preferably 5 minutes or more before the chemical sensitizer is added, 10 minutes or more after the chemical sensitizer is added, and further preferably 30 minutes or more.

Next, the non-photosensitive hydrophilic colloid layer of the present invention will be described. Gelatin amount of non-light-sensitive hydrophilic colloid layer of the present invention is preferably 1.5 g / m ² or less, more preferably 0.3-0.9 g / m ^2.

The non-photosensitive hydrophilic colloid layer of the present invention contains a mercapto compound, and the compound represented by the general formula (1) is preferable. In the general formula (1), Z represents a nitrogen-containing 5- or 6-membered heterocyclic group, and specifically, oxazole ring, thiazole ring, imidazole ring, selenazole ring, triazole ring, tetrazole ring, thiadiazole ring, oxa Diazole ring, pyrimidine ring, thiazine ring,
Triazine ring, thiodiazine ring or a ring bonded to another carbon ring or hetero ring, for example, benzothiazole ring, benzotriazole ring, benzimidazole ring, benzooxadiazole ring, benzoselenazole ring, naphthoxazole ring, triazaindolizine Ring, diazaindolizine ring, tetraazaindolizine ring and the like. Examples of preferred ones include an imidazole ring, a tetrazole ring, a benzoxazole ring, and a triazole ring, and particularly preferably 1-allyl-substituted tetrazoles,
The allyl group may be substituted or unsubstituted.

These heterocycles may be substituted with a monovalent organic group, but at least one group selected from --SO ₃ M ₁ , --COOR ₁ , --OH and --NHR ₂ may be directly or indirectly attached. Those substituted with are preferred. M ₁ represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group,
R ₁ is a hydrogen atom, an alkali metal atom or a carbon number of 1 to 6
Alkyl group, R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a -COR _3, -COOR ₃ or -SO ₂ R _3. R ₃ is a hydrogen atom or an aliphatic group (for example, having 1 to 2 carbon atoms).
0 alkyl group, specifically, methyl group, ethyl group, n-
Propyl group, i-propyl group, t-butyl group, n-octyl group, dodecyl group, cyclohexyl group, etc. or aromatic group (for example, aryl group having 6 to 20 carbon atoms, specifically, phenyl group, naphthyl group) Etc.), and these groups may have a substituent. M represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group.

Further, a so-called precursor type compound capable of releasing the compound represented by the general formula (1) over time and / or into the treatment liquid can also be preferably used.

Specific examples of the compound represented by the general formula (1) and its precursor type compound are shown below.

[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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The addition amount of the compound represented by the general formula (1) ^{may, 0.05mg / m 2 ~50mg / m} 2, more preferably from ^{0.2mg / m 2 ~2mg / m 2} . The addition amount is 0.
05 mg / m ^{2 to} 50 mg / m ² , more preferably 0.2
a ^{mg / m 2 ~2mg / m 2} .

The support that can be used in the silver halide photographic light-sensitive material of the present invention is, for example, a polyethylene terephthalate film, and a subbing layer is formed on the surface of these supports to improve the adhesion of the coating layer. Set up,
You may give corona discharge, ultraviolet irradiation, etc.

Next, development processing of the light-sensitive material of the present invention will be described.

As the developing agent of the developing solution for developing the light-sensitive material of the present invention, dihydroxybenzenes (hydroquinone etc.), para-aminophenols (p-aminophenol, N-methyl-p-aminophenol, 2,4-diamino) are used. Phenol, etc., 3-pyrazolidones (1-phenyl-3-pyrazolidone, 1-phenyl-4-methyl-4
-Hydroxymethyl-3-pyrazolidone, 5,5-dimethyl-1-phenyl-3-pyrazolidone, etc.) and reductones are mentioned, and it is preferable to use them in combination.

The preservative for the developing solution may include sulfites such as potassium sulfite and sodium sulfite, and reductones such as piperidinohexose reductone, which are preferably 0.2 to 1 mol / mol. It is used in liters, more preferably 0.3 to 0.6 mol / liter.
Further, adding a large amount of ascorbic acid also leads to processing stability.

As the alkaline agent, sodium hydroxide,
PH adjusters such as potassium hydroxide, sodium carbonate, potassium carbonate, sodium tertiary phosphate and potassium tertiary phosphate are included. Further, the borate described in JP-A-61-282808,
Buffers such as saccharose, acetoxime, 5-sulfosalicylic acid, phosphates and carbonates described in JP-A-60-93439 may be used. The content of these alkaline agents is such that the pH of the developer is 9.0 to 13, preferably 10 to 1.
Choose 2.5.

As dissolution aids, diethylene glycol, triethylene glycols and their esters, etc., sensitizers such as quaternary ammonium salts, etc., development accelerators, surfactants, etc. may be contained.

As an anti-sludge agent, Japanese Patent Laid-Open No. 56-
No. 106244, a silver stain preventing agent, JP-A-3-51
The sulfides and disulfide compounds described in JP-A No. 844, the cysteine derivatives or triazine compounds described in JP-A-5-289255 are preferably used.

Examples of the organic inhibitor include azole type organic antifoggants such as indazole type, imidazole type, benzimidazole type, triazole type, benzotriazole type, tetrazole type, thiadiazole type, mercaptoazole type (1-phenyl-5- Compounds such as mercaptotetrazole) are used. Inorganic inhibitors include sodium bromide, potassium bromide, potassium iodide and the like. In addition, L. F. A. Mason, "Photographic Processing Chemistry," published by Focal Press (1966), pages 226-229, U.S. Patents 2,193,015, 2,592,364,
Those described in JP-A-48-64933 may be used.

As a chelating agent for concealing calcium ions mixed in tap water used in the treatment liquid, a chelating agent having a chelate stabilization constant with iron of 8 or more as an organic chelating agent described in JP-A-1-193583. Agents are preferably used. Examples of the inorganic chelating agent include sodium hexametaphosphate, calcium hexametaphosphate and polyphosphate.

A dialdehyde compound may be used as the development hardener. In this case, glutaraldehyde is preferably used. However, for rapid processing, it is preferable that the hardener is allowed to act in the coating step of the photosensitive material in advance as described above, rather than the hardener is allowed to act in the development processing step.

The preferred processing temperature for developing the light-sensitive material is
Preferably 25 to 50 ° C, more preferably 30 to 40 ° C
It is. The development time is preferably 4 to 90 seconds, more preferably 6 to 60 seconds. Processing time is Dry to D
ry is preferably 15 to 210 seconds, more preferably 25.
~ 90 seconds.

The replenishment of the developing solution at the time of the development treatment is to replenish the amounts corresponding to the fatigue of the processing agent and the oxidative fatigue, the evaporated amount, and the taken-out amount of the film. As a replenishment method, JP-A-55-1262
No. 43, replenishment by width and feed speed.
Area supplementation described in 104946, JP-A-1-1491
Area replenishment controlled by the number of continuous treatments described in No. 56 may be used, and the preferable replenishment amount is 500 to 80 cc.
/ M ² .

The fixing liquid may include a fixing material generally used in the art. The pH is 3.8 or higher, preferably 4.2 or higher.

As a fixing agent, ammonium thiosulfate,
Thiosulfates such as sodium thiosulfate are preferred, and ammonium thiosulfate is particularly preferred from the viewpoint of fixing speed. The concentration of ammonium thiosulfate is preferably in the range of 0.1 to 5 mol / liter, more preferably 0.8 to 3 mol / liter.

In the present invention, the fixing solution may be one which performs acidic hardening. In this case, the hardener is preferably aluminum ion, and is preferably added in the form of, for example, aluminum sulfate, aluminum chloride, or potassium alum.

In addition, if desired, the fixer contains preservatives such as sulfites and bisulfites, pH buffers such as acetic acid and boric acid, mineral acids (sulfuric acid, nitric acid, etc.) and organic acids (oxalic acid, oxalic acid) , Phosphoric acid, apple acid, etc.), various acids such as hydrochloric acid, pH adjusting agents such as metal hydroxides (potassium hydroxide, sodium hydroxide, etc.), and chelating agents having a water softening ability.

As the fixing accelerator, for example, Japanese Patent Publication No. 45-
No. 35754, No. 58-122535, No. 58-12
2536, thiourea derivatives, US Pat.
Examples thereof include thioethers described in No. 6,459.

[0060]

Embodiments of the present invention will be described below. However, as a matter of course, the present invention is not limited to the examples described below.

Example 1 (Preparation of seed emulsion-1) Seed emulsion-1 was prepared by the following method.

[A ₁ ] Ocein gelatin 24.2 g Distilled water 9657 ml Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous methanol solution) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml [B ₁ ] 2.5N AgNO ₃ aqueous solution 2825 ml [C ₁ ] potassium bromide 837 g potassium iodide 5.86 g Finish with water to 2825 ml [D ₁ ] 1.75 N KBr aqueous solution Silver potential control amount at 42 ° C. JP-B-58-58288, Same as 58-5828
Using a mixing stirrer described in the specification of No. 9, 464.3 ml of each of the solution B ₁ and the solution C ₁ was added to the solution A ₁ by a simultaneous mixing method over 1.5 minutes to form nuclei. .

After stopping the addition of solution B ₁ and solution C ₁ ,
Over a period of 40 minutes of time to raise the temperature of the solution A ₁ to 50 ° C., after adjusting the pH to 5.0 with 3% KOH, the solution again B ₁ and solution C ₁ simultaneous mixing method, each 55 0.4 ml /
Min was added at a flow rate of 42 minutes. 50 from 42 ℃
The silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) during the temperature increase to ℃ and re-simultaneous mixing with the solutions B ₁ and C ₁ was +8 mV and +16 mV, respectively, using the solution D _1. Controlled to be.

After completion of the addition, the pH was adjusted to 6 with 3% KOH, and desalting and washing with water were immediately performed. In this seed emulsion, 90% or more of the total projected area of the silver halide grains is composed of hexagonal tabular grains having a maximum adjacent side ratio of 1.0 to 2.0, and the average thickness of the hexagonal tabular grains is 0.045 μm. It was confirmed by an electron microscope that the average particle size (circular diameter conversion) was 0.42 μm. The variation coefficient of the thickness was 42%, and the variation coefficient of the distance between twin planes was 45%.

Preparation of tabular silver bromide emulsion A tabular pure silver bromide emulsion was prepared using seed emulsion-1 and the following three solutions.

[A ₂ ] Ocein gelatin 34.03 g Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% aqueous solution of methanol) 2.25 ml Emulsion-1 1.218 mol equivalent Water is finished to 3669 ml [B ₂ ] Potassium bromide 1747 g Finish with water to 3669 ml [C ₂ ] Silver nitrate 2493 g Finish with water to 4193 ml Solution A ₂ was stirred vigorously while keeping it at 50 ° C., and the total amount of solution B ₂ and solution C ₂ was added thereto. It was added by the double-sided mixing method over 100 minutes. During this time, the pH was kept at 9.0 with the KOH solution, and the pAg was kept at 8.6 throughout. Here, the addition rates of the solution B ₂ and the solution C ₂ were changed functionally with respect to time so as to match the critical growth rate. That is, they were added at an appropriate addition rate so that no small particles were generated except for the seed particles that were growing, and that they did not become multicomponent due to Ostwald ripening.

After the completion of the addition, this emulsion was cooled to 40 ° C., and 1800 ml of an aqueous solution of 13.8% (weight) of modified gelatin modified with phenylcarbamoyl groups (substitution rate 90%) was added as an aggregating polymer agent. Stir for 3 minutes. Thereafter, a 56% (by weight) aqueous solution of acetic acid is added to adjust the pH of the emulsion.
Was adjusted to 4.6 and stirred for 3 minutes, allowed to stand for 20 minutes, and the supernatant was drained by decantation.
1.25 l was added, and after stirring and standing, the supernatant was drained.

Subsequently, an aqueous gelatin solution and sodium carbonate 1
A 0% (by weight) aqueous solution was added to adjust the pH to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redispersion, pH was adjusted to 5.80 and pAg was adjusted to 8.06 at 40 ° C.

Observation of the obtained silver halide emulsion with an electron microscope revealed that the average grain size was 0.84 μm, the average thickness was 0.16 μm, the average aspect ratio was about 5.3, and the grain size distribution was 20%. It was a tabular silver halide grain. The amount of gelatin at the end of physical ripening was 15.9 g per mol of silver halide.

After the emulsion prepared above was heated to 48 ° C., the spectral sensitizing dye dispersions D-1 and D-2 described below were added in the amounts shown in Table 1. The addition amount is the total amount of the spectral sensitizing dyes (A) and (B). After 10 minutes, 3.5 mg of chloroauric acid and 10 mg of sodium thiosulfate were used per mol of silver halide.
mg and ammonium thiocyanate 50 mg were added. After 40 minutes, 0.23 mol of silver iodide fine particles was added, after 10 minutes, triphenylphosphine selenide was added, and after 40 minutes, the azaindene compound (T-
(2) was added in an amount of 1.8 g, and 5 minutes later, 13 g of trimethylolpropane and 30 g of gelatin were added, followed by rapid cooling and gelation of the emulsion to complete the chemical sensitization.

Dispersion liquid of spectral sensitizing dye (D-1): 14.8 g of spectral sensitizing dye (B) and 0.2 g of (A) are taken, and methanol is added and dissolved at 27 ° C. to obtain a spectral sensitizing dye. To obtain a methanol solution.

(D-2): The spectral sensitizing dye (B) was replaced with 9.
After taking 87g and 0.13g of (A) and adding 490g of water whose temperature was previously adjusted to 27 ° C, a high-speed stirrer (dissolver)
A dispersion of the spectral sensitizing dye was obtained by stirring at 3,500 rpm for 30 to 120 minutes. The average particle size of the disperse dye was 0.7 μm.

[0073]

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By the addition of the silver iodide grains described above, the average iodine content of the outermost surface of the silver halide grains in the silver halide emulsion was about 8.5 mol%.

Next, the emulsion thus sensitized was heated and redissolved, and the additives described below were added to prepare an emulsion coating solution. At the same time, coating solutions for the first layer and the protective layer were also prepared. The amount of silver per side is the amount shown in Table 1, and the amount with gelatin is 0.15 g / m ² for the first layer and 1.3 for the second layer (emulsion layer).
g / m ² , protective layer 0.75 g / m ² (total 2.2 g /
m ² ), two slide hopper type coaters were used to simultaneously coat both sides on the undercoated support described below, followed by drying to obtain a sample. However, the sample No. with reduced gelatin was used. For No. 7, 0.4 g of gelatin in the emulsion layer
/ M ^{2 was} reduced to 0.9 g / m ² .

Preparation of Support (Preparation of Conductive Particle P1 Dispersion) Stannous Chloride Hydrate 65
g was dissolved in 2000 cc of a water / ethanol mixed solution to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The precipitate is taken out by decantation and washed with distilled water many times. Silver nitrate is dropped into distilled water after washing the precipitate, and after it is confirmed that there is no reaction of chlorine ions, the mixture is added to 1000 cc of distilled water to bring the total amount to 2000 cc. Further, 40 cc of 30% ammonia water was added and heated in a water bath to obtain a colloidal SnO ₂ gel dispersion.

(Preparation of support for silver halide photographic light-sensitive material) Thickness after biaxial stretching and heat setting 175 μm, density 0.1
Blue colored polyethylene terephthalate (PE)
T) Both sides of the film were subjected to a corona discharge treatment of 8 W min / m ² , and one side was coated with an undercoating coating solution B-1 having the following constitution to give a dry film thickness of 0.8 μm as described in JP-A-59-19941. It was applied as an undercoat layer B-1 so that it was dried at 100 ° C. for 1 minute. On the surface of the PET film opposite to the subbing layer B-1, a subbing coating solution B-2 having the following constitution was coated to a dry film thickness of 0.8 μm as described in JP-A-59-77439. It was applied as a coating layer B-2 and dried at 110 ° C. for 1 minute.

<Undercoating First Layer> Undercoating coating solution B-1 Copolymer latex of 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene, 25% by weight of 2-hydroxyethyl acrylate Liquid (solid content 30%) 270 g Compound A 0.6 g Hexamethylene-1,6-bis (ethyleneurea) 0.8 g Water is made up to 1 liter.

Subbing coating solution B-2 Copolymerized latex solution of butyl acrylate 40% by weight, styrene 20% by weight, glycidyl acrylate 40% by weight (solid content 30%) 23 g Conductive particle P1 dispersion 415 g Polyethylene glycol ( Molecular weight 600) 0.12 mg Water 568 g <Undercoating second layer> Further, a corona discharge treatment of 8 W min / m ² was applied on the above-mentioned undercoating layers B-1 and B-2, and an undercoating coating solution having the following constitution was obtained. B-3 was applied so as to have a dry film thickness of 0.1 μm and dried at 100 ° C. for 1 minute.

Subbing coating solution B-3 Gelatin 10 g Compound A 0.4 g Compound B 0.1 g Silica particles (average particle size 3 μm) 0.1 g Water is added to 1 liter.

[0081]

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(Photosensitive Material Coating Layer) The amount of <first layer> is the amount per m ^{2 on} one side.

Gelatin 0.45 g Crossover cut dye [Table 2] <Second layer> Additives added to the emulsion are as follows. The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 70 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Sodium polystyrene sulfonate 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.0 g Mercapto compound t-Butylcatechol 68 mg KBr 85 mg Dextran (average molecular weight 40,000) 5.8 g Thallium nitrate 57 mg Colloidal silica (Ludox AM) (DuPont) Made) 80 ml

[0085]

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<Third Layer> Protective Layer Solution Next, the following was prepared as a protective layer coating solution. Additives are shown in amounts per liter of coating solution.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2.0 g Sodium-i-amyl-n-decylsulfosuccinate 1.0 g Polymethylmethacrylate (matting agent having an area average particle diameter of 3.5 μm) 2.1 g Silicon dioxide particles (A matting agent having an area average particle size of 1.2 μm) 0.5 g C ₇ F ₁₅ CH ₂ (OCH ₂ CH ₂ ) ₁₃ OH 0.75 g C ₄ F ₉ SO ₃ K 0.1 g C ₁₂ H ₂₅ CONH (CH ₂ CH ₂ O) ₅ H 2.0 g Mercapto compound Amount described in Table 1

[0088]

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The development processing was carried out by modifying the automatic processor SRX-502 (manufactured by Konica Corp.) to a line speed of 1.8 times and using the developing solution and fixing solution having the following formulations.

Developer formulation Part-A (for 12 liter finish) potassium hydroxide 450 g potassium sulfite (50% solution) 2280 g diethylenetetraamine pentaacetic acid 120 g sodium hydrogen carbonate 132 g 5-methylbenzotriazole 1.2 g 1-phenyl- 5-mercaptotetrazole 0.2 g 1,4-dihydroxybenzene 340 g Add water to make 5000 ml Part-B (for finishing 12 liters) Glacial acetic acid 170 g Triethylene glycol 185 g 1-phenyl-3-pyrazolidone 22 g 5-nitroindazole 0 4 g Starter solution formulation (for 1 liter finish) Glacial acetic acid 120 g Potassium bromide 225 g Add water to finish to 1000 ml Fixer formulation Part-A (for 18 liter finish) Anion thiosulfate Monium (70 wt / vol%) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Gluconic acid 70 g 1- (N, N-Dimethylamino) -ethyl-5-mercaptotetrazole 18 g Part-B (18 liter finish) Aluminum sulfate 800 g Preparation of developer A developer is prepared by adding Part-A and Pa to about 5 liters of water.
rt-B was added at the same time, and water was added while dissolving with stirring.
After finishing to 1 liter, the pH was adjusted to 10.40 with glacial acetic acid to obtain a developer.

20 ml of the starter solution was added to 1 liter of the developer, and the pH was adjusted to 10.40 to prepare a working solution.

Preparation of Fixing Solution The fixing solution was prepared by adding Part-A and Par to about 5 liters of water.
t-B was added at the same time, and water was added while stirring and dissolving to give 18
Liters, p with sulfuric acid and sodium hydroxide
H was adjusted to 4.4, and this was used as a fixing solution working solution and a fixing solution replenisher.

The processing temperature is 35 ° C. for development, 33 ° C. for fixing, 20 ° C. for water washing, 50 ° C. for drying, and the processing time is Dry.
The time to dry (that is, the time from when the leading end of the photosensitive material starts to be immersed in the developing solution to when the leading end comes out of the drying zone through the processing step) is 25 seconds.

The replenishing amounts of the developing solution and the fixing solution were respectively 10 ml per four-cut film, and after processing 3,000 four-cut films of SR-ESG (manufactured by Konica Corporation),
The samples of the examples were processed and evaluated as follows.

Sensitometry For sample sensitometry, a cassette for medical X-ray photography was used for each sample, and a fluorescent intensifying screen SRO-250 (on the front side (X-ray source side) and the back side (rear surface)) was used. Exposure was performed under the following conditions using Konica Corporation. As the fluorescent intensifying screen, the front side was used for the front side and the back side was used for the back side.
There are two types of fluorescent intensifying screens, one for the front side used on the X-ray source side and the other for the back side, and the SRO series is divided into the front side and the back side. The tube voltage was 100 kVp, the exposure time was 50 sec, and the distance method was used for the exposure. Fog of 1 + 1.0
The relative sensitivity is shown when the reciprocal of the exposure amount that gives the blackening density is set to 100. The development processing conditions used were those described above.

The sensitivity ratio (SA / SB) of the front and back surfaces of the exposed sample in the case of single-sided exposure was SRO-2 under the same photographing conditions as in the case where sensitometry by uniform exposure on both sides was obtained.
Using 50 fluorescent back intensifying screens, the single back method was used to perform exposure from only one side in the same manner as in the case of both sides, and development processing was performed under the same conditions. After development, the emulsion layer was decomposed and removed with a proteolytic enzyme (pronase) solution so that the density of the exposed surface and the back surface could be measured, and the relative sensitivity of each surface was determined. SA / SB in Table 1 represents (exposure surface sensitivity) SA / (back surface sensitivity) SB when exposed on one side.

Measurement of γ As described above, γ (gamma) is a characteristic curve obtained by exposing both sides of the support at the same time with fluorescent intensifying screens of the same luminescence amount, and connecting the densities of 1.0 to 2.0. It was calculated from the slope of the straight line portion.

A bending blackening test was conducted as a substitute method for pressure blackening. As a method, JP-A-61-13294
The sample was conditioned at 23 ° C. and 40% RH for 2 hours by the method described in No. 3, and then bent at about 360 ° with a radius of curvature of 4 mm. The results obtained above are shown in Table 1.

[0099]

[Table 1]

As is clear from Table 1, the samples of the present invention are:
There was no deterioration in pressure resistance and no decrease in sensitivity, and it was possible to increase γ during rapid processing.

Example 2 After the physically ripened emulsion used in Example 1 was heated to 54 ° C.,
0.36 g of the spectral sensitizing dye dispersion D-2 used in Example 1 was added per mol of silver halide, and 10 minutes later, the azaindene compound shown in Table 2 (before addition of chemical sensitizer) was added. After 10 minutes, chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added in the same amounts as in Example 1, and after 40 minutes, silver iodide fine particles and after 10 minutes, triphenylphosphine selenide was added in Example 1. The same amount was added.

After that, chemical sensitization was continued for 30 minutes or longer, and
After adding the described azaindene compound (after addition of chemical sensitizer), 13 g of trimethylolpropane and 45 g of gelatin, the mixture was rapidly cooled and the emulsion was gelled to complete the chemical sensitization.

The same materials as in Example 1 were used as the undercoated support, the emulsion coating solution additive and the protective layer solution. However, the first layer (dye layer) used in Example 1 was not coated and a two-layer constitution of an emulsion layer and a protective layer was formed. The other sample preparation methods were the same as in Example 1. The performance evaluation of the sample was performed in the same manner as in Example 1. However, regarding relative sensitivity, No. 18 to 10
It is a value when 0 is set. Table 2 shows the results.

[0104]

[Table 2]

From Table 2, it can be seen that the samples of the present invention had no deterioration in pressure resistance and no decrease in sensitivity, and that γ during rapid processing could be increased.

[0106]

According to the present invention, it is possible to provide a silver halide photographic light-sensitive material having a high γ level, which is free from problems such as pressure blackening in rapid and low replenishment processing.

Claims (5)

[Claims] 1. A silver halide photographic light-sensitive material having a silver halide emulsion layer and a non-photosensitive hydrophilic colloid layer on both sides of a support, wherein both emulsion layers are emulsions on the exposed side when exposed from one side. When the sensitivity of the layer is SA and the sensitivity of the emulsion layer on the opposite side is SB, SA / SB is 4 or less, and the non-photosensitive hydrophilic colloid layer contains a mercapto compound. Photographic material. 2. An emulsion layer containing a chemically ripened silver halide emulsion and a non-photosensitive hydrophilic colloid layer containing a mercapto compound are added separately before and after the addition of the chemical sensitizer. A silver halide photographic light-sensitive material characterized by being provided on the body. 3. The silver halide photographic light-sensitive material according to claim 2, wherein the addition of the azaindene compound before addition of the chemical sensitizer is performed after addition of the sensitizing dye. 4. The silver halide photographic light-sensitive material according to claim 1, 2 or 3, wherein the mercapto compound is represented by the following general formula (1). General formula (1) Z-SM In the formula, Z represents a nitrogen-containing 5- or 6-membered heterocyclic group, and M represents a hydrogen atom, an alkali metal atom or a quaternary ammonium group. 5. The silver halide photographic light-sensitive material according to claim 2 or 3, wherein the azaindene compound is represented by the following general formula (T). Embedded image In the formula, R ¹¹ represents a hydrogen atom, a carboxylic acid group and its ester group, a mercapto group, an alkyl group, an aryl group, a heterocyclic group, an alkylthio group or an alicyclic group, and R ¹²
Represents a hydrogen atom, a halogen atom, a carboxylic acid group and an ester group thereof, an alkyl group, an aryl group, a heterocyclic group and an alicyclic group, and R ¹³ represents a hydrogen atom, a hydroxyl group, a carboxylic acid group and an ester group thereof. Represents an amino group, an alkyl group, an aryl group, a heterocyclic group, or an alicyclic group, and R ¹² and R ¹³ may combine with each other to form a heterocycle or a carbocycle.