JP2649717B2 - Silver halide photographic material - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a silver halide photographic material, and more particularly to a silver halide photographic material suitable for ultra-rapid processing.

[Conventional technology]

In recent years, the consumption of silver halide photographic materials has been steadily increasing. For this reason, the number of developed silver halide photographic materials has been increased, and it has been required to speed up the development processing, that is, to increase the processing amount within the same time.

The above tendency is also seen in the printing plate making field. That is,
Due to the rapid increase in the immediacy and the number of times of information, it is necessary to carry out printing plate making operations in a short delivery time and in a larger amount. In order to satisfy the demands of the printing plate making industry, it is necessary to promote simplification of the printing process and to process the printing plate making film more quickly.

In order to shorten the time for the development process (including the steps of development, fixing, washing and drying), one method is to increase the transport speed. However, when the developing process is performed by a roller transport type automatic developing machine, if the roller transport speed is increased in order to shorten the developing process time, (a) reduction in density (sensitivity, contrast, reduction in maximum density), etc. (b) ) Fixing is not sufficiently performed, (c) film is not sufficiently washed with water,
(D) Problems such as insufficient drying of the film occur. Insufficient fixing and insufficient washing change the color tone during storage of the film, causing image quality to deteriorate.

One of the reasons why the development time is shortened and the density is not sufficient is that the number of developed silver is not sufficient because the developer does not sufficiently penetrate to the lower layer portion in the emulsion layer. As a countermeasure to this problem, for example, if the amount of the development accelerator is increased in the developer to increase the development or the development temperature is increased, the upper layer portion of the emulsion layer preparation is overdeveloped, and the fog density increases. Developing unevenness increases.

As a method for solving these problems, it is effective to reduce the amount of gelatin in the silver halide photographic light-sensitive material. However, when the amount of gelatin is reduced, the graininess of a photographic image is likely to deteriorate. Further, when the films are rubbed with each other or the film is rubbed with another substance, the so-called scratch deterioration, which is higher in density than other portions after the development processing, is likely to occur.

[Object of the invention]

In view of the above problems, an object of the present invention is to provide a silver halide photographic light-sensitive material which has a small density reduction even when subjected to ultra-rapid processing with a total processing time of 20 to 60 seconds, and has excellent sensitivity and fog. It is to be.

[Configuration of the invention]

The object of the present invention is to provide a support having an average particle size of 0.
A silver halide photograph comprising at least one photosensitive silver halide emulsion layer having a thickness of from 0.05 to 0.3 .mu.m and at least one non-photosensitive layer containing gelatin on the upper and lower sides of the emulsion layer; A silver halide photographic light-sensitive material, characterized in that the light-sensitive material contains at least one development inhibitor in the upper layer of the emulsion layer and at least one development accelerator in the lower layer of the emulsion layer. Achieved.
Furthermore, in the present invention, and wherein the amount of gelatin on the side having emulsion layers of the photosensitive material is 2.0~4.0g / m ^2, and the total processing time by an automatic developing machine are processed in 20 to 60 seconds I do.

 Hereinafter, the present invention will be described in detail.

The ultra-rapid processing referred to in this specification means that the leading edge of the film is inserted into the automatic developing machine and then passed through a developing tank, a transfer section, a fixing tank, a transfer section, a washing tank, a transfer section, and a drying section. For the entire length of time (in other words, the total length (m) of the processing line is equal to the line transfer speed (m / se).
c.) divided by (sec.)] is less than 60 seconds. The reason why the time of the transition portion should be included here is well known in the art. However, in the transition portion, since the liquid of the previous process swells in the gelatin film, it is substantially used. This is because the processing step can be regarded as progressing.

In the present invention, as the development-inhibiting product added to the upper layer of the emulsion layer, a compound represented by the following general formula [Ia] and / or an alkali metal bromide and / or an alkali metal iodide are preferable.

General formula (Ia) (In the formula, Y ₁ and Y ₂ represent a hydrogen atom or a mercapto group, R ₁ is a substituted or unsubstituted alkyl group, alkenyl group, aryl group, or alkoxy group, or a hydrogen atom, a halogen atom, a nitro group, It represents an amino group, a cyano group, a hydroxycarbonyl group, an alkoxycarbonyl group, an alkylcarbonyl group, a hydroxy group, a mercapto group, or a sulfo group.

A represents a nitrogen atom, a carbon atom or an oxygen atom, and B represents a nitrogen atom or a carbon atom. When A represents a carbon atom, n ₂ is 2, and when A represents a nitrogen atom,
n ₂ is 1 and n ₂ is 0 when A represents an oxygen atom.

When B represents a carbon atom, n ₁ is 0. Next, typical specific examples of the compound represented by the general formula [Ia] will be described, but the present invention is not limited thereto.

(Ia-1) benzotriazole (Ia-2) 5-methylbenzotriazole (Ia-3) 5-chlorobenzotriazole (Ia-4) 5-nitrobenzotriazole (Ia-5) 5-ethyl Benzotriazole (Ia-6) hydroxycarbonylbenzotriazole (Ia-7) 5-hydroxybenzotriazole (Ia-8) 5-aminobenzotriazole (Ia-9) 5-sulfobenzotriazole (Ia-10 ) 5-cyanobenzotriazole (Ia-11) 5-methoxybenzotriazole (Ia-12) 5-ethoxybenzotriazole (Ia-13) 5-mercaptobenzotriazole (Ia-14) benzimidazole (Ia -15) 5-sulfobenbenzimidazole (Ia-16) 5-methoxybenzimidazole (Ia-17) 5-chlorobenzimidazole (Ia-1) 8) 5-nitroindazole (Ia-19) 6-nitroindazole (Ia-20) 5-sulfindazole (Ia-21) benzoxazole (Ia-22) 2-mercapto-5-benzimidazole (I a-23) 2-Mercaptobenzoxazole The alkali metal bromide or alkali metal iodide used in the present invention includes NaBr, KBr, LiBr and the like or NaI, K
I, Li I and the like.

In the light-sensitive material of the present invention, the amount of the formula amount of a compound of [I a] is m ² per 1~500mg is preferred, and an alkali metal bromide or alkali metal iodides m ² per 10mg~ 1 g is preferred.

The upper layer of the emulsion layer preferably contains a tetrazolium compound represented by the following general formula [Ib].

General formula [I b] In the general formula [Ib], preferred examples of the substituent represented by R ₁ to R ₃ include an alkyl group (eg, methyl, ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, cyclohexyl, etc.), amino Group, acylamino group (eg, acetylamino), hydroxyl group, alkoxy group (eg, methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.), acyloxy group (eg, acetyloxy), halogen atom (eg, fluorine, chlorine, bromine, etc.), carbamoyl Groups, acylthio groups (eg, acetylthio), alkoxycarbonyl groups (eg, ethoxycarbonyl), carboxyl groups, acyl groups (eg, acetyl), cyano groups, nitro groups, mercapto groups, sulfoxy groups, and aminosulfoxy groups. La That.

 The X Examples of the anion represented by
Halogens such as ions, bromide ions and iodide ions
On, nitric acid, sulfuric acid, perchloric acid, etc.
Acid radicals of organic acids such as carboxylic acids and carboxylic acids, anionic activities
Agents such as p-toluenesulfonic acid anion, etc.
Higher alkylbenzene sulfonic acid anion, p-dodecyl
Higher alkylbenzenes such as benzenesulfonate anion
Sulfonate anion, lauryl sulfate anion, etc.
Higher alkyl sulfate anion, tetraphenyl
Boric acid-based anions such as boron, di-2-ethylhexyls
Dialkyl sulfosuccinate such as rufosuccinate anion
Nate anion, cetyl polyethenoxy sulfate
Polyether alcohol sulfates such as Nion Anion
, Higher aliphatic anions such as stearic acid anions,
Polymers such as acrylate anions with acid radicals
And the like.

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

(Exemplary compound) The tetrazolium compound used in the present invention is described, for example, in Chemical Reviews, Vol. 55, No. 33.
It can be easily synthesized according to the method described on pages 5 to 483.

The tetrazolium compound represented by the general formula [Ib] of the present invention is used in an amount of about 1 mg to 10 g, preferably about 10 mg to about 2 g, per 1 mol of silver halide contained in the silver halide photographic light-sensitive material of the present invention. It is preferably used in the range up to.

In the present invention, as the development accelerator added to the lower layer of the emulsion layer, a) a hydrazine compound b) an amine compound c) a developing agent is preferable.

The hydrazine compound used in the present invention is preferably a compound represented by the following general formula [IIa].

In the general formula (IIa), Ar represents an aryl group containing at least one diffusion-resistant group or a silver halide adsorption promoting group,
As the diffusion-resistant group, a ballast group commonly used in immobile photographic additives such as couplers is preferable. The ballast group is a group having a carbon number of 8 or more, which is relatively inert to photographic properties. For example, the ballast group is selected from an alkyl group, an alkoxy group, a phenyl group, an alkylphenyl group, a phenoxy group and an alkylphenoxy group. Can be.

Silver halide adsorption promoting groups include thiourea groups, thiourethane groups, heterocyclic thioamide groups, mercapto heterocyclic groups,
Examples include groups described in U.S. Patent No. 4,385,108, such as triazole groups.

R ₁ represents a substituted alkyl group, and the alkyl group represents a linear, branched, or cyclic alkyl group, and examples thereof include groups such as methyl, ethyl, propyl, butyl, isopropyl, pentyl, and cyclohexyl.

Substituents introduced into these alkyl groups include alkoxy (eg, methoxy, ethoxy, etc.), aryloxy (eg, phenoxy, p-chlorophenoxy, etc.),
Heterocyclic oxy (e.g., pyridyloxy, etc.), mercapto, alkylthio (e.g., methylthio, ethylthio, etc.), arylthio (e.g., phenylthio, p-chlorophenylthio, etc.), heterocyclic thio (e.g., pyridylthio, pyrimidylthio, thiadiazolylthio, etc.), Alkylsulfonyl (eg, methanesulfonyl, butanesulfonyl, etc.),
Arylsulfonyl (for example, benzenesulfonyl and the like),
Heterocyclic sulfonyl (eg, pyridylsulfonyl, morpholinosulfonyl, etc.), acyl (eg, acetyl, benzoyl, etc.), cyano, chloro, bromine, alkoxycarbonyl (eg, ethoxycarbonyl, methoxycarbonyl, etc.), aryloxycarbonyl (eg, phenoxycarbonyl, etc.), Carboxy, carbamoyl, alkylcarbamoyl (for example, N-methylcarbamoyl, N, N-
Dimethylcarbamoyl, etc.), arylcarbamoyl (eg, N-phenylcarbamoyl), amino, alkylamino (eg, methylamino, N, N-dimethylamino, etc.), arylamino (eg, phenylamino, naphthylamino, etc.), acylamino (Eg, acetylamino, benzoylamino, etc.), alkoxycarbonylamino (eg, ethoxycarbonylamino, etc.), aryloxycarbonylamino (eg, phenoxycarbonylamino, etc.), acyloxy (eg, acetyloxy, benzoyloxy, etc.), alkylaminocarbonyl Oxy (eg, methylaminocarbonyloxy, etc.), arylaminocarbonyloxy (eg, phenylaminocarbonyloxy, etc.), sulfo, sulfamoyl, alkylsulfamoyl For example, such methylsulfamoyl), an arylsulfamoyl (for example, each group of phenyl sulfamoyl, etc.) and the like.

The hydrogen atom of hydrazine may be substituted with a substituent such as a sulfonyl group (eg, methanesulfonyl, toluenesulfonyl, etc.), an acyl group (eg, acetyl, trifluoroacetyl, etc.), an oxalyl group (eg, ethoxalyl, etc.). Good.

Representative compounds represented by the above general formula [IIa] include the following.

The preferred amine compound for the present invention is represented by the following formula.

General formula (IIb) In the formula, R ₁ is a hydroxyalkyl group having 2 to 10 carbon atoms, R ₂ and R ₃ are each a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, 2 to 10 carbon atoms And a group represented by the following formula:

In the above formula, n is an integer of 1 to 10, and X and Y are a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or a hydroxyalkyl group having 2 to 10 carbon atoms, respectively.

Another preferred class of amino compounds is alkylamines, especially represented by the formula:

In the above formula, R ₄ is an alkyl group having 1 to 10 carbon atoms, and R ₅ and R ₆ are each a hydrogen atom or
An alkyl group having up to 10 carbon atoms.

Among the many amino compounds that can be used in practicing the present invention, the following are examples of particularly typical ones.

(IIb-1) Triethanolamine (IIb-2) Diethanolamine (IIb-3) Ethanolamine (IIb-4) 2-Diethylamino-1-ethanol (IIb-5) 2-Methylamino-1- Ethanol (IIb-6) 3-Diethylamino-1-propanol (IIb-7) 5-Methylamino-1-pentanol (IIb-8) Diethylamine (IIb-9) Triethylamine (IIb-10) Diisopropyl Amine (II b-11) Quinuclidine (II b-12) 1-4-cyclohexanehexane (methylamine) (II b-13) 0-Aminobenzoic acid (II b-14) Amino guanine sulfate (II b -15) 4-Amino-1-butanol The amount of the amino compound used in the present invention is preferably about 1 mg to 10 g, more preferably 10 mg to 2 g, per 1 mol of silver halide. Used in box.

The developing agents preferably used in the present invention are as follows:
Pyrazolidone compounds and hydroxybenzene compounds are exemplified.

 The 3-pyrazolidone compound is represented by the following formula.

General formula (IIc) In the formula, R ₁ represents an optionally substituted aryl group, R ₂ ,
R ₃ and R ₄ each represent a hydrogen atom or an optionally substituted alkyl group. Substituent as is, for example, methyl group of the aryl group represented by R _1, chloro group, amino group, methylamino group, an acetylamino group, a methoxy group, and groups such as methyl sulfonamide ethyl group mentioned, R ₁ Examples of the aryl group represented by include a phenyl group, a p-aminophenyl group, a p-chlorophenyl group, a p-acetamidophenyl group, and a p-methoxyphenyl group.

The alkyl group represented by R ₂ , R ₃ and R ₄ is a straight-chain, branched,
It may be cyclic, preferably has 1 to 8 carbon atoms, and examples of the substituent include a hydroxy group, a carboxy group, a sulfo group and the like, and a methyl group, a hydroxymethyl group, an ethyl group, a propyl group and the like. Can be

Representative specific examples of the 3-pyrazolidone compound are shown below.

(IIc-1) 1-phenyl-3-pyrazolidone (IIc-2) 1-phenyl-4,4-dimethyl-3-pyrazolidone (IIc-3) 1-phenyl-4-methyl-4-hydro Xymethyl-3-pyrazolidone (IIc-4) 1-phenyl-4,4-dihydroxymethyl-3-pyrazolidone (IIc-5) 1-phenyl-5-methyl-3-pyrazolidone (IIc-6) 1-phenyl-4,4-dimethyl-3-pyrazolidone (IIc-7) 1-p-aminophenyl-4-methyl-4-propyl-3-pyrazolidone (IIc-8) 1-p-chlorophenyl- 4-methyl-4-ethyl-3-pyrazolidone (II c-9) 1-p-acetamidophenyl-4,4-
Diethyl-3-pyrazolidone (IIc-10) 1-p-methoxyphenyl-4,4-diethyl-3-pyrazolidone The compound of the present invention is present in the light-sensitive material in the light-sensitive silver halide emulsion layer. Desirably, a non-emulsion layer such as a protective film layer, an intermediate layer, an undercoat layer or a backing layer may be used. The amount of the compound to be added may be generally dissolved in an organic solvent. The amount of the compound added is 10 ^-6 to 10 ^-1 mol per mol of silver halide, but is most preferably in the range of 10 ^-4 to 10 ^-2 mol. Show good results.

The dihydroxybenzene compound contained in the photosensitive material used in the image forming method of the present invention is a compound represented by the following formula.

General formula (II d) In the above formula, each of R ₅ , R ₆ and R ₇ is a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group,-
It represents an O-R ₈ or -S-R _8. R ₈ represents a substituted or unsubstituted alkyl group, aryl group, or substituted or unsubstituted heterocyclic group. n represents 0 or 1.

 Specific examples are shown below.

(II d-1) Hydroquinone (II d-2) Chlorohydroquinone (II d-3) Brom hydroquinone (II d-4) Methyl hydroquinone (II d-5) 2,3-Dichlorohydroquinone (II d-6) 2 , 5-Dibenzoylaminohydroquinone (II d-7) 2,5-diacetaminohydroquinone (II d-8) hydroquinone monosulfonate This compound is present in the light-sensitive material in the light-sensitive silver halide emulsion layer. However, it may be in a non-emulsion layer such as a protective film layer, an intermediate layer, an undercoat layer or a backing layer. In general, the compound may be added by dissolving it in water or an organic solvent such as alcohols such as methanol and ethanol, glycols such as diethylene glycol and triethylene glycol, and ketones such as acetone. 0.001 to 0.10 mol is added per 1 mol, preferably 0.05 to 0.03 mol.

The silver halide photographic material preferably has a gelatin amount of 2.00 to 3.20 g / m ² on the side having the hydrophilic colloid layer including the photosensitive silver halide emulsion layer.

The silver halide used in the present invention can be sensitized by various chemical sensitizers.

Examples of the sensitizer include active gelatin, a sulfur sensitizer (sodium thiosulfate, allylthiocarbamide, thiourea, allylisothiocyanate, etc.), a selenium sensitizer (N,
N-dimethylselenourea, selenourea, etc.), reduction sensitizers (triethylenetetramine, stannous chloride, etc.), for example, potassium chloroaulite, potassium aurithiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methyl chloride And various noble metal sensitizers represented by ammonium chloroparadate, potassium chloroplatinate, sodium chloroparadiate and the like can be used alone or in combination of two or more. When a gold sensitizer is used, rhodamonmon can be used as an auxiliary agent. Further, the silver halide emulsion which can be used in the present invention may be optically sensitized using one or more sensitizing dyes in order to impart a desired photosensitive wavelength or sensitivity.

Although various sensitizing dyes can be used,
Optical sensitizing dyes that can be advantageously used in the present invention include cyanines, merocyanines, trinuclear or tetranuclear merocyanines, trinuclear or tetranuclear cyanines, styryls, holopolar cyanines, hemicyanines, oxinols And hemioxonols. These optical sensitizing dyes, as a nitrogen-containing heterocyclic nucleus, have a part of their structure as a basic group such as thiazoline or thiazole or a nucleus such as rhodamine, thiohidatoin, oxazolidinedione, barbituric acid, thiobarbituric acid or pyrazolone. Preferably, such a nucleus can be substituted with alkyl, hydroxyalkyl, halogen, phenyl, cyano, or alkoxy, and these optically ring-enhancing dyes may be condensed with a carbocyclic or heterocyclic ring. When the above-mentioned optical sensitizing dye, particularly a merocyanine-based sensitizing dye, is used, not only optical sensitization but also an effect of increasing the development latitude can be obtained. The silver halide emulsion used in the present invention is, for example, U.S. Pat.
No. 12982, West German Application Publication No. 1189380, No. 2058626, No. 211
No. 8411, JP-B-43-4133, U.S. Pat.No. 3,342,596, JP-B-47-4417, West German Application Publication No. 2149789, JP-B-39-282
No. 5, compounds described in No. 49-13566, preferably, for example, 5,6-trimethylene-7-hydroxy-S-
Triazolo (1,5-a) pyrimidine, 5,6-tetramethylene-7-hydroxy-S-triazolo (1,5-a) pyrimidine, 5-methyl-6-bromo-7-hydroxy-S
Triazolo (1,5-a) pyrimidine, gallic esters (eg isoamyl gallate, dodecyl gallate, propyl gallate, sodium gallate), mercaptanic acid (1-phenyl-5-mercaptotetrazole, 2-
It can be stabilized using mercaptobenzthiazole), benzotriazoles (5-bromobenzotriazole, 5-methylbenzotriazole), benzimidazoles (6-nitrobenzimidazole) and the like.

The hydrophilic colloid used particularly advantageously in the present invention is gelatin. Examples of hydrophilic colloids other than gelatin include colloidal albumin, agar, gum arabic, alginic acid, hydrolyzed cellulose acetate, acrylamide, and imidized polyamide. , Polyvinyl alcohol, hydrolyzed polyvinyl acetate, gelatin derivatives such as U.S. Pat.Nos. 2,614,928 and 2,5
No. 25,753, phenylcarbamyl gelatin, acylated gelatin, phthalated gelatin, or styrene acrylate, acrylic as described in U.S. Pat.Nos. 2,548,520 and 2,831,767. Acid esters, methacrylic acid, and those obtained by graft-polymerizing a polymerizable monomer having an ethylene group such as methacrylic acid ester onto gelatin, and the like, and these hydrophilic colloids are layers containing no silver halide, for example, It can also be applied to an antihalation layer, a protective layer, an intermediate layer and the like.

As the support used in the present invention, for example, baryta paper,
Polyethylene coated paper, polypropylene synthetic paper, glass plate, cellulose acetate, cellulose nitrate,
For example, typical examples include a polyester film such as polyethylene terephthalate, a polyamide film, a polypropylene film, a polycarbonate film, and a polystyrene film. These supports are appropriately selected depending on the purpose of use of the silver halide photographic light-sensitive material.

Various photographic additives as needed in the hydrophilic colloid layer used in the present invention, for example, gelatin plasticizer, hardener,
Surfactants, image stabilizers, ultraviolet absorbers, antistain agents, pH adjusters, antioxidants, antistatic agents, thickeners, graininess improvers, dyes, mordants, brighteners, development speed adjusters, Matting agents and the like can be used within a range that does not impair the effects of the present invention.

Various developing agents known in the art for the development processing of the present invention,
The treatment can be carried out using an additive, but it is preferable to carry out the treatment with a developer containing a compound represented by the following general formula [AI] and / or [AII].

General formula (AI) General formula (A II) In the formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom, a lower alkyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, a sulfo group, a halogen atom, an amino group or a nitro group, Each group includes those having a substituent.

Next, typical specific examples of the compound represented by the general formula [AI] or the general formula [A II] will be described.

Exemplary compound of the general formula [AI] AI-1 5-nitroindazole AI-2 5-aminoindazole AI-3 5-p-toluenesulfonamide-indazole AI-4 5-chloroindazole AI-5 5-benzoylacetamide -Indazole AI-6 5-cyanoindazole AI-7 5-p-nitrobenzoylamino-indazole AI-8 1-methyl-5-nitro-indazole AI-9 6-nitroindazole AI-10 3-methyl-5 -Nitro-indazole AI-11 4-Chloro-5-nitro-indazole Among the compounds of the general formula [AI], nitroindazoles are preferable for use in the developer of the present invention. A particularly preferred compound is 5-nitroindazole, which has the following structural formula:

Next, specific examples of the compound represented by the general formula [AII] are shown.

General formula (A II) [Examples] Examples of the present invention will be described in detail below, but it goes without saying that the present invention is not limited to these.

Example 1 A silver chlorobromide emulsion having a silver bromide content of 2 mol% was prepared as follows.

An aqueous solution containing 23.9 mg of pentabromorhodium potassium salt, sodium chloride and potassium bromide per 60 g of silver nitrate and an aqueous solution of silver nitrate were simultaneously mixed in an aqueous solution of gelatin for 25 minutes while stirring. Diameter 0.
Silver chlorobromide emulsions of 15 μm each were prepared.

200 mg of 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added to this emulsion as a stabilizer, followed by washing with water and desalting.

20 mg of 6-methyl 4-hydroxy-1,3,3a, 7-
After the addition of tetrazaindene, sulfur sensitization was performed. After sulfur sensitization, necessary amounts of gelatin were added, and 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer to prepare an emulsion E1, and then gelatin was added. It was adjusted so that the amount of gelatin was as shown in Table 1.

(Preparation of latex for emulsion addition (L)) 0.25 kg of each sugar industry KMDS (dextran sulfate sodium salt) and ammonium persulfate 0.05 in water 40
While stirring at a liquid temperature of 81 ° C. to the liquid to which Kg was added, n-
A mixed solution of 4.51 kg of butyl acrylate, 5.49 kg of styrene and 0.1 kg of acrylic acid was added over 1 hour, and then 0.005 kg of ammonium persulfate was added. After stirring for 1.5 hours, the mixture was cooled, and the pH was adjusted to 6 with aqueous ammonia. .

The obtained latex liquid was filtered off with a GF / D filter manufactured by Whotman and finished with water to 50.5 kg to prepare a monodisperse emulsion-adding latex (L) having an average particle diameter of 0.25 μm.

The following additives were added to the emulsion to prepare a silver halide emulsion coating solution as described below.

(Preparation of emulsion coating solution) A gelatin solution was added to the above emulsion solution, 9 mg of phenol was added as a bactericide, the pH was adjusted to 6.5 using 0.5N sodium hydroxide solution, and then 360 mg of the following tetrazolium compound (T) was added. In addition, 5 ml of a 20% aqueous solution of saponin per mole of silver halide, 180 mg of sodium dodecylbenzenesulfonate, 80 mg of 5-methylbenztriazole, and the latex solution (L) for adding an emulsion solution were added.
Thereafter, 60 mg of the compound (M) and 280 mg of a styrene-maleic acid copolymer aqueous polymer as a thickener were sequentially added, followed by finishing with water to prepare an emulsion coating solution.

Next, an upper layer coating solution of the emulsion layer was prepared as follows.

(Preparation of Upper Layer of Emulsion Layer) Pure water 10 was added to 1 kg of gelatin, and after swelling, dissolved at 40 ° C. Then, as a coating aid, a 1% aqueous solution of the following compound (Z) 2.9 was used. 80 g of N), 10 g of amorphous silica having an average particle diameter of 3 μm, 20 g of amorphous silica having an average particle diameter of 8 μm, and 200 mg of the following compound (T) were added as matting agents. Subsequently, the compounds shown in Table 1 were added as the compounds to be used in the present invention, and the mixture was further diluted with citric acid to pH 5.
After adjusting to 4, it was finished to 17 with water to prepare an upper layer coating solution of the emulsion layer.

(Preparation of Lower Layer of Emulsion Layer) Pure water 10 was added to 1 kg of gelatin, and after swelling, dissolved at 40 ° C. Then, as a coating aid, 2.9 of a 1% aqueous solution of the following compound (Z) was used. 80 g of N). Subsequently, the compounds shown in Table 1 were added as the compounds to be used in the present invention, and the mixture was further added with citric acid to pH 5.4.
After that, the mixture was finished to 17 with water to prepare an upper layer coating solution for the emulsion layer.

Next, a backing coating solution used for coating the backing lower layer was prepared as follows.

(Preparation of backing coating solution) 36 kg of gelatin was swollen in water, heated and dissolved, and 1.6 kg of the following compound (C-1) and 310 kg of (C-2) were used as dyes.
g, 1.9 kg of (C-3) and 2.9 kg of the compound (N) were added as an aqueous solution. Then, 11% of a 20% aqueous solution of saponin was added, and 5 kg of the following compound (C-4) was added as a physical property modifier. ,
As a methanol solution, 63 g of the following compound (C-5),
And 270 g of the following compound (C-6) were added. As a thickener, 800 g of a styrene-maleic acid copolymer water-soluble polymer was added to the solution to adjust the viscosity, and then an aqueous citric acid solution was used.
The mixture was adjusted to pH 5.4, and finally 144 g of glyoxal was added, and the mixture was adjusted to 960 with water to prepare a BC coating liquid B-1.

Next, a protective film coating solution was prepared as follows for coating the protective film layer of the backing layer.

(Preparation of coating solution for protective layer for BC layer) Gelatin (50 kg) was swelled in water, heated and dissolved, and then 2-sulfonate-bis (2-ethylhexyl) succinate sodium salt was added in an amount of 340 g. (Average particle size of about 0.4μ), 1.7Kg, 3.4Kg of sodium chloride, 1.1Kg of glyoxal and 540g of mucochloric acid were added, and finished to 1000 with water to prepare a protective film coating solution P-2, and backing. The amount of gelatin in the layer is 2mg /
It was applied as a m ^2.

[Preparation of evaluation sample]

Each of the above coating solutions was used in combination shown in Table 1
Example 1 of Example 1 was coated on both sides of a polyethylene terephthalate film (thickness: 100 μm) provided with an undercoat layer on each side to prepare evaluation samples shown in Table 1.

At that time, the backing lower layer was coated such that the gelatin dry weight is 2 g / m ² on one surface of the support was coated with a subbing layer, gelatin dry weight backing protective layer thereon simultaneously 1g / m ² and dried. Then, an emulsion layer was coated on the other side of the support so as to have a dry weight shown in Table 1 and a coated silver amount of 4.3 g / m ² , and an emulsion protective agent layer was formed thereon by gelatin drying. Evaluation samples 1 to 9 were prepared by coating and drying simultaneously with the emulsion layer while adding formalin in the amount shown in Table 1 as a hardener so that the weight became 1 g / m ² .

The above sample was brought into close contact with a halftone dot image prepared in advance as a manuscript and the emulsion surface, exposed using a printer for a light room photosensitive material, and developed.

 The development was performed using the following developer and conditions.

Developer formulation (Composition A) Pure water (ion-exchanged water) 150 ml Disodium ethylenediaminetetraacetate 2 g Diethylene glycol 50 g Potassium sulfite (55% W / V aqueous solution) 100 ml Potassium carbonate 50 g Hydroquinone 15 g 5-Methylbenzo Triazole 200 mg 1-Phenyl-5-mercaptotetrazole 30 mg Potassium hydroxide Amount to adjust the pH of the working solution to 10.4 Potassium bromide 4.5 g (Composition B) Pure water (ion-exchanged water) 3 ml Diethylene glycol 50 g Ethylenediaminetetraacetic acid Sodium salt 25 mg Acetic acid (90% aqueous solution) 0.3 ml 5-Nitroindazole 110 mg 1-phenyl-3-pyrazolidone 500 mg When using a developer, the above composition A and composition B are dissolved in 500 ml of water in this order, and Finished and used.

Fixer formulation (Composition A) Ammonium thiosulfate (72.5% W / V aqueous solution) 230 ml Sodium sulfite 9.5 g Sodium acetate trihydrate 15.9 g Boric acid 6.7 g Sodium citrate dihydrate 2 g Acetic acid (90% W / W solution) 8.1 ml (composition B) pure water (ion-exchanged water) aqueous solution of 17 ml sulfuric acid (aqueous solution of 50% W / W) 5.8g of aluminum sulfate (Al ₂ O ₃ in terms of content of 8.1% W / W) 26.5g fixing When the solution was used, it was dissolved in 500 ml of water in the order of the composition A and the composition B in this order, and finished to 1 before use. The pH of the fixing solution was about 4.3.

[Rapid development processing conditions]

 The processing time was the following two times.

(Process) (Temperature) (Time) (Time) Current 30 ° C 30 seconds 15 seconds Fixed 30 ° C 30 seconds 15 seconds Rinse at room temperature 20 seconds 10 seconds Dry 45 ° C 20 seconds 10 seconds Transfer speed 1450mm / min 2900mm / min Total processing time 100 seconds 50 seconds Here, total processing time refers to the time from when the leading edge of the film is put into the automatic processor until the leading edge of the film comes out after the drying process.

Sensitivity is expressed as the reciprocal of the exposure that gives a density of 3.0.
Was set to 100, and the fog was set to 100 for sample 1. Gamma was determined for densities between 0.3 and 3.0.

From the results shown in Table 1, it is clear that the sample of the present invention can significantly reduce the development processing time, that is, can perform ultra-rapid processing without decreasing the sensitivity and the maximum density (Dmax) and without increasing fog.

〔The invention's effect〕

According to the present invention, it was possible to provide a silver halide photographic light-sensitive material capable of performing an extremely rapid processing without lowering the maximum sensitivity density.

Claims (3)

(57) [Claims] An average particle size of 0.05 to 0.3 μm on one side of a support.
m, at least one photosensitive silver halide emulsion layer, and at least one non-photosensitive layer containing gelatin above and below the emulsion layer. A silver halide photographic material comprising at least one development inhibitor in the upper layer of the emulsion layer and at least one development accelerator in the lower layer of the emulsion layer. 2. A silver halide photographic material according to claim 1, wherein the amount of gelatin on the side having the emulsion layer of the silver halide photographic material is 2.0 to 4.0 g / m ² . 3. The silver halide photographic light-sensitive material according to claim 1, wherein the total processing time by the automatic developing machine is 20 to 60 seconds.