EP0316864A2

EP0316864A2 - Silver halide photographic light-sensitive material and processing method

Info

Publication number: EP0316864A2
Application number: EP88119019A
Authority: EP
Inventors: Takeo Arai; Toshiharu Nagashima; Hideaki Sakata
Original assignee: Konica Minolta Inc
Current assignee: Konica Minolta Inc
Priority date: 1987-11-17
Filing date: 1988-11-15
Publication date: 1989-05-24
Also published as: JPH0236A; EP0316864A3

Abstract

The method of processing a silver halide photographic light-sensitive material in a roller-transporting type processing equipment, comprising the steps of developing, fixing, washing and drying, is disclosed. The photographic material is comprised of a support having thereon at least one hydrophilic layer including a silver halide emulsion layer containing at least one selected from the group consisting of silver chloride, silver bromochloride and silver bromochloroiodide each containing silver chloride of not less than 60 mol %, and water content of the photographic material just after the washing step is 5 to 16 g/m².

Description

FIELD OF THE INVENTION

The present invention relates to a silver halide photographic light-sensitive material and a processing method therefor. The invention is applicable both to a light-sensitive material suitable for rapid processing, and to a processing method for the similar material, and is adaptable to a technical field such as photomechanical light-sensitive material technology.

BACKGROUND OF THE INVENTION

Recently, consumption of silver halide photographic light-sensitive materials has been constantly increasing. Accordingly, a number of frames of silver halide photographic light-sensitive materials to be processed has been increasing, and, therefore, rapid developing, i.e. an increase of processed quantity per time is strongly needed.
Reducing time for developing process (usually comprising developing, fixing, washing, and drying steps) entails, as one possible way, increase in a travelling speed of a light-sensitive material. In the course of a developing process using a roller-transporting type automatic developing equipment, however, reducing time for developing process by increasing a roller-transporting speed causes problems such as (a) insufficient optical density (decrease of sensitivity, contrast and maximum density); (b) insufficient fixing; (c) insufficiently washed film; and (d) insufficiently dried film. Insufficient fixing as well as insufficient washing result in discoloration and thus deterioration in image quality in preservation of a developed film.
One technique to solve these problems is to decrease an amount of gelatin used in a photographic film. A photographic film incorporating a smaller amount of gelatin, however, readily results in a photographic image of poor graininess. Additionally, when a piece of a film is rubbed with another piece of such a film, or with another material, a so-called "scratch-induced" image deterioration tends to occur after a developing process where the density of a rubbed area is higher than that of the remaining area.
A ultra-rapid processing is strongly needed because of the above-mentioned reasons. The term "ultra-rapid processing" according to this specification is defined as follows: a process wherein the leading edge of a film is inserted into an automatic developing equipment, and guided through a developing bath, travelling path, fixing bath, travelling path, washing bath, travelling path, drying unit, and then, the leading edge of the film comes out of a drying unit, and a total duration of this process [in other words, a quotient (sec.) obtained by dividing a total length (m) of a processing line by a travelling speed (m/sec.)] ranges from 20 to 60 seconds. The reason why time for the travelling path is included in the calculation above is, as well known in the art, that photographic processing continues even in a travelling path because a processing solution of a preceding process remains in a swollen gelatin layer.

SUMMARY OF THE INVENTION

The object of the invention is to provide a silver halide photographic light-sensitive material and an appropriate processing method therefor, wherein the light-sensitive material is free from the preceding problems of a prior art even when subjected to such a rapid processing as a ultra-rapid processing of which total processing time is 20 to 60 seconds, and the light-sensitive material excels in sensitivity, fogging, and graininess, and is less prone to a "scratch-induced" image quality deterioration and pressure desensitization even with a smaller amount of gelatin incorporated.
The object of the present invention above is achieved by a silver halide photographic light-sensitive material comprising a support having thereon at least one hydrophilic colloid layer, wherein the photographic material contains, as silver halide, silver chloride or silver bromochloride or silver bromochloroiodide each comprising not less than 60 mol% of silver chloride, and wherein the photographic material contains water of 5 to 16 g/m² just coming from a washing step in a roller-transporting type automatic developing equipment.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 illustrates an automatic developing equipment used in Examples of the invention, and the equipment has a variable travelling speed.
Reference numerals in the figure represent as follows:

1... Loading station
2... Detection-developing travelling rack
3....Developing rack
4... Developing-fixing travelling rack
5... Fixing rack
6... Fixing-washing travelling rack
7... Washing rack
8... Squeezing rack
9... Drying rack
10.. Guide
11.. Drying outlet guide
12.. Film basket

DETAILED DESCRIPTION OF THE INVENTION

With the silver halide photographic light-sensitive material, a preferred amount of gelatin in the hydrophilic colloid layers including a light-sensitive silver halide emulsion layer is at a range of 2.00 to 3.20 g/m².
According to the invention, an allowable water content is at a range of 5 to 16 g/m² as mentioned above. However, the preferred content is at a range of 8 to 13 g/m².
In this respect, a water content of a silver halide photographic material is determined as follows;
- the weight of an unprocessed sample is measured at 23°C and RH 50%.
- the sample coming out of a washing unit is put into a PE bag of a known weight to prevent water vaporization.
- the weight of the PE bag having therein the sample is measured and the water content of the photographic material after being processed is determined by the following formula;
Water content = (weight of PE bag including the sample - weight of unprocessed sample plus PE bag) ÷ surface area of the sample
It is well known that reduction of a gelatin amount involved in a photographic material results in decreasing water content thereof. As described previously, however, this step causes the problems. In the present invention, reduction of water content has been achieved by combining reduction of a gelatin amount with the means to maintain a developing solution swollen in a photographic material at a lower level and to promote development to a higher level. Combination of raising a processing line speed with the preceding means contributes to attaining the object of the invention. That is, development is expedited by raising a processing line speed which results in increase of a relative efficiency of contact and diffusion between a developing solution and a photographic material. As described previously, however, simply raising a line speed without changing the other conditions will result in causing such problems as lowering of density, lack of fixing etc; in this connection, the processing line speed is preferably faster than 1500 mm/minute, more preferably faster than 1900 mm/minute. These problems can be prevented by adjusting temperature of the processing solutions to optimum one and setting a travelling path ratio defined by (staying time of a photographic material in a processing bath)/(staying time plus travelling time from bath to bath) at a higher ratio than 0.75. As described so far, reduction of water content in a photographic material, which is necessary for a ultra-rapid processing, can be achieved by total and skilful combination of controlling gelatin and hardner amounts, raising a processing speed, adjusting a travelling path ratio and controlling processing temperature. Meanwhile, in order to develop efficiently a photographic material having as high silver content as more than 3.5 g/m², it is indispensable to raise a relative efficiency of contact and diffusion between a developing solution and a photographic material. One of the ways to meet this requirement is faster circulation or heavier agitation of a developing solution, however this way sometimes causes bubbling on a solution surface, which in turn results in an irregularly developed image. This antinomic problem can be solved by raising a processing line speed, which increases a relative efficiency of stirring a developing solution without causing any bubbling resulting in an irregularly developed image. In the present invention, the problems which are possibly caused by a faster processing line speed, i.e. lowering of an optical density, lack of fixing, can be prevented by raising a travelling path ratio to a higher ratio than 0.75. In this connection, a travelling path of a photographic material in a processing solution is preferably more than 250 mm, more preferably more than 330 mm.
The silver halide photographic light-sensitive material of the invention contains, as silver halide, silver chloride, silver bromochloride, or silver bromochloroiodide. Such silver bromochloride or silver bromochloroiodide contains not less than 60 mol%, preferably not less than 70 mol% of silver chloride.
The preferred average grain size of silver halide grains is at a range of 0.05 to 0.3 µm; and the silver halide grains are preferably in narrower size distribution not more than 15% in terms of a fluctuation coefficient defined as (standard deviation of grain size)/(average grain size)x 100.
The silver halide used in the invention can be sensitized by any of various chemical sensitizers.
The examples of such sensitizers include active gelatin, sulfur sensitizers (such as sodium thiosulfate, arylthiocarbamide, thiourea, and arylisothiacyanate), selenium sensitizers (such as N,N-dimethylselenourea, and selenourea), reducing sensitizers (such as triethylenetetramine, and stannous chloride), and various noble metal sensitizers such as potassium chloroaurate potassium aurothiocyanate, potassium chloroaurate, 2-aurosulfobenzothiazole methylchloride, ammonium chloropalladate, potassium chloroplatinate, and sodium chloropalladate. These sensitizers are used singly or in combination. A gold sensitizer may be used in conjunction with rhodan ammonium serving as coagent. Additionally, a silver halide emulsion used in the invention can be optically sensitized using one or more sensitizing dyes in order to provide it with sensitivity to an intended spectral region.
A wide range of sensitizing dyes can be used for this purpose. However, the optical sensitizing dyes useful in the invention are cyanines, merocyanines; trinuclear or tetranuclear merocyanines; trinuclear or tetranuclear cyanines; styryls; holopolar cyanines; hemicyanines; oxonols; and hemioxonols. These optical sensitizing dyes are preferably those having, therein a partial structure of nitrogen including heterocyclic rings comprising a basic group such as a thiazoline or thiazole group; or a group such as rhodamine, thiohydantoin, oxazolidinedione, barbituric acid, thiobarbituric acid, or pyrazolone. Such groups may have a substituent such as alkyl group, hydroxy alkyl group, halogen atom, phenyl group, cyano group, or alkoxy group. Additionally, these optical sensitizing dyes may be condensed with a carbocycle or heterocycle. The foregoing optical sensitizing dyes, especially a merocyanine sensitizing dye, are effective not only in optical sensitization but also in wider development latitude. The silver halide emulsion used in the invention can be stabilized using compounds described in, for example, U.S. Patent Nos. 2,444,607, 2,716,062, and 3,512,982; West German DAS Patent Nos. 1,189,380, 2,058,626, and 2,118,411; Japanese Patent Examined Publication No. 4133/1968; U.S. Patent No. 3,342,596; Japanese Patent Examined Publication No. 4417/1972; West German DAS Patent No, 2,149,789; or Japanese Patent Examined Publication Nos. 2825/1964, and 13566/1974. Among them, the preferred compounds are 5,6-trimethylene-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5,6-tetramethylene-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy-S-triazolo(1,5-a)pyrimidine, 7-hydroxy-S-triazolo(1,5-a)pyrimidine, 5-methyl-6-bromo-7-hydroxy-S-triazolo(1,5-a)pyrimidine, gallic acid esters (such as isoamyl gallate, dodecyl gallate, propyl gallate, and sodium gallate), mercaptan acids (such as 1-phenyl-5-mercaptotetrazole, and 2-mercaptobenzthiazole), benzotriazoles (such as 5-bromobenzotriazole, and 5-methylbenzotriazole), benzimidazoles (such as 6-nitrobenzimidazole).
The hydrophilic colloid favorably used in the invention is gelatin. The applicable hydrophilic colloids other than gelatin are colloidal albumin, agar agar, arabic gum, alginic acid, hydrolyzed cellulose acetate; polyacrylamide; substituted polyamide; polyvinyl alcohol; hydrolyzed polyvinyl acetate; gelatin derivatives. The other examples are described in U.S. Patent Nos. 2,614,928, and 2,525,753, such as phenylcarbamyl gelatin, acylated gelatin, and phthalated gelatin; as described in U.S. Patent No. 2,548,520, and 2,831,767, products made by graft-polymerizing with gelatin such monomers having ethylene groups as styrene, acrylic acid, acrylic acid ester, methacrylic acid, and methacrylic acid ester. These hydrophilic colloids can be applied to the layers not containing silver halide, such as an antihalation layer, protective layer and intermediate layer.
The typical supports possibly used in the invention include baryta paper, polyethylene coated paper, polypropylene synthesized paper, glass plate, cellulose acetate and cellulose nitrate; polyester film such as polyethylene terephthalate; polyamide film; polypropylene film, polycarbonate film, and polystyrene film. These supports are selected by application of a silver halide photographic light-sensitive material.
Upon requirement a hydrophilic collid layer in the invention can incorporate any of various photographic additives such as plasticizer for gelatin, hardener, surfactant, image stabilizer, ultraviolet absorber, anti-stain agent, pH adjuster, anti-oxidant, anti-static agent, thickener, graininess improving agent, dye, mordant, whitening agent, developing rate controller, and matting agent, to the extent where the invention is not badly affected.
The light-sensitive material of the invention preferably contains a tetrazolium compound or hydrazine compound.
The preferred tetrazolium compounds are those represented by the following Formula [IA].
In this formula, R₁, R₂, and R₃ independently represent a hydrogen atom, or a substituent group; X^⊖ represents an anion.
In Formula [IA], the examples of a preferred substituent group represented by R₁ through R₃ include an alkyl group (such as methyl, ethyl, cyclopropyl, propyl, isopropyl, cyclobutyl, butyl, isobutyl, pentyl, and cyclohexyl), an amino group, an acylamino group (such as acetylamino), a hydroxyl group, an alkoxy group (such as methoxy, ethoxy, propoxy, butoxy, and pentoxy), an acyloxy group (such as acetyloxy), a halogen atom (such as fluorine, chlorine, and bromine), a carbamoyl group, an acylthio group such as acetylthio), an alkoxy carbonyl group (such as ethoxy carbonyl), a carboxyl group, an acyl group (such as acetyl), a cyano group, nitro group, a mercapto group, a sulfoxy group, and an aminosulfoxy group.
The examples of the anion represented by X^⊖ include a halide ion such as a chloride ion, a bromide ion and an iodide ion; an acid radical of an inorganic acid such as nitric acid, sulfuric acid and perchloic acid; an acid radical of an organic acid such as sulfonic acid and carboxylic acid; a lower alkyl benzene sulfonate anion such as a p-toluene sulfonate anion, a higher alkyl benzene sulfonate anion such as a p-dodecylbenzene sulfonate anion, a higher alkyl sulfate ester anion such as a laurylsulfate anion, a boric acid anion such as tetraphenyl boron, a dialkylsulfosuccinate anion such as di-2-ethylhexyl sulfosuccinate anion, a polyether alcohol sulfate ester anion such as a cetylpolyethenoxy sulfate anion, a higher aliphatic ester anion such as a stearic acid anion, and polymer having an acid radical such as a polyacrylic acid anion.
The typical examples of a compound represented by Formula [IA] in the invention are as follows. However, the scope of useful compounds are not limited only to these examples.
The tetrazolium compounds used in the invention can be readily synthesized by the method described in Chemical Reviews, Vol. 55, pp. 335-483.
A tetrazolium compound represented by Formula [IA] is preferably used in an amount of approx. 1 mg to 10 g per mol of silver halide, in particular, approx. 10 mg to 2 g, per mol of silver halide in the silver halide photographic light-sensitive material of the invention.
The preferred hydrazine compound used in the invention is represented by the following Formula [IIA].
In this formula, R₂₁ represents a monovalent organic residue; R₂₂ represents a hydrogen atom, or a monovalent organic residue; Q₂₁ and Q₂₂ independently represent a hydrogen atom, an alkyl sulfonyl group (possibly substituted), an arylsulfonyl group (possibly substituted); while X₂₁ represents an oxygen atom or a sulfur atom. The particularly preferable one of the compounds represented by Formula [IIA] is the compound where X₂₁ is an oxygen atom and R₂₂ is a hydrogen atom.
The examples of a monovalent organic residue represented by R₂₁ or R₂₂ include an aromatic residue, a heterocyclic residue, and an aliphatic residue.
The examples of such an aromatic residue include a phenyl group, and a naphthyl group and a group where any of these groups is substituted with such group as an alkyl group, an alkoxy group, an acylhydrazino group, a dialkylamino group, an alkoxycarbonyl group, a cyano group, a carboxyl group, a nitro group, an alkylthio group, a hydroxy group, a sulfonyl group, a carbamoyl group, a halogen atom, an acylamino group, a sulfonamide group, and a thiourea group. The typical examples of the groups having a substituent group include a 4-methylphenyl group, 4-ethylphenyl group, 4-oxyethylphenyl group, 4-dodecylphenyl group, 4-carboxyphenyl group, 4-diethylaminophenyl group, 4-octylaminophenyl group, 4-benzylaminophenyl group, 4-acetamide-2-methylphenyl group, 4-(3-ethylthioureide)phenyl group, 4-[2-(2,4-di-tert-butylphenoxy)butylamido]phenyl group, and 4-[2-(2,4-di-tert-butylphenoxy)butylamido]phenyl group.
The examples of the above-mentioned heterocyclic residue are five or six membered monocylic or condensed-ring groups having at least one of oxygen, nitrogen, sulfur and selenium atoms, wherein they may have a substituent. The typical examples include such residual groups as a pyroline ring, a pyridine ring, a quinoline ring, an indole ring, an oxazole ring, a benzoxazole ring, a naphthoaxazole ring, an imidazole ring, a benzimidazole ring, a thiazoline ring, a thiazole ring, a benzothiazole ring, a naphthothiazole ring, a selenazole ring, a benzoselenazole ring, and a naphthoselenazole ring.
These heterocylces may be substituted with an alkyl group having 1 to 4 carbon atoms such as methyl and ethyl groups; an alkoxy group having 1 to 4 carbon atoms such as methoxy and ethoxy groups; an aryl group having 6 to 18 carbon atoms such as phenyl group; a halogen atom such as chlorine and bromine atoms; an alkoxy carbonyl group, and a cyano group, and an amide group.
The examples of the above-mentioned aliphatic residue include a linear or branched alkyl group, a cycloalkyl group, and a group where any of these groups has a substituent. The examples also include alkenyl groups, and alkynyl groups.
The examples of the linear or branched alkyl group are an alkyl group having 1 to 18, preferably 1 to 8 carbons such as methyl group, ethyl group, isobutyl group, and 1-octyl group.
The examples of the cycloalkyl group include those having 3 to 10 carbons such as a cyclopropyl group, a cyclohexyl group, and an adamantyl group. The examples of a substituent incorporated with an alkyl or cycloalkyl group include an alkoxy group such as methoxy group, ethoxy group, propoxy group and butoxy group, an alkoxycarbonyl group, a carbamoyl group, a hydroxy group, an alkylthio group, an amide group, an acyloxy group, a cyano group, a sulfonyl group, a halogen atom such as chlorine, bromine, fluorine, and iodine atoms, and an aryl group such as a phenyl group, a halogen-substituted phenyl group and an alkyl-substituted phenyl groups. The typical examples of the substituted alkyl or cycloalkyl group include 3-methoxypropyl group, ethoxycarbonyl methyl group, 4-chlorocyclohexyl group, benzyl group, p-methylbenzyl group, and p-chlorobenzyl group. The examples of an alkenyl group include an allyl group; the examples of an alkynyl group include a propargyl group.
The typical examples of the hydrazine compound used in the invention are as follows. However, the scope of the invention is not limited by these examples.

(IIA-1) 1-formyl-2-{4-[2-(2,4-di-tert-butylphenoxy) butylamido]phenyl}hydrazine
(IIA-2) 1-formyl-2-(4-diethylaminophenyl)hydrazine
(IIA-3) 1-formyl-2-(p-tolyl)hydrazine
(IIA-4) 1-formyl-2-(4-ethylphenyl)hydrazine
(IIA-5) 1-formyl-2-(4-acetamido-2-methylphenyl)hydrazine
(IIA-6) 1-formyl-2-(4-oxyethylphenyl)hydrazine
(IIA-7) 1-formyl-2-(4-N,N-dihydroxyethylaminophenyl) hydrazine
(IIA-8) 1-formyl-2-[4-(3-ethylthioureido)phenyl]hydrazine
(IIA-9) 1-thioformyl-2-{4-[2-(2,4-di-tert-butylphenoxy)butylamido]phenyl}hydrazine
(IIA-10) 1-formyl-2-(4-benzylaminophenyl)hydrazine
(IIA-11) 1-formyl-2-(4-octylaminophenyl)hydrazine
(IIA-12) 1-formyl-2-(4-dodecylphenyl)hydrazine
(IIA-13) 1-acetyl-2-{4-[2-(2,4-di-tert-butylphenoxy)butylamido]phenyl}hydrazine
(IIA-14) 4-carboxyphenylhydrazine
(IIA-15) 1-acetyl-1-(4-methylphenylsulfonyl)-2-phenylhydrazine
(IIA-16) 1-ethoxycarbonyl-1-(4-methylphenylsulfonyl)-2-phenylhydrazine
(IIA-17) 1-formyl-2-(4-hydroxyphenyl)-2-(4-methylphenylsulfonyl)-hydrazine
(IIA-18) 1-(4-acetoxyphenyl)-2-formyl-1-(4-methylphenylsulfonyl)-hydrazine
(IIA-19) 1-formyl-2-(4-hexanoxyphenyl)-2-(4-methylphenylsulfonyl)-hydrazine
(IIA-20) 1-formyl-2-[4-(tetrahydro-2H-pyrane-2-yloxy)-phenyl]-2-(4-methylphenylsulfonyl)hydrazine
(IIA-21) 1-formyl-2-[4-(3-hexylureidephenyl)]-2-(4-methylphenylsulfonyl)hydrazine
(IIA-22) 1-formyl-2-(4-methylphenylsulfonyl)-2-[4-(phenoxythiocarbonylamino)-phenyl]hydrazine
(IIA-23) 1-(4-ethoxythiocarbonylaminophenyl)-2-formyl-1-(4-methylphenylsulfonyl)hydrazine
(IIA-24) 1-formyl-2-(4-methylphenylsulfonyl)-2-[4-(3-methyl-3-phenyl-2-thioureide)-phenyl]hydrazine
(IIA-25) 1-{{4-{3-[4-(2,4-bis-t-amylphenoxy)-butyl]ureide}phenyl}}-2-formyl-1-(4-methylphenylsulfonyl) hydrazine

The hydrazine compound is added to a silver halide emulsion layer and/or a non-light-sensitive layer provided on the same side as the silver halide emulsion layer. It is added preferably to a silver halide emulsion layer and/or a layer below this layer. The preferred addition amount is 10⁻⁵ to 10⁻¹ mol per mol of silver, more preferably, 10⁻⁴ to 10⁻² mol per mol of silver.
In the present invention, a development is preferably performed in the presence of a compound represented by the following Formula [I] and/or Formula [II].
In these formulas, R₁, R₂, R₃, R₄, and R₅ independently 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, and each group may incorporate a substituent group.
The typical examples of the compound represented by Formulas [I] and [II] are as follows. However, the scope of the invention is not limited by these examples.

Example compounds of Formula [I]:

I-1 5-nitroindazole;
I-2 5-aminoindazole;
I-3 5-p-toluenesulfonamido-indazole;
I-4 5-chloroindazole;
I-5 5-benzoylacetamino-indazole;
I-6 5-cyanoindazole;
I-7 5-p-nitrobenzoylamino-indazole;
I-8 1-methyl-5-nitro-indazole;
I-9 6-nitroindazole;
I-10 3-methyl-5-nitro-indazole; and
I-11 4-chloro-5-nitro-indazole.

Those preferable for adding to a developer, among the compounds represented by Formula [I], are nitroindazoles. 5-nitroindazoles are more preferable, and these compounds have the following structural formula.
Next, the typical examples of the compound represented by Formula [II] are as follows. However, the scope of the invention is not limited only to these examples.

Example compounds of Formula [II]

The addition amount of the compound represented by Formula [I] or [II, is preferably 1 x 10⁻⁵ to 1 x 10⁻² mol/ℓ of a developing solution, and more preferably, 5 x 10⁻⁵ to 5 x 10⁻³ mol/ℓ of a developing solution.
The present invention is applied to the ultra-rapid processing, where a photographic material is processed by an automatic developing equipment in 20 to 60 seconds.

EXAMPLES

The detailed examples of the invention are as fo]lows. It should be noted that these examples by no means limit the applicability of the invention.

Example 1

Silver halide photographic light-sensitive materials were prepared in a manner specified below.

Preparation of silver halide emulsions

Silver bromochloride emulsions of which silver bromide content was 2 mol% and 50 mol% were prepared in a manner specified below.
In preparing each emulsion, an aqueous solution containing 23.9 mg of potassium pentabromorhodium per 60 g silver nitrate, sodium chloride and potassium bromide, and an aqueous silver nitrate solution were added simultaneously to an aqueous gelatin solution with stirring at 40°C in 25 minutes to form a silver bromochloride emulsion with an average grain size of approx. 0.20 µm.
To this emulsion was added 200 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene as a stabilizer, and then the emulsion was washed for desalting.
To the above emulsion was added further 20 mg of preceding tetrazaindene, and then, the emulsion was subjected to sulfur-sensitization. Thereafter, was added again, preceding tetrazaindene as a stabilizer, and than water was added to make total quantity 260 mℓ.

Preparation of Latex (L) for addition to emulsion

To 40ℓ of water were added 0.25 kg of KMDS (sodium salt of dextran sulfate ester) manufactured by Meito Sangyo, and 0.05 kg of ammonium persulfate, and then was added with stirring in 1 hour a mixture solution comprising 4.51 kg of n-butyl acrylate, 5.49 kg of styrene and 0.1 kg of acrylic acid at a solution temperature of 81°C in a nitrogen atmosphere. Further, 0.005 kg of ammonium persulfate was added, and the solution was stirred for 1.5 hours. After cooling, pH was adjusted to 6 by aqueous ammonium solution. The resultant latex solution was filtered by GF/D filter manufactured by Whotman, and water was added to make total quantity 50.5 kg. This was a monodispersed latex having an average grain size of approx. 0.25µ.
To each of the preceding emulsions were added the following additives to prepare silver halide coating emulsion.

Preparation of Silver Halide Coating Emulsion EM-C

To each of the preceding silver halide emulsions was added gelatin solution to prepare emulsions having various amounts of gelatin, and then 9 mg of phenol as a germicide was added. Then, using 0.5 N aqueous sodium hydroxide solution, pH was adjusted to 6.5, and 360 mg of Compound (IA-2) specified below was added. Next, to the mixture were added in sequence, each as per mol of silver halide, 5 mℓ of 20% aqueous saponin solution, 180 mg of sodium dodecylbenzenesulfonate, 80 mg of 5-methylbenztriazole, 43 mℓ of Latex (L), Compound (M), and 280 mg of water soluble styrene-maleic acid copolymer serving as a thickener, and then water was added to make total quantity 475 mℓ.

Preparation of Coating Solution P-1 for protecting an emulsion layer

10ℓ of pure water was added to 1 kg of gelatin, and after swollen, it was dissolved at 40°C. Then, to the gelatin solution were sequentially added 2.9ℓ of 1% aqueous solution of Compound (Z) as a coating coagent, 80 g of Compound (N) as a filter dye, 20 g of amorphous silica as a matting agent, and 62 g of Compound (B) below. Next, pH was adjusted to 5.4 by a citric acid solution, and then water was added to make total quantity 17ℓ.

Preparation of Back Coating Solution B-1

36 kg of gelatin was swollen in water and dissolved by heating, and then, to the gelatin solution were added, each as a dye in an aqueous solution, 1.6 kg of Compound (C-1), 310 g of compound (C-2), 1.9 kg of Compound (C-3), and 2.9 kg of Compound (N). Next, to the above solution were added 11ℓ of 20% aqueous saponin solution, and 5 kg of Compound (C-4) as a physical property modifier, and 63 g of Compound (C-5) in a methanol solution. To the resultant solution was added, as a thickener, 800 g of water soluble styrene-maleic acid copolymer to adjust viscosity, and then pH was adjusted to 5.4 by an aqueous citric acid solution. Finally, 144 g of glyoxal was added, and then water was added to make total quantity 960ℓ.

Preparation of Coating Solution P-2 for protecting a back coating layer

50 kg of gelatin was swollen in water and dissolved by heating, and then 340 g of 2-sulfonate succinate bis(2-ethylhexyl) ester sodium salt was added. Further, to the gelatin solution were added 1.7 kg of polymethyl methacrylate (average grain size, approx. 0.4µ) as a matting agent, 3.4 kg of sodium chloride, 1.1 kg of glyoxal, and 540 g of mucochloric acid. Water was further added to make total quantity 1000ℓ.

Preparation of samples for evaluation

The preceding emulsions and coating solutions were used in combination as listed in Table 1 and were coated on both sides of polyethylene terephthalate film (thickness, 100µ) having thereon a subbing lay as specified in Example 1 of Japanese Patent Publication Open to Public Inspection (hereinafter referred to as Japanese Patent O.P.I. Publication) No. 09941/1984. The samples for evaluation listed in Table 1 were prepared by the following procedure. First, a back coating solution B-1 was coated on a subbing layer, to form a back coating layer containing gelatin of 2 g/m², and, then a coating solution P-2 was coated thereon to form a protective layer containing gelatin of 1 g/m². Next, a silver halide coating emulsion EM-C was coated on the other side of the support to form a light-sensitive emulsion layer having a gelatin amount as specified in Table 1 and a silver amount of 4.3 g/m², and then a coating solution P-1 containing formalin as a hardner, of an amount as specified in Table 1 was coated thereon to form a protective layer containing gelatin of 1 g/m². Thus, the samples for evaluation A-1 through A-37 were prepared.

Photographic performance evaluation

Each of the preceding samples was subjected to wedge exposure using a daylight printer equipped with an electrodeless discharge tube as a light source manufactured by FUSION in U.S.A. The exposed and unexposed samples were processed with the automatic developing equipment illustrated in FIG. 1, wherein the samples were processed by a developing solution which had the following composition and contained Compound I-1 (5-nitroindazole) as represented by Formula [I] and/or Compound II-11 (5-methyl benzotriazole) as represented by Formula [II] in the amounts specified in Table 1, and were processed by a fixing solution of the following composition. In the course of processing, a film travelling speed was varied to control total processing time. The processing conditions are specified below.

Developing	30°C	30 sec.	15 sec.
Fixing	30°C	30 sec.	15 sec.
Washing	normal temp.	20 sec.	10 sec.
Drying	45°C	20 sec.	10 sec.
Travelling speed	1450 mm/min.	2900 mm/min.
Total processing time	100 sec.	50 sec.

The term "total processing time" means a duration necessary for a photographic film to travel from an inlet of an automatic developing equipment to an exit of a drying unit of the developing equipment.

Developing solution compositions

Composition A
Pure water (deionized 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
1-phenyl-5-mercaptotetrazole	30 mg
Potassium hydroxide	amount for adjusting pH of solution to 10.4
Potassium bromide	4.5 g

Composition B
Pure water (deionized water)	3 mℓ
Diethylene glycol	50 g
Disodium ethylenediaminetetraacetate	25 mg
Acetic acid (90% aqueous solution)	0.3 mℓ
1-phenyl-3-pyrazolidone	500 mg

These compositions were dissolved, in the order of Composition A and then Composition B, in 500 mℓ water, and water was further added to make total quantity 1ℓ.

Fixing solution compositions

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/v aqueous solution)	8.1 mℓ

Composition B
Pure water (deionized water)	17 mℓ
Sulfuric acid (50%w/v aqueous solution)	5.8 g

Aluminum sulfate (8.1%w/w aqueous solution as converted to Aℓ₂O₃	26.5 g

These compositions were dissolved, in the order of Composition A and then Composition B, in 500 mℓ water, and water was further added to make total quantity 1ℓ. pH of this fixing solution was approx. 4.3.
A sensitivity is expressed in term of a reciprocal of exposure providing density of 3.0, where the sensitivity of Sample A-1 is set at 100. γ was measured for density ranging from 0.3 to 3.0.
Residual silver was measured as follows: to a processed samples was applied dropwise Kodak ST-1 solution, and 5 minutes later the solution was absorbed by a filter paper, and then an amount of yielded Ag₂S was measured by a transmission type densitometer, Model PDA65 manufactured by Konica Corporation, equipped with a blue filter.

Kodak ST-1 solution

An original solution was diluted ten times with pure water before use.
Dryness of a sample was evaluated based on a five level evaluation system, where dryness of an emulsion layer face and a back coating layer face of each sample coming out of a drying process was observed.
Degree of scratches occurred was also evaluated based on a five level evaluation system.

5-4 well enought for practical use

3 minimum level for practical use

2-1 practical use virtually impossible
An amount of residual silver not more than 1.5 mg/m² can meet well a usual preservation (1.5 years).
As can be found from the results summarized in Table 1, the photographic light-sensitive materials of the invention exhibits good performance in terms of developability, fixability and dryness even in the course of the ultra-rapid processing of which total processing time is as short as 50 seconds.

Example 2

Preparation of samples:

With pH being settled at 3.0 by nitric acid and silver potential (EAg) being maintained at 170 mv by adding 1 N sodium chloride, Solution B and C were added to Solution A at an addition speed specified in an adding patern below by a controlled double jet method, wherein the addition speed of Solution C was the same as that of Solution B for two minutes after the addition started, and then it was maintained at 0.99 times the speed of Solution B.

Solution A
Gelatin	5.6 g

10% ethanol solution of sodium salt of polyisopropylene-polyethyleneoxydisuccinate ester	0.56 mℓ
Sodium chloride	0.12 g
Nitric acid conc.	0.43 mℓ
Distilled water	445 mℓ

Solution B
Silver nitrate	60 g
Nitric acid conc.	0.208 mℓ
Distilled water	85.2 mℓ

Solution C
Gelatin	3 g

10% ethanol solution of sodium salt of polyisopropylene-polyethyleneoxydisuccinate ester	0.3 mℓ
Potassium bromide	4.2 g
Sodium chloride	18.6 g
Na₃RhCℓ₆ 1% aqueous solution	0.02 mℓ
Distilled water	87.3 mℓ

Solution D
Gelatin	1.4 g

10% methanol solution of sodium salt of polyisopropylene-polyethyleneoxy disuccinate ester	0.14 mℓ
Distilled water	48.8 mℓ

Adding pattern

(34°C)

Time for adding Solution B (min.) Adding velocity (mℓ/min.)

0 min. 11.74

2 min. 11.74

3 min. 11.93

4 min. 12.14

5 min. 12.34

6 min. 12.55

7 min. 12.75

8 min. 12.96
The average grain size of silver halide grains of the preceding silver halide emulsion was 0.075µ. The silver chloride content in silver halide grains was 90 mol%; rhodium content was 2 x 10⁻⁶ mol per mol of silver halide; monodispersability was approx. 10%.
In measuring EAg value, a metal silver electrode as well as a double-junction type saturated Ag/AgCℓ reference electrode was used (the constitution of the electrode used is as disclosed in Japanese Patent O.P.I. Publication No. 197534/1982).
In adding Solution B and Solution C, a variable flow-rate roller-tube metering pump was used.
During addition, the emulsion mixture was sampled in order to confirm by observation with an electron microscope that there was no further generation of new grains and that adding speed did not exceed a critical grain growth rate in this emulsion forming system.
To each of the prepared emulsions was added 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene of 200 mg per mol of silver halide, and pH was adjusted to 5.7 with sodium carbonate, and then Solution D was added. Thereafter, each silver halide emulsion was washed for desalting by a conventional method, and then 58 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene and 150 mg of potassium bromide per mol of silver halide were added. After each silver halide emulsion was subjected to sulfur sensitization, 570 mg of 6-methyl-4-hydroxy-1,3,3a,7-tetrazaindene as a stabilizer was added per mol of silver halide, and gelatin was added in an amount as specified in Table 2. Furthermore, the additives were added in a way similar to Example 1 to prepare a coating solution for an emulsion layer. Next, a coating solution for protecting an emulsion layer was prepared, and then both solutions were coated on a support of 100 µm thickness polyethylene terephthalate film by a simultaneous coating method to prepare the emulsion and protective layers having the following compositions, respectively, wherein prior to the foregoing coating, the support was provided with a subbing layer in the same way as Example 1 and then, with a back coating (BC) layer and a protective layer for the BC layer, having the following compositions, respectively. Thus, Sample No. B-1 through B-9 in Table 2 were prepared. Additionally, water content of each sample just after coming from a drying unit was controlled by varying the gelatin amounts in an emulsion layer and a protective layer and/or amount of formaldehyde added thereto. A silver amount in each sample was 3.5 g/m².

Composition of an emulsion layer

Composition of a protective layer for an emulsion layer

Composition of a back coating layer

Composition of a protective layer for a BC layer

Dioctyl sulfosuccinate ester	300 mg/m²
Matting agent: polymethyl methacrylate (average grain size, 4.0 µm)	100 mg/m²
Ossein gelatin (isoelectric point, 4.9)	1.0 g/m²
Fluorinated sodium dodecylbenzenesulfonate	50 mg/m²

Sensitivity evaluation:

Each of the samples was exposed through an optical wedge using a daylight printer equipped with an electrodeless discharge tube as light source manufactured by FUSION U.S.A and with a filter (Kodak, Wratten filter-No. 2B) which eliminates a shorter wave length than approx. 400 nm. The exposed samples were processed with the automatic developing equipment used in Example 1, using the developer where 110 mg/ℓ of Compound [I-1] was added to the developer used in Example 1, and the same fixer as in Example 1. A processing temperature in both developing and fixing was 30°C, while drying was performed at 45°C. The developing time was varied as specified in Table 2. A sensitivity was indicated in terms of a reciprocal of an exposure which provided density of 3.0, wherein the sensitivity of Sample B-1 was referred as 100. The other evaluation ways were identical with those in Example 1.

The evaluation results are summerized in Table 2.

Table 2

Experiment No.	AgX composition AgCℓ/Br	Gelatin mg/m² EC/Pro	Total	Hardener mg/m²	Water content g/m²	Dev. (sec)	Fix (sec)	Dry (sec)	Total processing time (sec)	Sensitivity	γ	Residual silver mg/m²	Dryness	Scratch	Invention or not
B-1	90/10	2/1	3	75	11	30	30	20	100	100	10.9	0.8	5	5	o
B-2	90/10	2/1	3	35	20	15	15	10	50	86	10.8	0.7	3	5	x
B-3	90/10	2/1	3	50	16	15	15	10	50	83	10.6	0.7	4	5	o
B-4	90/10	2/1	3	70	11	15	15	10	50	82	10.9	1.1	4	4	o
B-5	90/10	2/1	3	100	8	15	15	10	50	79	10.4	1.2	5	5	o
B-6	90/10	2/1	3	160	5	15	15	10	50	77	11.1	1.5	5	5	o
B-7	90/10	2/1	3	250	2	15	15	10	50	52	3.1	2.2	5	5	x
B-8	90/10	3/1	4	70	15	15	15	10	50	82	10.8	1.3	4	5	o
B-9	90/10	1/1.5	1.5	35	4	15	15	10	50	58	4.2	0.4	5	3	x
EC : emulsion layer
Pro: protective layer
o : invention
x : comparison

As can be found from the results summarized in Table 2, the samples of the invention exhibited good performance in terms of developability, fixability and dryness even in case of a ultra-rapid processing where total processing time was as short as 50 seconds, as well as in case where a total processing time was 100 seconds (Experiment B-1).

[Effects of the invention]

As described above, according to the invention, the preceding problems in the prior art have been solved even an ultra-rapid process where total processing time is 20 to 60 seconds. The present invention can provide a silver halide photographic light-sensitive material which is improved in sensitivity, fogging and graininess of an image, and in scratch-induced fogging and pressure desensitization even in a smaller amount of gelatin, and the invention also can provide a processing method to meet the preceding object.

Claims

1. A method of processing a silver halide photographic light-sensitive material in a roller-transporting type processing equipment, comprising the steps of developing, fixing, washing and drying, wherein the photographic material comprising a support having thereon at least one hydrophilic layer including a silver halide emulsion layer containing at least one selected from the group consisting of silver chloride, silver bromochloride and silver bromochloroiodide each containing silver chloride of not less than 60 mol %, and water content of the photographic material just after the washing step is 5 to 16 g/m².

2. The method of claim 1, wherein the photographic material contains gelatin in the hydrophilic layer.

3. The method of claim 2, wherein the content of gelatin in the photographic material is 2.0 to 3.5 g/m².

4. The method of claim 1, the water content of the photographic material just after the washing step is 8 to 13 g/m².

5. The method of claim 1, wherein a transporting speed of the photographic material in the processing equipment is not slower than 1500 mm/ minute.

6. The method of claim 5, wherein the transporting speed is not slower than 1900 mm/minute.

7. The method of claim 1, the total processing time of the photographic material in the processing equipment, which is obtained by deviding a processing line length with a transporting speed of the photographic material, is 20 to 60 seconds.

8. The method of claim 1, wherein a total travelling path length for the photographic material in the processing steps is not shorter than 250 mm.

9. The method of claim 8, wherein the total path length is not shorter than 330 mm.

10. The method of claim 1, wherein a travelling path ratio defined by the following formula is not lower than 0.75;
Travelling path ratio = staying time of a photographic material in a processing step ÷ (said staying time + travelling time from step to step)

11. The method of claim 1, wherein silver chloride contained in silver bromochloride or silver bromochloroiodide is not less than 70 mol %.

12. The method of claim 1, wherein the photographic materi al is developed in the presence of at least one of the compounds represented by the following Formulas [I] and [II];

wherein, R₁, R₂, R₃, R₄ and R₅ independently represent a hydrogen atom, a lower alkyl group, an alkoxy group, a carboyl group, an alkoxycarbonyl group, a sulfoxy group, a halogen atom, an amino group or a nitro group.

13. The method of claim 12, wherein the compound represented by Formula [I] is nitroindazoles.

14. The method of claim 13, wherein the compound is 5-nitroindazole.

15. The method of claim 12, wherein an addition amount of the compound represented by Formula [I] or [II] is 1 x 10⁻⁵ to 1 x 10⁻² mol/liter of a developing solution.

16. The method of claim 15, wherein the addition amount is 5 x 10⁻⁵ to 5 x 10⁻³ mol/liter of a developing solution.

17. The method of claim 1, wherein said photographic material contains a tetrazolium compound represented by Fromula [IA]

wherein R₁, R₂, and R₃ independetly represent a hydrogen atom or a substituent, and X^⊖ represents an anion.

18. The method of claim 17, wherein said R₁, R₂ and R₃ are selected independently from the group consisting of an alkyl group, an amino group, a hydroxyl group, an alkoxy group, an acyloxy group, a halogen atom, a carbamoyl group, an acylthio group, an alkoxycarbonyl group, a carboxyl group, an acyl group, a cyano group, a nitro group, and an aminosulfoxy group.

19. The method of claim 17, wherein X^⊖ is selected from the group consisting of a halogen ion, an inorganic acid radical, an organic acid radical, a lower alkylbenzene sulfonic acid anion, a higher alkylbezene sulfonic acid anion, a higher alkylsulfuric ester anion, a boric acid derivative anion, a di-alkylsulfosuccinate anion, a polyether alcohol sulfuric ester anion, a higher fatty acid anion, and an acid radical attached to polymer.

20. The method of claim 17, wherein the content of the tetrazolium compound in the photographic material is 1 mg to 10 g per mol of silver halide.

21. The method of claim 20, wherein the content is 10 mg to 2 g per mol of silver halide.

22. The method of claim 1, wherein the photographic material contains a hydrazine compound represented by Formula [IIA];

wherein R₂₁ represents a monovalent organic residue, and R₂₂ represents a hydrogen atom or a monovalent organic residue; Q₂₁ and Q₂₂ independently represent a hydrogen atom, an alkylsulfonyl group or an arylsulfonyl group; X₂₁ represents an oxygen atom or a sulfur atom.

23. The method of claim 22, wherein X₂₁ is an oxygen atom and R₂₂ is a hydrogen atom.

24. The method of claim 22, wherein said monovalent organic residue represented by R₂₁ or R₂₂ includes an aromatic residue, an aliphatic residue or a heterocyclic residue.

25. The method of claim 22, wherein the content of said hydrazine compound contained in the photographic material is 10⁻⁵ to 10⁻¹ mol per mol of silver.

26. The method of claim 25, wherein the content is 10⁻⁴ to 10⁻² mol per mol of silver.

27. A silver halide photographic light sensitive material processed by a roller-transporting type processing equipment consisting of a developing unit, a fixing unit, a washing unit and a drying unit, wherein the photographic material comprising a support having thereon at least one hydrophilic layer including a silver halide emulsion layer containing at least one selected from the group consisting of silver chloride, silver bromochloride and silver bromochloroiodide each containing silver chloride of not less than 60 mol %, and water content of the photographic material just after coming out of the washing unit is 5 to 16 g/m².

28. The photographic material of claim 27, wherein the photographic material contains gelatin in the hydrophilic layer.

29. The photographic material of claim 28, wherein the content of gelatin in the photographic material is 2.0 to 3.5 g/m².

30. The photographic material of claim 27, wherein said water content of the photographic material is 8 to 13 g/m².

31. The photographic material of claim 27, wherein silver chloride contained in silver bromochloride or silver bromochloroiodide is not less than 70 mol %.

32. The the photographic material of claim 27, wherein the photographic material is developed in the presence of at least one of the compounds represented by the following Formulas [I] and [II];

33. The photographic material of claim 32, wherein the compound represented by Formula [I] is nitroindazoles.

34. The photographic material of claim 33, wherein the compound is 5-nitro-indazole.

35. The photographic material of claim 32, wherein an addition amount of the compound represented by Formula [I] or [II] is 1 x 10⁻⁵ to 1 x 10⁻² mol/liter of a developing solution.

36. The photographic material of claim 35, wherein the addition amount is 5 x 10⁻⁵ to 5 x 10⁻³ a mol/liter of a developing solution.

37. The photographic material of claim 27, wherein said photographic material contains a tetrazolium compound represented by Fromula [IA]

wherein R₁, R₂ and R₃ independetly represent a hydrogen atom or a substituent, and X represents an anion.

38. The photographic material of claim 37, wherein said R₁, R₂ and R₃ are selected independently from the group consisting of an alkyl group, an amino group, a hydroxyl group, an alkoxy group, an acyloxy group, a halogen atom, a carbamoyl group, an acylthio group, an alkoxycarbonyl group, a carboxyl group, an acyl group, a cyano group, a nitro group, and an aminosulfoxy group.

39. The photographic material of claim 37, wherein X^⊖ is selected from the group consisting of a halogen ion, an inorganic acid radical, an organic acid radical, a lower alkylbenzene sulfonic acid anion, a higher alkylbezene sulfonic acid anion, a higher alkylsulfuric ester anion, a boric acid derivative anion, a di alkylsulfosuccinate anion, a polyether alcohol sulfuric ester anion, a higher fatty acid anion, and an acid radical attached to polymer.

40. The photographic material of claim 37, wherein the content of the tetrazolium compound in the photographic material is 1 mg to 10 g per mol of silver halide.

41. The photographic material of claim 40, wherein the content is 10 mg to 2 g per mol of silver halide.

42. The photographic material of claim 27, wherein the photographic material contains a hydrazine compound represented by Formula [IIA];

43. The photographic material of claim 42, wherein X₂₁ is an oxygen atom and R₂₂ is a hydrogen atom.

44. The photographic material of claim 42, wherein said monovalent organic residue represented by R₂₁ or R₂₂ includes an aromatic residue, an aliphatic residue or a heterocyclic residue.

45. The photographic material of claim 42, wherein the content of said hydrazine compound contained in the photographic material is 10⁻⁵ to 10⁻¹ mol per mol of silver.

46. The photgraphic material of claim 45, wherein the content is 10⁻⁴ to 10⁻² mol per mol of silver.