JPH06258780A - Processing method for silver halide photographing sensitive material - Google Patents

Abstract

PURPOSE:To provide the processing method for a silver halide photographic sensitive material with which a highly sensitive picture having no development processing unevenness is obtainable causing no silver sludge when the material is processed using a automatic developing machine. CONSTITUTION:In the method processing the silver halide photographic sensitive material containing the hydrophilic colloidal layer containing a supporting body and at least one layer of photosensitive silver halide emulsion using the automatic developing machine, the polymer latex whose at least one part is polymerized in a solvent containing gelatin in the polymerization reaction of the polymer, is contained in the emulsion layer and/or protective layer, and the developer containing at least one silver sludge preventing agent is replenished as the developer used at the developing stage of the automatic developing machine.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for processing a silver halide photographic light-sensitive material, and more specifically, an image having high sensitivity and no unevenness in processing when silver sludge is not generated during processing using an automatic processor. The present invention relates to a method for processing a silver halide photographic light sensitive material.

[0002]

2. Description of the Related Art Sulfites such as sodium sulfite and potassium sulfite which are used as antioxidants for photographic developers have a dissolving effect on silver halides.
Therefore, when the light-sensitive material is processed, a large amount of silver complex salt with sulfite is generated and eluted in the developing solution. The eluted silver complex salt is easily reduced by the main agent and accumulates precipitated silver called so-called silver sludge. This silver sludge floats in the developing solution and adheres to the film or adheres to the roller or belt of the automatic developing machine in the continuous processing by the automatic developing machine. Therefore, a serious trouble such as generation of yellowish brown streak-like stains and scratches may occur on the conveyed film.

Particularly in recent years, the amount of replenishment of the photographic processing solution has been reduced from the viewpoint of environmental protection, so that the processing solution retention time in the developing machine bath has become longer. Therefore, the amount of accumulated silver sludge is also increasing compared to the past.

There have been many reports as techniques intended to prevent silver sludge, for example, JP-A-58-114035 using thiouracils, British Patent No. 1144481 using mercaptobenzoic acids, and aliphatic mercaptocarboxylic acids. JP-B-47-14953 using acids, JP-A-3-51844 using disulfides, JP-A-48-26136 using sulfur-containing α-amino acids, and various mercaptoazoles It has been disclosed, and all of them disclose compounds that easily form a water-soluble silver salt.

However, most of these prior arts have the following drawbacks, and few of them are practically satisfactory.

That is, (1) the sludge-preventing effect is reduced by air oxidation in the developing solution (2) a large amount is required to obtain the sludge-preventing effect (3) The use of a large amount deteriorates the sensitivity and gamma of the film (4) An unpleasant odor is generated. In addition, there are high costs for processing liquids, and there has been a strong demand for the development of new technologies that clear these problems.

In Japanese Patent Application No. 4-92947, by using a developing solution containing acetylpenicillamines, even if the developer replenishing amount is reduced, the sensitivity and the maximum density are not lowered, and the silver sludge preventing effect is obtained. Although the technology possessed is shown, on the other hand, there is a drawback that development unevenness occurs, which is not always satisfactory.

[0008]

SUMMARY OF THE INVENTION In contrast to the problems described above, an object of the present invention is to provide an image which is free from silver sludge when processed by an automatic processor, has high sensitivity, and is free from uneven development processing. The present invention provides a method for processing a silver halide photographic light-sensitive material which can obtain

[0009]

The above object of the present invention is to provide a silver halide photographic light-sensitive material containing a support and a hydrophilic colloid layer containing at least one light-sensitive silver halide emulsion using an automatic processor. In the method for processing, the emulsion layer and / or the protective layer contains a polymer latex in which at least a part of the polymerization reaction of the polymer is carried out in a solvent containing gelatin, and the development step of an automatic processor is performed. It is achieved by a method of processing a silver halide photographic light-sensitive material, characterized in that a developer containing at least one silver sludge inhibitor is replenished and used as a developer to be used.

The present invention will be specifically described below.

Silver halide grains are generally prepared and used in the form of silver halide emulsions containing the grains. The silver halide grains used in the present invention may have any shape, and may be, for example, spherical or tabular.
Preferably, 50% or more of the total projected area is a monodisperse twin particle having a thickness of less than 0.3 μm and a ratio of particle diameter / particle thickness of 2: 1 or more, and more preferably 50% or more of the total projected area. Has a thickness of less than 0.2 μm and a particle diameter / particle thickness ratio of 5: 1 to
8: 1 monodispersed twin grains.

In the present invention, the particle size is a diameter when a projected image of particles is converted into a circular image having the same area. Grain thickness refers to the distance between two principal planes of tabular grains facing each other. The projected area of a grain can be calculated from the sum of the grain areas. The total projected area and the projected area for obtaining the grain diameter are both 10,000 times to 50,000 times with an electron microscope for a silver halide crystal sample distributed on the sample stage to the extent that grains do not overlap. It can be obtained by enlarging and photographing and measuring the particle diameter on the print or the area at the time of projection. (The number of measurement is indiscriminately 10
It is assumed that there are 00 or more. ) The thickness of the particles can be obtained by observing the sample obliquely with an electron microscope.

A particularly preferred highly monodisperse emulsion of the present invention has a distribution breadth defined by (grain size standard deviation) / (mean grain diameter) × 100 = (breadth of distribution) (%) of 30% or less. Is something
It is more preferably 20% or less. Here, the particle size measuring method is based on the above-described measuring method, and the average particle size is a simple average.

(Average particle size) = Σdini / Σni As a method for obtaining a monodisperse emulsion, pAg of a water-soluble silver salt solution and a water-soluble halide solution in a gelatin solution containing seed particles is used.
And the double jet method under the control of pH, and such means can be used. In determining the addition rate, reference can be made to JP-A-54-48521 and JP-A-58-49938.

In the present invention, the twin means a silver halide crystal having one or more twin planes in one grain. The twin morphology is classified by Klein and Moiser in the report "Photographie Correspondents" (Photographi
sche Korrespondenz) 99, 99, 100, 57. Two or more twin planes of a twin may or may not be parallel to each other. The twin plane can be observed directly with an electron microscope, but it can also be observed from the cross section as an ultrathin section sample obtained by dispersing and solidifying silver halide in a resin.

The above-mentioned silver halide twin crystal grains constituting the silver halide emulsion according to the present invention are preferably those mainly having two or more parallel twin crystal planes, more preferably an even number, particularly preferably. Has two twin planes.

The term "mainly composed of twins having two or more parallel twin planes" means that the number of twin grains having two or more parallel twin planes is the number when counted from the large-sized grains. 50% or more, preferably 60% or more, particularly preferably 70%
This is the case.

The monodispersed twin crystal in the present invention is one having a particle size distribution of the twin crystal particles of 30% or less, more preferably 20% or less.

Regarding the halogen distribution in the silver halide grains in the silver halide emulsion of the present invention, it may be a uniform composition or a halogen composition having different internal and external halogen compositions.
It may have a layered structure (core / shell structure).

The silver halide emulsion used in the present invention is formed by using a previously formed silver halide emulsion as a seed emulsion and further growing grains. The silver halide photographic emulsion which can be used in the present invention may be prepared by any method such as an acid method, a neutral method and an ammonia method, but a double jet method ( Simultaneous mixing method) is used. As one form of the simultaneous mixing method, a method of keeping pAg constant in a liquid phase in which silver halide is produced, that is,
A so-called controlled double jet method can also be used. According to this method, a silver halide emulsion having a regular crystal form and a substantially uniform grain size can be obtained.

The silver halide emulsion used in the practice of the present invention can be brought to a pAg ion concentration suitable for chemical sensitization by a suitable method after the growth of silver halide grains is completed. Research Disclosure 17643 (Research Disclos
ure 17643)).

In the case of chemical sensitization, ordinary sulfur sensitization,
Reduction sensitization, precious metal sensitization and combinations thereof are used. More specific chemical sensitizers include sulfur sensitizers such as allyl tio-carbamide, thiourea, thiosulfate, thioether and cystine; potassium chloroaurate, aura thiosulfate and potassium chloroparadate. (Potassium chlor
noble metal sensitizers such as o palladate); reduction sensitizers such as tin chloride, phenylhydrazine and retactone.

The photographic emulsions used in the practice of this invention may be spectrally sensitized with cyanine dyes and the like. The sensitizing dyes may be used alone, or a combination thereof may be used, and the combination of the sensitizing dyes is often used particularly for the purpose of supersensitization.

Various hydrophilic colloids can be used as a binder in the photographic emulsion used in the present invention. Examples of colloids used for this purpose include hydrophilic colloids generally used in the photographic field, such as gelatin, colloidal albumin, polysaccharides, cellulose derivatives, synthetic resins, polyvinyl compounds including polyvinyl alcohol derivatives, acrylamide polymers, and the like. be able to.

The ordinary latex is dispersed in water by a surfactant, but the latex usable in the present invention is characterized in that it is dispersed and stabilized by gelatin bonded to a polymer latex. The polymer constituting the latex and gelatin may have some kind of bond. In this case, the polymer and gelatin may be bound directly or may be bound via a crosslinking agent. Therefore, the monomers constituting the latex include carboxyl group, amino group, amide group, epoxy group, hydroxyl group, aldehyde group, oxazoline group, ether group, ester group, methylol group, cyano group, acetyl group, unsaturated carbon bond. It is desirable to include those having a reactive group such as. When a cross-linking agent is used, it is possible to use one that has been used as a usual cross-linking agent for gelatin. For example, an aldehyde-based, glycol-based, triazine-based, epoxy-based, vinyl sulfone-based, oxazoline-based, methacrylic-based, acrylic-based, etc. crosslinking agent can be used.

The polymer latex used in the present invention is characterized in that at least a part of the polymerization reaction of the polymer is carried out in a solvent containing at least gelatin. During synthesis (finally obtained as latex)
The weight ratio of gelatin to polymer is Gel / Poly = 1
/ 100 to 2/1 is preferable, and 1/50 to 1 is particularly preferable.
/ 2.

The effects of the present invention give particularly preferable results when the amount of the polymer component added to the latex is 20% or more based on the gelatin in the layer to which the latex is added.
The amount of polymer added is 0.05 to 5 g / m ² , particularly preferably 0.1.
~ 2.5 g / m ² . Further, according to the present invention, the particle size of latex is
It is preferably 0.3 μm or less. Particularly preferred particle size is
It is 0.01 to 0.27 μm.

Examples of the constitution of the monomer of the polymer latex contained in the photographic light-sensitive material of the present invention include, for example, US Pat. Nos. 2,772,166, 3,325,286 and 3,411,911.
, 3,311,912, 3,525,620, Research Disclosure No. 195 19551 (19)
(July 1980), acrylic acid ester,
There are hydrates of vinyl polymers such as methacrylic acid esters and styrene.

As the gelatin used for binding the gelatin and the latex of the present invention, lime-processed gelatin, acid-processed gelatin, Bulletin of Society of Japan (Bull.Soc.Sci.Phot.Japan) No. 16, 30 Acid-treated gelatin as described on page (1966) may be used, or a hydrolyzate or an enzymatic hydrolyzate of gelatin may be used.
Examples of the gelatin derivative include various compounds such as acid halides, acid anhydrides, isocyanates, bromoacetic acid, alkane sultones, vinyl sulfonamides, maleinimide compounds, polyalkyleonoxides, and epoxy compounds in gelatin. What is obtained by reacting is used. Specific examples thereof are U.S. Patent Nos. 2,614,928 and 3,132,94.
5, 3,186,846, 3,312,553, British Patent 861,4
No. 14, No. 1,033,189, No. 1,005,784, Japanese Patent Publication No. 42-26845
No. etc.

Examples of proteins include albumin, casein,
As the cellulose derivative, hydroxyethyl cellulose, carboxymethyl cellulose, a sulfuric acid ester of cellulose, or as the sugar derivative, sodium alginate, and a starch derivative may be used in combination with gelatin.

The polymer latex combined with gelatin used in the present invention may be added to at least one hydrophilic colloid layer, but the photosensitive hydrophilic colloid layer and the non-photosensitive layer on the side of the photosensitive hydrophilic colloid layer. A preferable result is obtained when it is added in both layers of the hydrophilic hydrophilic colloid layer. It may be contained only on one side with respect to the support,
It may be contained on both sides. A conventionally known latex may be added to the layer to which the latex of the present invention is added and / or not added. When included on both sides of the support, the type and / or amount of polymer latex included on each side may be the same or different. Specific examples of the latex which can be used in the present invention include L-1 to L-1 described in Japanese Patent Application No. 3-117519.
The compound of L-26 can be preferably used. Of course, the specific examples of the latex shown here are typical examples of the latex that can be used, and it goes without saying that the constituent components (not only the composition ratio) of the latex used in the present invention are not limited to these specific examples. Yes.

The present invention can use generally known silver anti-sludge agents in developing solutions. For example, British Patent No. 94
No. 0169 (2-mercapto-1,3,4-thiadiazoles), U.S. Pat.No. 3,173,789 (2-mercapto-1,3,4-oxadiazoles or 1-phenyl-5-mercaptotetrazole), U.S. Pat. 3,318,701 (DL-6,8-dithiooctanoic acid), British Patent No. 1144481 (o-mercaptobenzoic acid), JP-B-47-14953 (aliphatic mercaptocarboxylic acid), J. Photogr. Sci., 13,233 ( 1965) (L-thiazoline-4-carboxylic acid), JP-A-3-51844 (disulfide compound), Photogr. Sci. Eng., 20, 220 (1976) (2-benzoxazolethiol, 2-benzimidazolethiol),
JP-A-55-95947 (acetylene glycols), JP-A-SHO
The compounds disclosed in JP-A-56-72441 (2-mercaptobenzothiazole-5-sulfonic acid), JP-A-58-114035 (thiouracils) and the like can be used.

Particularly preferably, the compound represented by the following general formula [1] or general formula [2] can be used.

[0034]

[Chemical 1]

[In the formula, R ₁ and R ₂ are hydrogen atoms and have 1 to 1 carbon atoms.
It represents up to 3 alkyl groups. However, R ₁ and R ₂ cannot be hydrogen atoms at the same time. R ₃ and R ₄ are hydrogen atoms and have 1 carbon atom
Up to 3 alkyl groups, R ₅ represents a hydroxyl group, an amino group or an alkyl group having 1 to 3 carbon atoms. R _6, R ₇ represents a hydrogen atom, an alkyl group having up to 5 carbon atoms, an acyl group or a -COOM ₂ group up to 18 carbon atoms. However, R ₆ and R ₇
Cannot be hydrogen atoms at the same time. M ₁ is a hydrogen atom,
Represents an alkali metal atom and an ammonium group. M ₂ represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkali metal atom, an aryl group, or an aralkyl group having 15 carbon atoms.
m represents 0, 1 or 2. Examples of the alkyl group having 1 to 4 carbon atoms in the compound represented by the general formula [1] or the general formula [2] include a methyl, ethyl, propyl or butyl group.

Examples of the acyl group having up to 18 carbon atoms include acetyl group and benzoyl group, and examples of the aralkyl group having up to 15 carbon atoms include benzyl group and phenethyl group. Examples of the aryl group include a phenyl group and a naphthyl group. The alkali metal atom of M ₁ is, for example, sodium ion or potassium ion.

Although various synthetic methods are known for these compounds described above, for example, the Strecker amino acid synthetic method known as an amino acid synthetic method may be used. The acetic acid is added alternately.

Next, specific examples of the compounds represented by the general formulas [1] and [2] used in the present invention are shown. Of course,
The present invention is not limited to these.

[0039]

[Chemical 2]

[0040]

[Chemical 3]

These compounds of the present invention may be used alone or in combination. Further, at least one compound of the general formula [1] and the compound of the general formula [2] may be used in combination. The amount of the compound of the general formula [1] or the compound of the general formula [2] used in the present invention is 1 × 10 ⁻⁵ mol to 3 × 10 ⁻² mol, preferably 1 × 10 ⁵ mol / liter of the developing solution.
Used at concentrations from ^-4 molar to 1 x ^10-2 molar. The replenishment amount of the developer containing these compounds is not uniform depending on the type of the light-sensitive material and the developing machine, but is usually 0.05 to 0.65 liter per liter of the light-sensitive material, and particularly preferably 0.10 to 0.35 liter.

The silver halide light-sensitive material of the present invention comprises a photographic hardener usually used in the coating solution, for example, an aldehyde type or an aziridine type (eg PB Report 19,921, US Pat. Nos. 2,950,197 and 2,964,404, Ibid. 2,983,611
No. 3,271,175, each specification, Japanese Examined Patent Publication No. 46-40898,
JP-A-51-91315), isoxazole-based (eg, those described in US Pat. No. 331,609), epoxy-based (eg, US Pat. No. 3,047,394,
West German Patent No. 1,085,663, British Patent No. 1,033,518, each specification described in Japanese Patent Publication No. 48-35495), vinyl sulfone system (for example, PB Report 19,920, West German Patent No. 1,10).
0,942, British Patent No. 1,251,091, Japanese Patent Publication No. 49-13563,
JP-A-51-91315, U.S. Pat.Nos. 353,964, and 3,490,9
No. 11), acryloyl type (for example, Japanese Patent Publication No. 53-778, US Pat. No. 3,640,720 described in each specification), carbodiimide type (for example, US Patent No.
2, 938,892 and JP-B-46-38715), and other maleimide-based, acetylene-based, methanesulfonic acid ester-based, triazine-based, and polymer-type hardeners can be used. Further, as a thickener, for example, US Pat.
7,410, Belgian Patent No. 558,143, polyols as a gelatin plasticizer (e.g., U.S. Pat.No. 2,960,404, Japanese Patent Publication No. 43-4939, JP-A-48)
-63715), and latexes as described in U.S. Patent No. 766,979, French Patent No. 1,395,544, Japanese Patent Publication No. 48-43125, and as a matting agent in British Patent No. Those described in the specification of 1,221,980 can be used.

Further, a desired coating aid can be used in the constituent layers of the silver halide photographic light-sensitive material of the present invention. For example, as saponin or sulfosuccinic acid type surfactants, for example, British Patent No. 548,532, Japanese Patent Publication No. 52-25246, or as anionic surfactants, for example, Japanese Patent Publication No. 43-18166, U.S. Patent No. 3,514,293, French Patent No. 2,025,688, Japanese Patent Publication No. 43-10247.
Those described in the publication can be used.

In the above photographic emulsion, the process for producing a light-sensitive material,
Various compounds can be added in order to prevent sensitivity deterioration and fog generation during storage or processing. These compounds include 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene, 3-methyl-benzothiazole, 1-phenyl-3-mercaptotetrazole, many heterocyclic compounds, and mercury-containing compounds. A large number of compounds such as compounds, mercapto compounds and metal salts have been known for a long time.

One example of a compound that can be used is The Theory of the Photographi by K. Mees.
c Process) (3rd edition, 1966) with reference to the original documents, and JP-A-49-81024, 50-6306 and 50-19.
Any of the antifoggants well known in the art such as those described in US Pat. No. 4,29,3,850,639 may be used.

In addition, in implementing the present invention, various techniques used in the photographic technique can be applied.

The development processing method of a silver halide photographic light-sensitive material according to the present invention comprises steps from development to drying when processed by an automatic processor including the steps of development, fixing, washing (or stabilizing) and drying. Is preferably completed within 90 seconds.

That is, the time from the time when the front end of the photosensitive material starts to be dipped in the developing solution to the time when the front end of the photosensitive material comes out of the drying zone (so-called Dry to Dry time).
Within 90 seconds, more preferably this Dry to Dry
The time is within 60 seconds.

The fixing temperature and time are about 20 ° C to 50 ° C for 6 seconds to
20 seconds is preferable, and 6 seconds to 15 seconds at 30 ° C to 40 ° C is more preferable.

The developing time with the developing solution of the present invention is 5 to 45 seconds, preferably 8 to 30 seconds. Development temperature is 25-50 ° C
Is preferable, and 30-40 degreeC is more preferable.

The drying temperature is usually 35 to 100 ° C., preferably 4
The temperature is 0 to 80 ° C., and a drying zone provided with a blowing means of hot air or a heating means using far infrared rays may be installed in the automatic processor.

Further, the automatic developing machine is equipped with a mechanism for applying water or a rinse solution of an acidic solution having no fixing ability to the light-sensitive material during each of the developing, fixing and washing steps (special feature). Kaihei 3-264953) may be used. Further, the automatic developing machine may have a built-in device capable of preparing a developing solution and a fixing solution.

[0053]

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

Example 1 (Preparation of tabular seed emulsion) A hexagonal tabular seed emulsion was prepared by the following method.

<Solution A> 60.2 g of ossein gelatin 20.0 l of distilled water Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% aqueous solution of ethanol 5.6 ml KBr 26.8 g 10% H ₂ SO ₄ 144 ml <Solution B> Silver nitrate 1487.5 g Distilled water to 3500 ml <Solution C> KBr 1029g KI 29.3g Distilled water to 3500 ml <Solution D> 1.75N KBr aqueous solution At the following silver potential control amount 35 ° C, JP-B-58-58288 and 58-58289 Using the mixing stirrer shown in the specification, 64.1 ml of each of solution B and solution C was added to solution A by the simultaneous mixing method over a period of 2 minutes to perform nucleation.

After stopping the addition of solution B and solution C, 60
The temperature of solution A was raised to 60 ° C. over a period of minutes, and solution B and solution C were again added by the simultaneous mixing method at a flow rate of 68.5 ml / min for 50 minutes. During this period, the silver potential (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was controlled to be +6 mV using the solution D. After the addition was completed, the pH was adjusted to 6 with 3% KOH, and the mixture was immediately desalted and washed with water to obtain a seed emulsion EM-A. The seed emulsion EM-A thus prepared contained 90% of the total projected area of silver halide grains.
It was found by electron microscope observation that the above consisted of hexagonal tabular grains with the maximum adjacent side ratio of 1.0 to 2.0, the average thickness of the hexagonal tabular plate was 0.07 μm, and the average diameter (circle diameter conversion) was 0.5 μm.

(Preparation of Monodisperse Twin Crystal Emulsion) A monodisperse twin silver iodobromide emulsion EM-1 of the present invention containing 1.53 mol% AgI was prepared using the following four kinds of solutions.

<Solution A> 29.4 g of ossein gelatin Polyisopropylene-polyethyleneoxy-disuccinic acid ester sodium salt 10% aqueous ethanol solution 2.5 ml Seed emulsion EM-A 0.588 mol equivalent Distilled water to 4800 ml <Solution B> Silver nitrate 1404.2 g Distilled water to 2360 ml <Solution C> KBr 968g KI 20.6g Distilled water to 2360 ml <Solution D> 1.75N KBr aqueous solution At the silver potential control amount 60 ° C. below, Japanese Patent Publication Nos. 58-58288 and 58-58289 Using the mixing stirrer shown in the specification, the total amount of the solution B and the solution C is added to the solution A by the simultaneous mixing method at a flow rate of 21.26 ml / min.
It took a minute and additional growth was performed.

During this period, the silver potential was controlled to be +25 mV by using the solution D.

After the addition was completed, the following sensitizing dyes (A) and (B) were added in an amount of 300 mg and 15 mg, respectively, per mol of silver halide.
After addition, in order to remove excess salts, precipitation desalting was performed using a demol (Kao Atlas) aqueous solution and a magnesium sulfate aqueous solution, and a gelatin aqueous solution containing 92.2 g of ossein gelatin was added to 2500 ml with stirring and redispersion. did.

Sensitizing dye (A): 5,5'-dichloro-9-ethyl-3,3'-di (3-sulfopropyl) oxacarbocyanine salt anhydride Sensitizing dye (B): 5,5'- Di- (butoxycarbonyl) -1,
1'-Diethyl-3,3'-di- (4-sulfobutyl) benzimidazolocarbocyanine-sodium salt anhydride About 3000 particles of EM-1 were observed and measured by an electron microscope, and the shape was analyzed. The particle diameter was 1.05 μm, the average particle thickness was 0.25 μm, and the distribution was 18%.

(Synthesis of Latex A for Comparison) A solution of 0.01 kg of sodium dodecylbenzenesulfonate and 0.05 kg of ammonium persulfate in 40 liters of water was stirred at a liquid temperature of 60.degree. kg (a) methyl methacrylate (3.0 kg), (u) ethyl acrylate (3.2 kg) and (d) 2-acrylamido-2-methylpropanesulfonic acid (0.8 kg) were added over 1 hour, and then the mixture was stirred for 1.5 hours and then steam distilled for 1 hour. After removing the residual monomers by cooling, the mixture was cooled to room temperature, and the pH was adjusted to 6.0 with sodium hydroxide. The latex solution obtained is 55 with water.
Finished to kg. As described above, a monodisperse latex having an average particle size of 0.11 μm was obtained.

(Synthesis of Latex Lx-8) A solution prepared by adding 1.0 kg of gelatin, 0.01 kg of sodium dodecylbenzenesulfonate and 0.05 kg of ammonium persulfate to 60 liters of water was stirred at a liquid temperature of 60 ° C. under a nitrogen atmosphere. (A) Styrene 3.0 kg (B) Methyl methacrylate 3.0 kg and (C)
A mixture of 3.2 kg of ethyl acrylate and 0.8 kg of 2-acrylamido-2-methylpropanesulfonic acid sodium salt
The mixture was added over a period of time, and after stirring for 1.5 hours, steam distillation was performed for another hour to remove residual monomers, and then the mixture was cooled to room temperature and adjusted to pH 6.0 with ammonia.
The obtained latex liquid was made up to 75 kg with water.

As described above, a monodisperse latex having an average particle size of 0.1 μm was obtained.

(Synthesis of Latex Lx-17) To a liquid obtained by adding 1.0 kg of gelatin, 0.01 kg of sodium dodecylbenzenesulfonate and 0.05 kg of ammonium persulfate to 40 liters of water, while stirring at a liquid temperature of 80 ° C., under a nitrogen atmosphere. Then, (a) ethyl acrylate 9.3 kg, (b) a mixture of epichlorohydrin and acrylic acid 0.4 kg, and (u) acrylic acid 0.3 kg was added over 1 hour, and after stirring for 1.5 hours, gelatin 1.0 kg and ammonium persulfate were added. 1.5 plus 0.005 kg
After stirring for a while, steam distillation was carried out for an additional 1 hour after completion of the reaction to remove residual monomers, and after cooling to room temperature,
The pH was adjusted to 6.0 with ammonia. The obtained latex liquid was made up to 55 kg with water. As described above, a monodisperse latex having an average particle size of 0.12 μm was obtained.

(Preparation of sample) 50 for each emulsion
The sensitizing dyes (A) and (B) were added in an amount of 150 mg and 15 mg per mol of silver halide in the state of being kept at ° C, and then ammonium thiocyanate was added in an amount of 7.0 × 10 ^-4 mol per mol of silver, and appropriately. Chemical ripening was performed by adding various amounts of chloroauric acid and hypo, and 6 × 1 of AgI fine grain emulsion having an average grain size of 0.06 μm was obtained.
After adding 0 ^-4 mol / Ag 1 mol, 4-hydroxy-6-methyl-
Stabilized with 1,3,3a, 7-tetrazaindene 3 × 10 ^-2 mol.

Various additives described below were added to each emulsion.

The additives used in the emulsion liquid (light-sensitive silver halide coating liquid) are as follows. The addition amount is indicated by the amount per mol of silver halide.

[0069]

[Chemical 4]

T-butyl-catechol 400 mg polyvinylpyrrolidone (molecular weight 10,000) 1.0 g styrene-maleic anhydride copolymer 2.5 g trimethylolpropane 10 g diethylene glycol 5 g nitrophenyl-triphenyl-phosphonium chloride 50 mg 1,3-dihydroxybenzene-4 -Ammonium sulfonate 4g 2-Mercaptobenzimidazole-5-sodium sulfonate 1.5mg

[0071]

[Chemical 5]

NC ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1 g The additives used in the protective layer liquid are as follows. The addition amount is shown as the amount per 1 g of gelatin.

Matting agent composed of polymethylmethacrylate having an area average particle size of 7 μm 7 mg Colloidal silica (average particle size 0.013 μm) 70 mg 2,4-dichloro-6-hydroxy-1,3,5-triazine sodium salt 30 mg (CH ₂ = CHSO ₂ -CH _2- ) ₂ O 36mg

[0074]

[Chemical 6]

F ₁₉ C ₉ -O- (CH ₂ CH ₂ O) ₁₀ CH ₂ CH ₂ -OH 3 mg The obtained coating solution was uniformly applied onto a blue-colored polyethylene terephthalate film base with an undercoating thickness of 180 μm. And then dried.

The amount of gelatin in the photographic emulsion layer was 2.0 g / m ^{2 on} one side, and the amount of coated silver was 2.0 g / m ^{2 on} one side.
A protective layer is such that one side 1.15 g / m ² as a gelatin with the amount, two-sided simultaneously coated on the support at a speed per minute 80m using two slide hopper type coaters, 2
A sample was obtained by drying in 20 minutes. Further, the polymer components of the latex were adjusted so as to have the amounts shown in Tables 1 to 4.

(Developer and Fixer) Next, the compositions of the developer and fixer used in the present invention are shown.

<Developer Formulation> Part-A (12 liter finish) Potassium hydroxide 450 g Potassium sulfite (50% solution) 280 g Diethylenetetraamine pentaacetic acid 120 g Sodium bicarbonate 132 g 5-Methylbenzotriazole 1.2 g 1-phenyl- 5-Mercaptotetrazole 0.2g Hydroquinone 340g Add water to make 5000ml.

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 glacial acetic acid 120 g Potassium bromide 225 g Add water to make 1000 ml.

<Fixer Formula> Part-A (for 18 liter finish) Ammonium thiosulfate (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 18g Part-B Aluminum sulphate 800g Preparation of developer is Part-A, Par in about 5 liters of water.
t-B was added at the same time, water was added while stirring and dissolved to make 12 liter, and the pH was adjusted to 10.40 with glacial acetic acid. This is used as a development replenisher. To the developer replenisher, 20 ml / l of the above-mentioned starter was added to adjust the pH to 10.26 to prepare a working solution.

The fixing solution was prepared by adding Part to about 5 liters of water.
-A and Part-B were added at the same time, water was added while dissolving with stirring to make 18 liters, and sulfuric acid and NaOH were used to p
The H was adjusted to 4.4. This is the fixing replenisher.

Using the above developing solution and fixing solution as basic compositions,
As shown in Tables 1 to 4, developing solutions containing the compounds usable in the invention and the comparative compound were prepared and developed.

Development is carried out by a roller-conveying type automatic developing machine SRX-50.
Dry to Dry 45 seconds using 2 (manufactured by Konica Corp.). Processing is performed at development 35 ° C, fixing 33 ° C, washing with water 20 ° C, and drying 50 ° C.

The treated sample was evaluated as follows.
The results are shown in Tables 1 to 4.

[Evaluation of Sensitivity] The obtained sample was sandwiched between two X-ray fluorescent intensifying screens, KO-250, and the tube voltage was 80 kV.
After exposure through an aluminum wedge at a tube current of 100 mA and an irradiation time of 50 msec, development processing was performed using the automatic developing machine. For the obtained sample, the reciprocal of the amount of exposure energy required to give a density of the base density + fog density + 1.0 was determined and shown as a relative value with the sensitivity of Sample 1 as 100.

[Evaluation of silver sludge] Next, a developing sample exposed by X-rays so that the entire surface of the sample had a density of 1.0 was developed and replenished by the automatic developing machine, and samples to be developed are shown in Tables 1 to 4.
And the fixer replenishment rate is 300 cc / m ² .
It was developed daily for 70 sheets for 30 days. At that time, the developing rack, roller stains and wall stains, and the developed samples were visually evaluated. The evaluation was made into the following four-level evaluation.

4: Almost no silver sludge was observed, and the roller and the wall surface were completely free from contamination. 3: The developer was turbid and a slight stain was found on the wall surface of the processing tank. 2: Silver sludge was generated and the developing rack was removed. Dirt does not easily come off even after washing 1: A large amount of silver sludge was generated in the developer tank and adhered to the film to be processed, resulting in image contamination [Evaluation of development unevenness] The entire surface of the sample had a density of 2.0 ± 0.1 The developing sample exposed to X-rays as described above was developed using the automatic developing machine. The developed sample was visually evaluated as a sample for evaluating uneven development. The evaluation was made into the following four-level evaluation.

4: No development unevenness is observed 3: Some development unevenness occurs, but no problem 2: Development unevenness occurs frequently 1: Development unevenness occurs remarkably

[0089]

[Table 1]

[0090]

[Table 2]

[0091]

[Table 3]

[0092]

[Table 4]

[0093]

[Chemical 7]

From the results of Tables 1 to 4, the samples of the present invention are
Prevents the generation of silver sludge even with low replenishment developer,
It is also understood that an image with high sensitivity and no unevenness in the development process can be obtained.

[0095]

According to the present invention, there is provided a method of processing a silver halide photographic light-sensitive material, which can produce an image having high sensitivity and no unevenness in development processing when silver sludge is not generated when processing using an automatic processor. We were able to.

Claims (1)

[Claims] 1. A method of processing a silver halide photographic light-sensitive material containing a support and a hydrophilic colloid layer containing at least one light-sensitive silver halide emulsion using an automatic processor, in which the emulsion layer and At least a part of the polymerization reaction of the polymer is contained in the protective layer and the polymer latex is contained in a solvent containing gelatin, and at least a silver sludge inhibitor is used as a developer for the developing step of an automatic processor. A method of processing a silver halide photographic light-sensitive material, which comprises replenishing and using a developer containing one of them.