JPH06317884A - Processing method for silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To provide a processing method for a silver halide photographic sensitive material by which such a silver halide photographic sensitive material is obtd. that has high sensitivity, high covering property, and scratching resistance against high-temp. rapid processing in an automatic developing machine and causes no contamination due to after color on a film after processed. CONSTITUTION:This silver halide photographic sensitive material contains at least one kind of polymer expressed by general formula and is processed in a roller-carrying automatic developing machine at a specified speed. In formula, R1 is a hydrogen atom or alkyl group of <=6 carbon number, R2 and R3 are hydrogen atoms, alkyl groups, aryl groups or aralkyl groups of (10 carbon number, and R2 and R3 may be bonded to form a nitrogen-contg. heteroring. A is a monomer unit of the polymer obtd. by copolymn. of copolymerizable ethylene-type unsatd. monomers, L is a bivalent connecting group, (n) is 0 or 1, (m) is 1 or 2, and (x) is 70-100.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention provides a halogenating agent having a high covering power, a scratch resistance in a rapid processing at a high temperature by an automatic developing machine, and a high sensitivity and a high covering power with no residual color stain on the processed film. It is an object of the present invention to provide a method for processing a silver halide photographic light-sensitive material, which can obtain a silver photographic light-sensitive material.

[0002]

2. Description of the Related Art In recent years, in the field of X-ray photosensitive materials,
Rapid processing is progressing rapidly. In order to rapidly process a silver halide photographic light-sensitive material, it is an essential condition that the silver halide has excellent developability as well as good fixability, washability and dryness.

Many proposals have hitherto been made as a method for increasing the developability of silver halide and increasing the covering power. For example, polyacrylamide described in US Pat. No. 2,271,158 is used as a silver halide photographic light-sensitive material. Method used, or U.S. Pat. Nos. 4,411,986 and 4,4, which use tabular silver halide grains having a high aspect ratio and a small grain thickness
Nos. 34,226 and 4,413,053 are disclosed.

However, these prior arts have a problem in terms of physical properties while increasing the covering power. For example, when rapid developing treatment is performed, rubbing-like fog is apt to occur at a portion contacting with a conveying roller, which is called a scratch. Is. In particular, tabular grains have a drawback that they are easily fogged by pressure due to contact with others.

As a general method for eliminating scratches on a film, for example, it is known to increase the amount of binder in the emulsion to lower the silver / binder ratio. However, an increase in the amount of the binder naturally deteriorates the fixability, water washability and dryability, resulting in loss of suitability for rapid processing.

Further, an increase in the amount of the binder has a problem that a clear image cannot be obtained because the residual color is liable to be contaminated due to insufficient processability.

[0007]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide a coating film which has excellent covering power, has scratch resistance in a high-speed rapid processing by an automatic processor, and has no residual color contamination on the processed film, and has high sensitivity and high sensitivity. It is an object of the present invention to provide a method for treating a silver halide photographic light-sensitive material, which can obtain a silver halide photographic light-sensitive material having a covering power.

[0008]

The above problems have been solved by the present invention described below. That is, a silver halide photographic light-sensitive material containing at least one of the polymers represented by the following general formula [I] is represented by the following formula in a roller-conveying type automatic developing machine comprising developing, fixing, washing and drying steps. It is achieved by a method for processing a silver halide photographic light-sensitive material, which is characterized in that the processing is carried out under the following conditions.

L ₁ ^0.75 × T = 15.0 to 40.0 L ₂ <L ₃ where L ₁ is the line length (m) from the entry of the developer surface of the developing tank to the entry of the liquid surface of the washing tank L ₂ is the development of the developing tank Line length from the liquid surface plunge to the fixing liquid surface of the fixing tank (m) L ₃ is the line length from the fixing liquid surface plunging to the washing tank liquid surface (m) T is the time required from the developing liquid surface plunging to the washing tank plunging (Se
represents c).

[0010]

[Chemical 2]

In the formula, R ₁ represents a hydrogen atom or an alkyl group having 6 or less carbon atoms, and R ₂ and R ₃ respectively represent a hydrogen atom and a carbon number.
It represents 10 or less substituted or unsubstituted alkyl group, aryl group or aralkyl group, and R ₂ and R ₃ may combine with each other to form a nitrogen-containing heterocycle. A represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer, and L
Is a divalent linking group, n is 0 or 1, m is 1 or 2, and x is 70 to 100 in terms of mole percentage.

The present invention will be described in detail below.

The above L ₁ , L ₂ and L ₃ are, for example, 175 μm
It can be determined based on a photosensitive material having a photographic constituent layer on a polyethylene terephthalate film support having a thickness of 1. Further, the above T is the time from when the leading edge of the film rushes into the surface of the developing solution until it rushes into the liquid level of the washing tank after passing through the developing tank, the transition portion, the fixing tank and the transition portion (in other words, the processing line length. L ₁ (m) is the line transfer speed (m / S
It can be called the quotient (Sec) divided by ec). ) Represents.

The reason why the time of the crossover portion should be included here is that it is well known in the industry that even in the crossover portion, the liquid of the preceding process is substantially swollen in the gelatin film, so that the treatment step is substantially the same. This is because it can be considered that is progressing.

The number of transport rollers of the automatic processor according to the present invention is preferably a value obtained by dividing the line length in each processing tank by the number of rollers in each processing tank in the range of 0.01 to 0.04. Further, it is preferable that the time of each treatment site is as follows.

[0016] The roller used is preferably 12 mm to 60 mm in diameter in the transport section and 30 cm to 110 cm in length, and various materials can be used, for example, bakelite (glass) in the developing, fixing, washing and drying parts. Powder, metal powder, plastic powder, etc.) or rubber type (neoprene, isoprene, silicone rubber, etc.) can be used. Hydrophobic and elastic silicone rubber, or synthetic leather having a high water absorption, "Clary" (manufactured by Kuraray Co., Ltd.) can be used for the transitional portion and the squeeze portion.

In the present invention, when the product of L ₁ ^0.75 in the above formula and the processing time T is less than 15.0, not only the sensitivity is sharply decreased but also a sensitizing dye is contained and a binder such as gelatin is used. In the case of a light-sensitive material containing 3 g / m ² or more, the residual color contamination of the dye increases.

On the other hand, the product of L ₁ ^0.75 and the processing time T is 40.0.
It was found that when the value exceeds, the sensitivity is hardly increased, but the graininess of the image is deteriorated and the fog is increased.

Therefore, L ₁ ^0.75 × T = 15.0 to 40.0, L ₂ <L
It is most preferable to treat under the condition of ₃ .

Next, the polymer represented by the general formula [I] used in the silver halide photographic light-sensitive material of the present invention will be described.

The polymer represented by the general formula [I] is a polymer in which x in the formula is 70 mol% or more, preferably 80 mol% or more, more preferably 90 mol% or more as a polymer constitutional unit.

In the formula, A represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer.

The ethylenically unsaturated monomer in the preferred polymer of the present invention includes ethylene, propylene, 1-
Butene, isobutene, styrene, chloromethylstyrene, humanoxymethylstyrene, vinylbenzene sulfonate sodium, vinylbenzyl sulfonate sodium, N, N, N-
Trimethyl-N-vinylbenzylammonium chloride, N, N-dimethyl-N-benzyl-N-vinylbenzylammonium chloride, α-methylstyrene, vinyltoluene, 4-vinylpyridine, 2-vinylpyridine, benzylvinylviridinium chloride , N-vinylacetamide,
N-vinylpyrrolidone, 1-vinyl-2-methylimidazole, monoethylenically unsaturated esters of aliphatic acids (eg vinyl acetate, allyl acetate), ethylenically unsaturated monocarboxylic or dicarboxylic acids and their salts (eg acrylic Acid, methacrylic acid, itaconic acid, maleic acid, sodium acrylate, potassium acrylate, sodium methacrylic acid), maleic anhydride, ethylenically unsaturated monocarboxylic acid or dicarboxylic acid ester (for example, n-butyl acrylate, n- Hexyl acrylate, hydroxyethyl acrylate, cyanoethyl acrylate, N, N-
Diethylaminoethyl acrylate, methylmethacrylate, n-butylmethacrylate, benzylmethacrylate, hydroxyethylmethacrylate, chloroethylmethacrylate, methoxyethylmethacrylate, N, N-diethylaminoethylmethacrylate, N, N, N-triethyl
-N-methacryloyloxyethylammonium p-toluenesulfonate, N, N-diethyl-N-methyl-N-methacryloyloxyethylammonium-p-toluenesulfonate, dimethyl itaconic acid, maleic acid monobenzyl ester) 56-151937, 57-104927, 56-142
There are monomers disclosed in No. 524 and the like.

Preferred examples of the compound of the polymer according to the present invention will be given below. (The number of the degree of polymerization represents a mole percentage.)

[0025]

[Chemical 3]

[0026]

[Chemical 4]

The polymers according to the present invention have an average molecular weight of 5,000 to 20,000, preferably 7,000 to 100,000, more preferably 15,000 to 70,000.

The above-mentioned polymer may be added to any of the layers constituting the silver halide photographic light-sensitive material of the present invention. The term "silver halide photographic light-sensitive material constituent layer" as used herein means a photosensitive or substantially non-photosensitive silver halide emulsion layer, a protective layer, an intermediate layer, a filter layer,
It refers to all the constituent layers of a silver halide photographic light-sensitive material such as an ultraviolet absorbing layer and an antihalation layer.

For these hydrophilic colloid layers, various synthetic polymer compounds such as gelatin can be used as a binder or protective colloid.

As the gelatin, in addition to lime-processed gelatin, acid-processed gelatin or gelatin derivative may be used.

The polymer of the present invention may be added to any of these hydrophilic layers, but is preferably added to the photosensitive emulsion layer or a protective layer coated on the photosensitive emulsion layer. Satisfactorily achieves the intended effects of the present invention.

When the polymer is added to the silver halide emulsion layer, it is a preferred embodiment to add it after the chemical ripening and before the coating. The polymer may be added as a powder, but it is preferable to add it as an aqueous solution. The addition amount is not uniform depending on the type of polymer or emulsion, but is usually 1 × 10 ^-2 g to 5.0 g per 1 m ² of the light-sensitive material, preferably
It is 0.1 g to 2 g.

As the silver halide composition of the emulsion used in the silver halide photographic light-sensitive material of the present invention, silver chloride, silver bromide, silver chlorobromide, silver iodobromide, silver chloroiodobromide or the like is used. However, a silver iodobromide emulsion is preferred because of high sensitivity.

The silver halide grain may be of any crystal type as long as it has the constitution of the present invention, for example, a single crystal such as a cube, an octahedron or a tetrahedron, and a polytwin crystal of various shapes. It may be a particle.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can be produced by a known method. For example, Research Disclosure (RD) No.17643 (December 1978), 22
Can be prepared by the method described in "Emulsion Preparation and Types" on page 23 or the method described in (RD) No. 18716 (November 1979), page 648.

The emulsion used in the silver halide photographic light-sensitive material of the present invention is described, for example, in "The Theory of the" by TH James.
Photographic process ”4th edition, published by Macmillan (1977
Year) Method described on pages 38-104, GF Duffin, “Photograph
ic Emulsion Chemistry ”, published by Focal Press (1966),
“Chimie et Physique Photographique” by P. Glafkides
Published by Paul Montel (1967) or VL Zelikman et al. “Makin
g And Coating Photographic Emulsion "can be prepared by the method described in Focal Press (1964).

That is, the mixing conditions such as the forward mixing method, the reverse mixing method, the double jet method and the control double jet method under the solution conditions such as the acidic method, the ammonia method and the neutral method,
It can be produced using a particle preparation condition such as a conversion method, a core / shell method, or a combination thereof.

The silver halide grains may be fine grains having a grain size of 0.1 μm or less or large grains having a projected area of 10 μm, and may be a monodisperse emulsion having a narrow grain size distribution or a polydisperse emulsion having a wide grain size distribution. . The monodisperse emulsion referred to herein means a silver halide emulsion having a grain size variation coefficient of 0.20 or less as defined in JP-A-60-162244.

Monodisperse emulsions include those emulsions having an average grain size of greater than 0.1 μm, at least 95 wt% of which are within ± 40% of the average grain diameter. Also, the average particle size is 0.25 μm to 2 μm and at least 9
Also included are silver halide emulsions in which 5 wt% or at least 95% of silver halide grains are contained within the range of average grain size ± 20%.

The method for producing the above monodisperse emulsion is known, and for example,
J. Phot. Sci, 12.242 to 251, (1963), JP-A-48-36890,
52-16364, 55-142329, 58-49938, British Patent 1,413,748, US Patents 3,574,628, 3,655,394 and the like. The emulsion used in the silver halide photographic light-sensitive material of the present invention can be grown by, for example, using a seed crystal as a method for obtaining the above monodisperse emulsion, and using this seed crystal as a growth nucleus to supply silver ions and halide ions. Other emulsions may be used.

The emulsion used in the silver halide photographic light-sensitive material of the present invention has an aspect ratio (grain diameter) / (grain thickness) of 2.
The tabular grains described above may be used.

Preferred tabular grains may have an aspect ratio of 2 or more and 20 or less.

The advantage of such tabular grains is that they can improve spectral sensitization efficiency and image graininess and sharpness. For example, British Patent No. 2,112,157, US Patent Nos. 4,414,310, and 4,434,226. Is disclosed in
The emulsion can be prepared by the methods described in these publications.

The crystal structure of silver halide may have a silver halide composition different from the inside and the outside, or may have a layered structure. A particularly preferred embodiment of the emulsion is silver halide grains having substantially two distinct layered structures (core / shell structure) consisting of a high iodine core portion and a low iodine shell layer.

The high-iodity core portion is silver iodide, and the silver iodide content is 20 to 40 mol%, preferably 20 to 30 mol%. The silver halide composition other than silver iodide in the core portion may be either silver bromide or silver chlorobromide, but a composition having a high silver bromide ratio is desirable.

The outermost shell layer is a silver halide containing 5 mol% or less of silver iodide, preferably 2 mol%.
It is a layer containing the following silver iodide. Silver halide other than silver iodide in the outermost layer may be any of silver chloride, silver bromide, and silver chlorobromide, but a composition having a high silver bromide ratio is desirable.

A method for producing the above core / shell type emulsion is known, for example, J. Phot. Sci, 24.198. (1976), US Pat.
The methods described in 250, 3,505,068, 4,210,450, 4,444,877 or JP-A-60-143331 can be referred to.

The emulsion may be subjected to a Nudel water washing method, a flocculation sedimentation method or the like in order to remove soluble salts. Preferred water washing methods include, for example, aromatic hydrocarbons containing a sulfo group described in JP-B-35-16086. Examples thereof include a method using a system aldehyde resin and a desalting method using a polymer flocculant such as Exemplified G-3 and G-8 described in JP-A-63-158644.

The emulsion used in the silver halide photographic light-sensitive material of the present invention can use various photographic additives in the steps before and after physical ripening or chemical ripening.

Examples of the compound used in such a process include Research Disclosure (RD) No. 1764
3, various compounds described in (RD) No. 18716 and (RD) No. 308119 (December 1989) can be used. The types and locations of the compounds described in these three (RD) are listed below.

Additive RD-17643 RD-18716 RD-308119 Page Classification Page Page Classification Chemical sensitizer 23 III 648 Upper right 996 III Sensitizing dye 23 IV 648-649 996-8 IV Desensitizing dye 23 IV 998 IV B Dye 25 to 26 VIII 649 to 650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006 to 7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004 to 5 X Surfactant Agent 26-27 XI 650 Right 1005-6 XI Plasticizer 27 XII 650 Right 1006 XII Sliding Agent 27 XII Matting Agent 28 XVI 650 Right 1008-9 XVI Binder 26 XXII 1003-4 IX Support 28 XVII 1009 XVII Halogen of the Invention Examples of the support used in the silver halide photographic light-sensitive material include those described in the above RD,
A suitable support is a plastic film or the like, and the surface of the support may be provided with an undercoat layer to improve the adhesiveness of the coating layer, or subjected to corona discharge or ultraviolet irradiation.

The processing method of the silver halide light-sensitive material of the present invention, when processed by an automatic processor including the steps of development, fixing, washing (or stabilizing) and drying, the steps from development to drying are 90 seconds. It is to be completed within.

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

Incidentally, the development time in the rapid processing is within 20 seconds,
It is preferably within 15 seconds, and the developing temperature is preferably 25 to 50 ° C, more preferably 30 to 40 ° C.

The drying time is usually 35 to 100 ° C., preferably 40.
A drying zone in which hot air of -80 ° C is blown or a heating means using far infrared rays is provided may be installed in the automatic developing machine.

The developer used in the present invention is based on a developer containing 1,4-dihydroxybenzenes as a developer or, if necessary, a p-aminophenol-based developer and / or pyrazolidone.

As the 1,4-dihydroxybenzene developing agent, hydroquinone, chlorohydroquinone, bromhydroquinone, isopropylhydroquinone, methylhydroquinone, 2,3-dichlorohydroquinone, 2,5-dichlorohydroquinone, 2,3-dibromohydroquinone, 2 ,Five-
There are dimethylhydroquinone and the like, but hydroquinone is particularly preferable. As a p-aminophenol type developing agent
N-methyl-p-aminophenol, p-aminophenol, N
-(β-hydroxyethyl) -p-aminophenol, N- (4-
(Hydroxyphenyl) glycine, 2-methyl-p-aminophenol, p-benzylaminophenol, and the like, among which N-methyl-p-aminophenol is preferable.

Examples of the pyrazolidone compound that can be used in the present invention include 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, 1-phenyl-4-ethyl-3-pyrazolidone. 1-phenyl-5-methyl-3-pyrazolidone, 1-phenyl-4-methyl-3-pyrazolidone, 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone, 1-phenyl-4,4- Dihydroxymethyl-3-pyrazolidone, 1,5-diphenyl-3-pyrazolidone, 1-p-tolyl-3-pyrazolidone, 1-phenyl-2-acetyl-4,4-dimethyl-3-pyrazolidone, 1-p-hydroxy Phenyl-4,4-
Dimethyl-3-pyrazolidone, 1- (2-benzothiazolyl) -3-
Examples thereof include pyrazolidone compounds such as pyrazolidone and 3-acetoxy-1-phenyl-3-pyrazolidone.

The developer used in the present invention may contain a hardening agent that strengthens the physical properties of the film by undergoing a hardening reaction with gelatin in the light-sensitive material during the development processing. Examples of the hardener include glutaraldehyde, α-methylglutaraldehyde, β-methylglutaraldehyde, maleindialdehyde, succindialdehyde, methoxysuccindialdehyde, methylsuccindialdehyde, α-methoxy-β-ethoxyglutaraldehyde, α-n-butoxyglutaraldehyde, α, α-dimethoxysuccindialdehyde, β-isopropylsuccindialdehyde,
α, α-diethylsuccindialdehyde, butylmaleindialdehyde, or bisulfite adducts thereof are used.

In the developer used in the present invention, a sulfite (for example, sodium sulfite or potassium sulfite) can be used as a preservative for the developing agent. Further, as additives used in addition to the above components, development inhibitors such as sodium bromide and potassium iodide, ethylene glycol,
Organic solvent such as diethylene glycol, triethylene glycol, dimethylformamide, methyl cellosolve, hexylene glycol, ethanol, methanol, or
1-Phenyl-5-mercaptotetrazole, 2-mercaptobenzimidazole 5-mercapto compounds such as sodium salt of 5-sulfonic acid, may contain an antifoggant such as benztriazole compounds such as 5-methylbenztriazole, and further required Toning agent, surfactant, antifoaming agent,
A water softener may be included.

The pH of the developing solution may be 9.0 to 12, preferably 9.0 to 11.5. The alkaline agent or buffer used for setting the pH includes a pH adjusting agent such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium triphosphate and potassium triphosphate.

In the fixing solution used in the present invention, sodium thiosulfate, ammonium thiosulfate or the like can be used as a fixing agent, and ammonium thiosulfate is preferable from the viewpoint of fixing speed.

Water-soluble aluminum such as aluminum chloride, aluminum sulfate or potassium alum may be used as a hardening agent in the fixing solution. In addition, tartaric acid,
You may use citric acid, gluconic acid, or those derivatives individually or in combination.

Further, a preservative such as sulfite or bisulfite, a pH adjuster such as sulfuric acid, and a water softener such as a chelating agent may be used. The pH of the fixer is 3.
8 or more, preferably 4.2 ~ 7.0, more preferably 4.2 ~
5.5.

The fixer replenisher used in the present invention usually has the same composition as the above fixer composition,
Depending on the case, you may use what contains other components.

The fixer replenisher may be mixed and prepared as a concentrated solution in the form of, for example, two or more agents at the time of use.

The silver halide photographic light-sensitive material used in the present invention can be used in a wide range of light-sensitive materials such as general-purpose black-and-white light-sensitive materials, X-ray light-sensitive materials, printing plate-making light-sensitive materials, microfilms and color reversal light-sensitive materials. However, a black-and-white photosensitive material such as an X-ray photosensitive material is preferable.

[0068]

EXAMPLES The present invention will be described below with reference to examples.

Example 1 [Preparation of Emulsion 1] 1) Preparation of seed emulsion 1 2 mol% of silver iodide having an average grain size of 0.3 μm by the double jet method while controlling at 60 ° C., pH = 8 and pH = 2.0. Monodisperse cubic crystal grains of silver iodobromide containing were prepared.

The emulsion thus obtained was desalted at 40 ° C. using an aqueous solution of DEMO N (an aldehyde condensate of sodium salt of naphthalene sulfonic acid) manufactured by Kao Atlas and magnesium sulfate, and then redispersed in an aqueous gelatin solution. A seed emulsion was obtained.

2) Grain growth from seed emulsion 1 The above seed emulsion was dispersed in a gelatin aqueous solution kept at 40 ° C., and the pH was adjusted to 9.7 with aqueous ammonia and acetic acid. An aqueous ammoniacal silver nitrate solution and an aqueous solution of potassium bromide and potassium iodide were added to this solution by the double jet method.

During the addition, the pH was controlled to be 7.3 and pH = 9.7 to form a layer having a silver iodide content of 35 mol%. Then, an aqueous ammoniacal silver nitrate solution and an aqueous potassium bromide solution were added by the double jet method, the pAg was kept at 9.0 up to 95% of the target particle size, and the pH was continuously changed from 8.0 to 9.0. Then p
Ag was adjusted to 11.0, and the grain size was grown to a target grain size while maintaining pH = 8.0. Subsequently, the pH was lowered to 6.0 with acetic acid, and 5,5'-dichloro-9-ethyl-3,3'-di- was added as a spectral sensitizing dye.
Anhydrous sodium salt of (3-sulfopropyl) oxacarbocyanine was added at 400 mg / mol AgX, desalted in the same manner as above, and then dispersed in an aqueous gelatin solution.

By this method, the average silver iodide content is 2.0.
In mol%, the average particle size of the tetrahedron with rounded vertices is
0.40μm, 0.65μm, 1.00μm, coefficient of variation 0.1
7, 0.16, 0.16 monodisperse silver iodobromide emulsions (A), (B) and
(C) was prepared.

[Preparation of Emulsion 2] 1) Preparation of Seed Emulsion 2 Including hydrogen peroxide-treated gelatin vigorously stirred at 40 ° C.
A double jet method was used to add an equimolar potassium bromide aqueous solution containing a silver nitrate aqueous solution and hydrogen peroxide-treated gelatin to a 05N potassium bromide aqueous solution.
After the liquid temperature was lowered to 5 ° C., 80 ml of ammonia water (28%) was added per mol of silver nitrate, and stirring was continued for 5 minutes. Thereafter, the pH was adjusted to 6.0 with acetic acid, desalting was carried out in the same manner as described above, and then an aqueous gelatin solution was added and redispersed.

The resulting seed emulsion was spherical grains having an average grain size of 0.23 μm and a coefficient of variation of 0.28.

2) Grain growth from seed emulsion 2 An aqueous solution of ossein gelatin and polyethyleneoxy / polypropyleneoxy-di-succinate-di-sodium salt vigorously stirred at 75 ° C. was added to an aqueous solution of potassium bromide and potassium iodide. And an aqueous solution of silver nitrate were added by the double jet method.

During this time, pH = 5.8 and pH = 9.0 were maintained. After the addition was completed, adjust the pH to 6.0 and use it as a spectral sensitizing dye.
400 mg of anhydrous 5,5'-dichloro-9-ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt
/ Mol AgX was added, desalted in the same manner as above, and then dispersed in an aqueous gelatin solution.

By this method, a tabular iodobromide having an average silver iodide content of 1.5 mol%, a projected area diameter of 0.96 μm, a coefficient of variation of 0.25, and an aspect ratio (projected area diameter / grain thickness ratio) of 4.0. A silver emulsion (D) was prepared.

[Preparation of Sample] Obtained emulsions (A), (B),
5,5'-dichloro-9-at 55 ° C for each of (C) and (D)
Ethyl-3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt anhydride and 5,5'-di- (butoxycarbonyl) -1,1'-di-ethyl-3,3'- Di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt anhydrous
(A) is 975 m per mol of silver halide at a weight ratio of 200: 1.
g, (B) 600 mg, (C) 390 mg, and (D) 500 mg, respectively.

After 10 minutes, appropriate amounts of chloroauric acid, sodium thiosulfate and ammonium thiocyanate were added for chemical ripening. 15 minutes before the end of ripening, 200 mg of potassium iodide was added per mol of silver halide, and then 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene was added in an amount of 3 × 10 per mol of silver halide. ^-After adding ² mol, gelatin was dispersed in an aqueous solution containing 70 g.

Of these four types of ripened emulsions, (A), (B) and (C) were mixed at a weight ratio of 15:65:20 to give Emulsion-I, and (D) was Emulsion-II was used as it was.

The following additives were added to each of the obtained emulsion-I and emulsion-II. The addition amount is shown as the amount per mol of silver halide.

Polymer of General Formula [I] of the Present Invention Amount Described in Table 1 1,1-Dimethylol-1-bromo-1-nitromethane 70 mg t-Butylcatechol 400 mg Polyvinylpyrrolidone (Molecular weight 10.000) 1.0 mg Styrene-maleic anhydride Copolymer 2.5 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 4 g 2-Mercaptobenzimidazole-5-sodium sulfonate 15 mg 2-Mercaptobenzothiazole 10 mg 1-Phenyl-5- Mercaptotetrazole 10mg Trimethylolpropane 9.0g 1,1-Dimethylol-1-bromo-1-nitromethane 10mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1g

[0084]

[Chemical 5]

The additives used in the protective layer liquid are as follows. The added amount is shown as an amount per 1 l of the coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 0.3 g Polymethylmethacrylate (matting agent having an area average particle size of 3.5 μm) 1.1 g Silicon dioxide (area average particle size 1.2 μm matting agent) 0.5g Ludox AM (manufactured by DuPont) colloidal silica 30mg Glyoxal 40% aqueous solution (hardening agent) 1.5ml Bis (vinylsulfonylmethyl) ether (hardening agent) 500mg

[0087]

[Chemical 6]

The coating solution thus obtained was uniformly applied onto a blue-colored polyethylene terephthalate film base having a thickness of 180 μm, which had been undercoated, and dried.

[0089] The coating amount of 0.99 g / m ² at 2.0 g / m ² emulsion layer per side in terms of silver value, the protective layer is a quantity with gelatin
Every two minutes with two slide hopper type coaters
A sample was obtained by simultaneously coating both sides of the emulsion layer and the protective layer at a speed of 90 m.

Composition of processing liquid used (Developer) potassium sulfite 70 g hydroxyethylethylenediamine 15 g trisodium triacetate 8 g 1,4-dihydroxybenzene 28 g boric acid 10 g 5-methylbenzotriazole 0.04 g 1-phenyl-5-mercaptotetrazole 0.01 g Sodium metabisulfite 5g Acetic acid (90%) 13g Triethylene glycol 15g 1-Phenyl-3-pyrazolidone 1.8g 5-Nitroindazole 0.2g Potassium bromide 4g 5-Nitrobenzimidazole 1g Make an aqueous solution of 1l and add sodium hydroxide. The solution was pH 10.5.

To 1.0 l of this developing solution, 3 g of potassium bromide and 4 ml of glacial acetic acid were added as a starter, and the developing tank was filled at the start of running to obtain a working solution.

(Fixer) Sodium thiosulfate-5-hydrate 45g Ethylenediaminetetraacetic acid disodium 0.5g Ammonium thiosulfate 150g Anhydrous sodium sulfite 8g Potassium acetate 10g Aluminum sulfate 10-18 hydrate 10g Sulfuric acid (50wt%) 5g Citric acid 1g Boric acid The pH was adjusted to 4.2 with glacial acetic acid to make an aqueous solution of 7 g 1 l.

The roller transfer type automatic developing machine used in the present invention will be described with reference to the drawings.

In FIG. 1, 1 is a first roller, 2 is a final roller, 3a is a developing tank, 3b is a fixing tank, 3c is a washing tank, 4 is a photosensitive material, 5 is a squeeze section, 6 is a drying section, and 7 is a drying section. The air outlet, a is the developing solution surface, b is the fixing solution surface, and c is the washing water surface. The silver halide photographic light-sensitive material according to the present invention is
It is inserted from the first roller of No. 1 and processed by the processing method of the present invention, and the processing is completed by the last roller of No. 2.

Using the automatic processor of FIG. 1, the transport speed and the number of rollers are increased or decreased as shown in Table 1, and T
And it was evaluated for the following items by changing the _{L 1, L 2, L 3} .
The developing temperature was 35 ° C., the fixing temperature was 30 ° C., and the washing temperature was 18 ° C., and the flow rate of washing water was 3 liters per minute. When the light-sensitive material was subjected to development processing, the circulation stirring amount of the developing solution was 20 liters / minute, and the circulation stirring amount of the fixing solution was 20 liters / minute.

[Sensitometry] The prepared sample was sandwiched between fluorescent intensifying screens KO-250 (manufactured by Konica Corporation), and a tube voltage of 90 KV was applied.
After irradiating with an X-ray of P, 20 mA for 0.05 seconds and exposing by the distance method, the treatment shown in Table 1 was performed.

Sensitometric curves were prepared for the obtained samples to determine the sensitivity. The sensitivity value was obtained as the reciprocal of the X-ray dose required to obtain the density of fog +1.0. The results are expressed as relative sensitivity when the sensitivity of Sample No. 1 is 100.

[Evaluation of Color Remaining Property] The prepared sample was subjected to the developing treatment shown in Table 1 without exposing it, and the transmission density of green light of the treated sample was measured. The larger the value, the more the residual color contamination and the less excellent it is.

[Evaluation of Scratch Resistance] 25 samples were prepared.
After conditioning the humidity for 1 hour under the condition of ℃ and 30% RH, under the same conditions, use a commercially available nylon scrubbing tool and apply a weight of 10 to the area of 2 × 2 cm.
It was rubbed with 0g and at a speed of 2cm per second. After performing the above-mentioned automatic development treatment in an unexposed state, the number of blackened scratches was counted. The obtained results are shown in Table 2.

[0100]

[Table 1]

[0101]

[Table 2]

As shown in Table 2, in the treatment of L ₁ ^0.75 × T = less than 15, the sensitivity is lowered and the residual color is deteriorated.
Further, it can be seen that the fog is increased in the case of processing exceeding L ₁ ^0.75 × T = 40, although there is almost no sensitizing effect.

Also, in the processing of L ₂ > L ₃ , there are problems in fog and residual color. However, it can be seen that an image with high sensitivity and good scratch resistance can be obtained by the processing method according to the present invention, in which the water-soluble polymer of the present invention is added, without causing problems such as deterioration of residual color and increase of fog.

The roller transfer type automatic developing machine used in the present invention will be described with reference to the drawings.

In FIG. 1, 1 is a first roller, 2 is a final roller, 3a is a developing tank, 3b is a fixing tank, 3c is a washing tank, 4 is a photosensitive material, 5 is a squeeze section, 6 is a drying section, and 7 is a drying section. The air outlet, a is the developing solution surface, b is the fixing solution surface, and c is the washing water surface. The silver halide photographic light-sensitive material according to the present invention is
It is inserted from the first roller of No. 1 and processed by the processing method of the present invention, and the processing is completed by the last roller of No. 2.

[0106]

According to the present invention, a high-sensitivity silver halide photographic light-sensitive material having scratch resistance in a rapid processing by an automatic processor and having no residual color contamination on a film after processing can be obtained.

[Brief description of drawings]

FIG. 1 is a cross-sectional view of a roller transport type automatic developing machine.

[Explanation of symbols]

 1 First Roller 2 Final Roller 3a Developing Tank 3b Fixing Tank 3c Water Washing Tank 4 Photosensitive Material 5 Squeeze Section 6 Drying Section 7 Dry Air Outlet a Developer Surface b Fixing Liquid Surface c Washing Water Surface

Claims (1)

[Claims] 1. A silver halide photographic light-sensitive material containing at least one of the polymers represented by the following general formula [I] is subjected to the following steps in a roller-conveying type automatic developing machine comprising development, fixing, washing and drying steps. A method for processing a silver halide photographic light-sensitive material, which comprises processing under the condition represented by the formula. L ₁ ^0.75 × T = 15.0 to 40.0 L ₂ <L _{3 In the} formula, L ₁ is the line length (m) from the entry of the developing tank to the washing tank, and L ₂ is the entry of the developing tank into the developing tank. Line length from the fixing solution surface to the fixing tank surface (m) L ₃ is the line length from the fixing solution surface entry to the washing tank surface (m) T is the time required from the developing solution surface entry to the washing tank entry (Se
represents c). [Chemical 1] In the formula, R ₁ represents a hydrogen atom or an alkyl group having 6 or less carbon atoms, R ₂ and R ₃ each represent a hydrogen atom, a substituted or unsubstituted alkyl group having 10 or less carbon atoms, an aryl group or an aralkyl group, R ₂ and R ₃ may combine with each other to form a nitrogen-containing heterocycle. A represents a monomer unit obtained by copolymerizing a copolymerizable ethylenically unsaturated monomer, L represents a divalent linking group, n represents 0 or 1, m represents 1 or 2, and x represents a mole.
It represents 70 to 100 at a rate of 100 minutes.