JP2001209148A - Silver halide photographic sensitive material for rapid processing and processing method for same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material which does not undergo uneven processing in rapid processing and retains good conveyability and to provide a processing method in which processing is carried out with a boron-free fixing solution. SOLUTION: The side of the silver halide photographic sensitive material with a photosensitive silver halide emulsion layer has a coefficient of kinematic friction of 0.2-0.5 and 6-20 kPa matte degree.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic material, and more particularly, to a silver halide photographic material suitable for rapid processing and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, in the medical field, development processing has been accelerated,
Low replenishment has progressed, and rapid processing such as 45-second processing and 30-second processing has become widespread especially in Japan. In large hospitals, automatic transport devices such as daylight devices are often used. Here, the development processing refers to the steps from development, fixing, washing or stabilization processing, drying and the like of the silver halide photographic material to drying.

A photosensitive material used with the rapid processing requires a reduction in the amount of silver and a reduction in the film thickness in order to improve the developing, fixing and drying properties. Thinning is achieved by reducing the amount of binders such as gelatin, water-soluble polymers, and hydrophobic polymers.However, there is a tendency for the matting agent to peel off, and it is necessary to optimize the particle size and composition of the matting agent. was there.

[0004] A matting agent is usually used for photosensitive materials.
If the amount of the matting agent is less than an appropriate amount or the particle size is too small, the photosensitive materials stick to each other due to moisture or close contact with a vacuum, which causes transport failure. On the other hand, if the amount of the matting agent is too large or if the amount of the matting agent is large, the matting agent tends to peel off.

When a photosensitive material from which a matting agent is easily peeled is transported for a long time by a suction cup transport system, the time during which the matting agent adheres and accumulates on the suction cup and the photosensitive material can be held is shortened. Become.

In the rapid processing, the development time is greatly reduced, so that development unevenness is likely to occur. Developing unevenness may easily occur depending on the components and amounts of the surfactant and the matting agent on the surface of the light-sensitive material, and it is necessary to pay close attention to their use.

On the other hand, in the developing method, a developing solution,
Boron compounds typified by boric acid have often been used in fixing solutions for various purposes, such as pH stabilizers, chelating agents and antioxidants. However, boron compounds are substances that are pointed out in the Water Pollution Law and require careful handling. Therefore, boron compounds need to be reduced or removed.

[0008]

The object of the present invention is to provide a silver halide photographic light-sensitive material which maintains good transportability without deteriorating processing unevenness in rapid processing, and develops with a boron-free fixing solution. It is to provide a processing method.

[0009]

The above object has been attained by the following means.

[0010] 1. A silver halide photographic material characterized by having a dynamic friction coefficient of 0.2 to 0.5 on the side having a photosensitive silver halide emulsion layer and a matte degree of 6 to 20 kPa.

2. A silver halide photograph containing a matting agent having a hydrophilic group on the side having the photosensitive silver halide emulsion layer, and having a contact angle with water of 40 ° or less on the surface having the emulsion layer. Photosensitive material.

3. A silver halide photograph wherein the coefficient of kinetic friction on the side having the photosensitive silver halide emulsion layer is 0.2 to 0.5 and the matting agent on the side having the emulsion layer contains a hydrophilic group. Photosensitive material.

4. 4. The silver halide photographic light-sensitive material according to the above item 3, wherein a contact angle of water on the surface having the photosensitive silver halide emulsion layer is 40 ° or less.

5. 4. The silver halide photographic material as described in the above item 3, wherein the matting degree on the side having the photosensitive silver halide emulsion layer is 6 to 20 kPa.

6. 6. A processing method comprising developing the silver halide photographic light-sensitive material according to any one of the above 1 to 5 with a fixing agent containing no boron.

Hereinafter, the present invention will be described in detail. A matting agent is usually used for a photosensitive material. The main characteristic values of the matting agent include a suction pressure when the photosensitive material is sucked by a smoother described later and a matte degree. In the present invention, the matte degree is 6
The range of ２０20 kPa is preferred. In order to set the matting degree within a preferable range, the average particle diameter of the matting agent is preferably 3 to 9 μm, and is preferably 1.3 to 3 times the dry film thickness of the photosensitive material constituting layer. In addition, 15μ
The number of coarse particles of m or more is preferably 5% or less of the total number, more preferably 2% or less, and particularly preferably 1% or less. The addition amount is preferably from 5 to 100 mg / m ^2, more preferably 20-50 mg / m ^2. The shape is preferably a spherical polymer matting agent. The glass transition temperature (Tg) is preferably from 60 to 150 ° C, and from 80 to 120 ° C.
Is more preferable. Table 1 shows specific examples of matting agents.
Shown in

[0017]

[Table 1]

The monomer of the matting agent containing a hydrophilic group used in the present invention will be described. As the hydrophilic group in the monomer, a carboxyl group, a phosphate group, a sulfonic acid group,
Sulfate groups are preferred. Specifically, acrylic acid, methacrylic acid, styrene sulfonic acid and the like are preferably used. The ratio of the monomer containing a hydrophilic group is 5 to 40 mol%, preferably 10 to 30 mol%. The monomer containing no hydrophilic group used for polymerization is not particularly limited,
Acrylic esters, methacrylic esters, styrenes, vinyl esters and the like are preferably used. For example, methyl methacrylate, ethyl methacrylate, methyl acrylate, ethyl acrylate, styrene and the like are particularly preferable.

The drying conditions for coating and drying the light-sensitive material affect the degree of matting. In the present invention, the drying time is 1 to
For 5 minutes, when the water content of the web with respect to gelatin is 1000% or less, the wet-bulb temperature of the dry air is preferably 15 to 30 ° C.

In the present invention, the dynamic friction coefficient of the photosensitive material is 0.2
~ 0.5 is preferred. Keep the dynamic friction coefficient in the preferred range
For this purpose, for example, an amorphous Si having an average particle size of 1 to 10 μm
O_TwoIncreasing the coefficient of friction by including particles in the outermost layer
There is a law. In addition, mats with a larger particle size than the film thickness of the photosensitive material
It can also be increased by including an agent. Dynamic friction
As means for lowering the coefficient, use a fluorine-containing surfactant
0.2-30mg / m ^TwoIt is preferable to add
10mg / m^TwoIt is more preferred to use.

The preferred fluorine-containing surfactant of the present invention is water-soluble, specifically, 0.1 g / 25 g of water at 25 ° C.
L or more, more preferably 10 g / L or more. Further, those having a surface tension of 150 to 230 μN / cm as measured by a vertical plate method (Wilhelmy method) using a platinum plate with a 0.1 g / L aqueous solution at 25 ° C. are preferable because they are appropriately oriented on the photosensitive material film surface. .

The structural formula of the most preferred fluorine-containing surfactant compound is Rf- (CH ₂ ) _m- (OCH ₂ CH ₂ ) _n -OH.

In the formula, Rf represents a substituted or unsubstituted alkyl, alkenyl or aryl group having at least 3 fluorine atoms and having 1 to 30 carbon atoms. m is 0
5, n is 2 to 50, more preferably 5 to 20.

Preferred fluorine-containing surfactant compounds include the following.

[0025]

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[0026]

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As a means for reducing the dynamic friction coefficient, there is a method described in JP-A-11-65011 in which oils are contained in the outermost layer.

Here, oil is defined as having a solubility in water of 25.
Those which are 10% or less at 0 ° C and liquid at 25 ° C. The average particle size of the dispersed oil droplets may be such that the individual particle size distribution is wide or narrow,
A case where the size of about 0.4 μm occupies 75% or more of the whole is effective in generating fingerprint marks or silver tone. Various surfactants can be used for dispersion. For example, anionic surfactants described in U.S. Pat. Nos. 2,332,027, 2,801,170 and 2,801,171, and anionic and nonionic surfactants described in JP-B-48-9979. Etc. can be used.

Hereinafter, representative examples of the oil that can be used in the present invention will be described. Diethyl adipate, dibutyl adipate, diisobutyl adipate, di-n-hexylethyl adipate, dioctyl adipate, dicyclohexyl azelate, di-2-ethylhexyl azelate, dioctyl sebacate, diisooctyl sebacate, dibutyl succinate, octyl stearate, Dibenzyl phthalate, tri-o-cresyl phosphate, diphenyl-mono-p-tert-butylphenyl phosphate, monophenyl-di-o-chlorophenyl phosphate, monobutyl-dioctyl phosphate, 2,4-di-n-amylphenol, 2,4-di-tert-amylphenol, 4-n-nonylphenol, 2-methyl-4-n-octylphenol, N, N-diethylcaprylamido, N, N-diethyllau Ruamido, glycerol tripropionate, glycerol tributyrate, glycerol mono lactate acetate, tributyl citrate, acetyl triethyl citrate, di -2
-Ethylhexyl adipate, dioctyl sebacate,
Diisooctyl azelate, diethylene glycol dibenzoate, dipropylene glycol benzoate, triethyl citrate, tri (2-ethylhexyl) citrate, acetyl tri-n-butyl citrate, di (isodecyl) 4,5-epoxytetrahydrophthalate,
Oligovinyl ethyl ether, dibutyl phthalate, diisodecyl phthalate, polyethylene oxide (degree of polymerization> 16), glycerol tribubutyrate, ethylene glycol diprolobionate, di (2-ethylhexyl) isobutyrate, butyl laurate, tri- (2-
Ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, silicone oil, dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, isooctyl phthalate,
Diaminophthalate, di-n-octyl phthalate, diamylnaphthalene, triamylnaphthalene, monocaprin, monolaurin, monomyristine, monopalmitin,
Monostearin, monoolein, dicaprin, diproline, dimyristine, dipalmitin, distearin, diolein, 1-stearo-2-palmitin, 1-palmit-3-stearin, 1-palmit-2-stearin,
Triacetin, tricaprin, trilaurin, trimyristin, tripalmitin, tristearin, triolein, tripetroserin, trielsin, triricinolein, linoleostearsin, oleoziercin, linoleoziersin, palmito oleolinorenin, paraffin, linseed oil, large Soybean oil, eno oil, drill oil, thistle oil, kaya oil, walnut oil, soy sauce oil, poppy oil, sunflower oil, azusa oil,
Dry oils such as kwai oil and safflower oil; semi-dry oils such as cottonseed oil, corn oil, sesame oil, rapeseed oil, rice bran oil, lotus oil, mustard oil, pumpkin oil, dehydrated castor oil; peanut oil, olive oil, Examples include camellia oil, sasanqua oil, tea oil, castor oil, hydrogenated castor oil, almont oil, bundling oil, ben oil, and large scale oil. Further, a compound represented by the following general formula (1) can also be used as the oil of the present invention.

[0030]

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In the formula, R represents an alkyl group having 1 to 8 carbon atoms. Other Japanese Patent Application Laid-Open Nos. 50-23823 and 50-626
No. 32, No. 51-26035, No. 51-26036
And the compounds described in JP-A-51-26037 and the like can also be used in the same manner.

Among them, adipic acid, phthalic acid, sebacic acid, esters such as succinic acid, citric acid, fumaric acid, mazeleiic acid, isophthalic acid and phosphoric acid, glycerin esters and paraffins have no adverse effect on photographic light-sensitive materials. It can be conveniently used because it is easily available, chemically stable and easy to handle. Further, dibutyl phthalate, diisodecyl phthalate, di-n-octyl phthalate, glycerol tripropionate, dioctyl sebacate, paraffin and silicone oil are particularly preferred oils in the present invention.

In the present invention, if necessary, a water-soluble or water-insoluble organic low-boiling compound may be used in combination. After the photographic light-sensitive material is coated and dried, it evaporates and almost no longer exists in the layer. Specific examples of these include, for example, methanol, ethanol, propyl alcohol, fluorinated alcohol, acetonitrile, dimethylamide, dioxane, methyl isobutyl ketone, diethylene glycol monoacetate, chloroform, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, cyclohexinol And cyclohexanetetrahydrofuran.

In the present invention, the oil droplets are mainly composed of the above-mentioned oils. The lipophilic photographic coupler, ultraviolet absorber, development inhibitor releasing compound, hydroquinone derivative,
An image fading inhibitor or the like may be contained in the oil droplets.
However, when a large amount of lipophilic photographic additives is used, the pressure resistance of the silver halide photographic light-sensitive material is deteriorated.

The oil used in the present invention is one which can be dispersed in a coating solution without being mixed with the solution and which does not lose oil droplets even when the coating solution is coated and dried under ordinary conditions. To be elected. Among these, preferred are those having a melting point of 25 ° C. or less even when used alone or as a mixture of two or more kinds.
Those that are liquid at ° C. are more preferred.

In the present invention, one or more oil droplets may be formed simultaneously by using oil.
You may mix and use what was separately emulsified and dispersed.

The following are specific examples of oil dispersions. Illustrative oil dispersion Dispersion particle size (μm) O-1: Tris (isopropylphenyl) phosphate 0.20 O-2: Trixylyl phosphate 0.25 O-3: Tributyl phosphate 0.15 O-4: Dioctyl phthalate 0 .15 O-5: dibutyl phthalate 0.20 O-6: dihexyl phthalate 0.15 O-7: tricresyl phosphate 0.20 O-8: o-acetyltriethyl citrate 0.15 O-9: N, N-dimethyl lauryl amide 0.10 O-10: diisodecyl phthalate 0.20 The amount of oil added is 10 to 1 m ² per side of the photosensitive material.
1000 mg is preferable, and 20 to 300 mg is more preferable. The layer to which the oil is added is preferably an emulsion layer or a layer farther from the support than the emulsion layer. Most preferably, it is the outermost layer.

In the present invention, the contact angle of the light-sensitive material is preferably 40 ° or less both before and after the development processing. The contact angle may exceed 50 ° when the amount of the surfactant present on the surface of the outermost layer is small. In order to reduce the contact angle, it is preferable that the surfactant of the general formula (2) is contained in the outermost layer.
g / m ² is preferred. The contact angle can be reduced by using a matting agent having a hydrophilic group or a fluorinated surfactant used in the present invention in combination.

[0039]

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In the formula, R ₁ represents a substituted or unsubstituted alkyl or alkenyl group having 1 to 30 carbon atoms. m1, n
1 may be the same or different, and m1 and n1 are each 1 to 50. M2 and n2 are each 0 to 50;
It is. Specific examples of the compound of the general formula (2) are shown below.

[0041]

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[0042]

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The fixing solution in the method for developing a light-sensitive material of the present invention is characterized in that it does not contain a boron compound represented by boric acid (borate-free). It is preferably prepared.

As the fixing solution in the method for developing a light-sensitive material of the present invention, a composition having a commonly used composition can be used. The fixing solution is generally an aqueous solution comprising a fixing agent and other components.
8-5.8 is preferred. As the fixing agent, those generally known as fixing agents can be used. If necessary, compounds such as a hardening agent, a preservative, a pH buffer, a pH adjuster, and a chelating agent can be added to the fixing solution.

As a mother liquor and a replenisher such as a developing solution, a fixing solution, and other processing solutions (such as a stabilizing solution), it is usual to supply a working solution or a concentrated solution diluted immediately before.

The stock of the mother liquor and the replenisher may be in the form of a working solution, a concentrated solution, a viscous liquid in a semi-kneaded state having a high viscosity, or a method of dissolving a simple substance or a mixture of solid components at the time of use. When a mixture is used, a method in which components that are difficult to react with each other are placed adjacent to each other in layers and then vacuum-packaged, and then opened and dissolved when used, or a method of tableting can be used.

The developer replenishing rate and fixing replenishing amount is preferably not more than the light-sensitive material 1 m ² per 330ml in order to reduce the amount of waste, and more preferably the photosensitive material 1 m ² per replenishing amount is 20 to 200, fixing replenishing amount Is 20-2
00 ml.

As a replenishment method, JP-A-55-12624
No. 3, replenishment by width and feed speed.
Japanese Patent Application Laid-Open No. 1-149515
The controlled area replenishment by the number of continuous processing described in No. 6 may be used.

In the development processing, the total processing time (Dry to Dry) is preferably from 10 to 45 seconds, and more preferably from 10 to 30 seconds, in view of a demand for shortening the time. Here, the total processing time means that the leading end of the photosensitive material is immersed in a developing solution of an automatic developing machine, and then developed, fixed, washed or stabilized,
It refers to the time from drying and other steps to drying.

[0050]

EXAMPLES The present invention will be described below in detail with reference to examples, but embodiments of the present invention are not limited thereto.

Example 1 << Preparation of photosensitive material >> <Preparation of seed emulsion> [A1] Ossein gelatin 24.2 g Distilled water 9657 ml Polypropyleneoxy-polyethyleneoxy-disuccinate sodium salt (10% methanol aqueous solution) 6.78 ml Potassium bromide 10.8 g 10% nitric acid 114 ml [B1] 2.5 mol / L silver nitrate aqueous solution 2825 ml [C1] Potassium bromide 841 g Finished with water to 2825 ml.

[D1] 1.75 mol / L Potassium Bromide Aqueous Solution The following silver potential control amount The solution A1 was added at 42 ° C. using a mixing stirrer described in JP-B-58-58288 and JP-B-58-58289. 464.3 ml of each of the solution B1 and the solution C1 were added by the simultaneous mixing method over 1.5 minutes to form nuclei.

After the addition of the solution B1 and the solution C1 was stopped, the temperature of the solution A1 was raised to 50 ° C. in 40 minutes, the pH was adjusted to 5.0 with 3% KOH, and then the solution B1 was added again. 55.4 ml of the solution C1 was mixed by a double-jet method.
/ Min at a flow rate of 42 minutes. From 42 ℃
The silver potential between the temperature rise to 0 ° C. and the second simultaneous mixing of the solutions B1 and C1 (measured with a silver ion selective electrode using a saturated silver-silver chloride electrode as a reference electrode) was + using the solution D1.
It was controlled to be 8 mV and +16 mV.

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

<Preparation of Tabular Silver Bromide Emulsion> A tabular silver bromide emulsion was prepared using a seed emulsion and the following three kinds of solutions.

[A2] Ossein gelatin 34.03 g Polypropylene oxy-polyethylene oxy-disuccinate sodium salt (10% aqueous methanol solution) 2.25 ml Seed emulsion 1. Equivalent to 1.218 mol Make up to 3669 ml with water.

[B2] Potassium bromide 1747 g Finished to 3669 ml with water.

[C2] Silver nitrate 2493 g Finished to 4193 ml with water.

The solution A2 was vigorously stirred in the reaction vessel while maintaining the temperature at 50 ° C., and the total amount of the solution B2 and the solution C2 was added to the solution A1.
It took 00 minutes to add by the simultaneous mixing method. During this time, pH
Was kept at 9.0 by KOH solution, and pAg was kept at 8.6. Here, the addition rates of the solution B2 and the solution C2 were changed functionally with respect to time to match the critical growth rate. That is, they were added at such a rate that no new small particles were generated and that they did not become multi-components due to Ostwald ripening.

Thereafter, the emulsion was cooled to 40 ° C., and 1800 ml of an aqueous solution of 13.8% phenylcarbamoyl-modified gelatin having a substitution rate of 90% was added as a flocculant, followed by stirring for 3 minutes. Further, the pH of the emulsion was adjusted to 4.6 by adding a 56% aqueous solution of acetic acid, stirred for 3 minutes, and allowed to stand for 20 minutes. The supernatant was drained by decantation, and 11.25 L of distilled water was further added and stirred. After placement, the supernatant was drained.

Subsequently, an aqueous solution of gelatin and sodium carbonate 1
A 0% aqueous solution was added to adjust the pH to 5.80, and the mixture was stirred at 50 ° C. for 30 minutes and redispersed. After redistribution, 4
The pH was adjusted to 5.80 and the pAg to 8.06 at 0 ° C.

When the obtained silver halide emulsion was observed with an electron microscope, the average grain size was 0.84 μm and the average thickness was 0.1 mm.
Tabular silver halide grains having a size of 16 μm, an average aspect ratio of about 5.3, and a variation coefficient of the particle size distribution of 20% were obtained. The amount of gelatin at the end of physical ripening was 15.9 g per mol of silver halide.

The above-prepared emulsion was treated at 55 ° C. with 11.3 mg of adenine per mol of silver halide and the following spectral sensitizing dye A
450 mg and B45 mg were added, and 4-hydroxy-6-methyl-1,3,3a, 7-tetrazaindene 1 was further added.
00 mg was added. After 10 minutes, 3.5 mg of chloroauric acid, 10 mg of sodium thiosulfate and 100 mg of ammonium thiocyanate were added. After 40 minutes, 0.3 mol of the following silver iodide fine grains was added, and after 10 minutes, 5 mg of triphenylphosphine selenide was added.
500 mg of hydroxy-6-methyl-1,3,3a, 7-tetrazaindene were added. Five minutes later, 13 g of trimethylolpropane and 30 g of gelatin were added, followed by rapid cooling to gel the emulsion to complete the chemical sensitization.

(Spectral sensitizing dye) Spectral sensitizing dye A: 5,5'-di-chloro-9-ethyl-
Anhydride of 3,3'-di- (3-sulfopropyl) oxacarbocyanine sodium salt Spectral sensitizing dye B: 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3 ' -Anhydride of di- (4-sulfobutyl) benzimidazolocarbocyanine sodium salt <Preparation of silver iodide fine particles> [A3] Ossein gelatin 100 g Potassium iodide 8.5 g Finished to 2,000 ml with distilled water.

[B3] 360 g of silver nitrate Finished to 605 ml with distilled water.

[C3] 352 g of potassium iodide Finished to 605 ml with distilled water.

Solution A3 was added to the reaction vessel, and while stirring at 40 ° C., solution B3 and solution C3 were added at a constant speed over 30 minutes by the simultaneous mixing method. The pAg during the addition was kept at 13.5 by a conventional pAg control means. The formed silver iodide was a mixture of β-AgI and γ-AgI having an average grain size of 0.06 μm.

<Preparation of Subbed Support> Thickness of 175 μm
m, 8 W · min / m ^{2 on} both sides of a polyethylene terephthalate (PET) base colored blue at a concentration of 0.17
After the corona discharge treatment, the undercoating liquid is applied, and 110 ° C.
For 1 minute to obtain a subbed support.

<Preparation of Photosensitive Material> Three layers were simultaneously coated on both surfaces of the undercoated support as the first layer from the side closer to the support.

[First Layer: Dye Layer] Amount added per side Inert ossein gelatin 0.1 g / m ² Filter dye A (solid dispersion) 30 mg / m ² Polymer latex (glass transition point 40 ° C.) 70 mg / m ²

[0071]

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[Second Layer: Emulsion Layer] The addition amounts of the components other than the chemically sensitized emulsion and gelatin are shown per mol of silver halide.

The above chemically sensitized emulsion (silver amount per side) 1.5 g / m ² inert ossein gelatin (per side) 1.45 g / m ² 1,1-dimethylol-1-bromo-1-nitromethane 70 mg polyvinylpyrrolidone (Molecular weight 10,000) 0.7 g Styrene-maleic anhydride copolymer 0.85 g Nitrophenyl-triphenylphosphonium chloride 2.8 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 0 g 1-phenyl-5-mercaptotetrazole 8.5 mg colloidal silica (Ludox AM manufactured by DuPont) 13 g t-butylcatechol 150 mg ammonium 2,4-dihydroxybenzenesulfonate 1.7 g thallium nitrate 55 mg trimethylolpropane 6.5 g dextran ( Average molecular weight 40,000) .2g sodium polystyrene sulfonate (average molecular weight 300,000) 1.3 g Third Layer: Protective Layer] per surface amount Inner toe Sane gelatin 0.70 g / m ² Sodium - di (n- hexyl) sulfosuccinate 5mg / m ² sodium-i-amyl-n-decylsulfosuccinate 15 mg / m ² C ₁₁ H ₂₃ -CONH- (CH ₂ CH ₂ O) ₅ H 25 mg / m ² surfactant 2-2 25 mg / m ² dextran ( (Average molecular weight: 40,000) 0.15 g / m ² 1,2-bis (vinylsulfonylacetamido) ethane 50 mg / m ² Preservative 1 mg / m ² Matting agent Table 2 Dynamic friction coefficient reducing agent Table 2

[0074]

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[0075]

[Table 2]

When the dry film thickness of the obtained sample was measured by an electron microscope, it was about 3 μm.

<< Evaluation >> This sample was evaluated by the following method, and the results are shown in Table 2.

<Matte Degree> After the sample has been conditioned for 2 hours at 23 ° C. and 55% RH, the suction pressure is measured using a smoother (manufactured by Toden Kogyo Co., Ltd.). A larger value indicates a higher matte degree.

<Dynamic friction coefficient> Measured according to the method specified in JIS K7125.

<Contact angle> After developing with an automatic developing machine,
The contact angle is measured 15 seconds after water at 25 ° C. is dropped on the surface of the photosensitive material.

<Processing Unevenness> A sample cut to 18 cm × 30 cm was uniformly exposed to a density of 1.1 ± 0.05, developed by the following automatic developing machine, and visually observed for density unevenness. . The larger the value, the smaller the processing unevenness.

Evaluation Criteria 3. No processing unevenness 2. Processing unevenness is slight but not noticeable. Processing unevenness, but practically acceptable level Processing irregularities are noticeable and impractical. [Developing process] The developing process was performed in a 30-second processing mode of an automatic developing machine SRX-701 (manufactured by Konica Corporation). In addition,
The washing of the transfer rack between development and fixing was stopped, and the pressure spring of the transfer rack was removed to set conditions under which development unevenness was likely to occur.
The amount of replenisher for development and fixing is quadruple (25.4 cm × 30.5
cm) Set to 7 ml per sheet, and Konica Medical Film SR-G (manufactured by Konica Corporation)
After processing 00 sheets, the sample of the present invention was processed.

(Developer Formulation) Part-A (for finishing 10 liters) Potassium hydroxide 450 g Potassium sulfite (50% solution) 2280 g Diethylenetetraminepentaacetic acid 120 g Sodium hydrogen carbonate 132 g 5-methylbenzotriazole 1.2 g 1-phenyl -5-mercaptotetrazole 0.2 g 1,4-dihydroxybenzene 340 g Water is added to make up to 5000 ml.

Part-B (for 10 liter finishing) Glacial acetic acid 170 g Triethylene glycol 185 g 1-phenyl-3-pyrazolidone 22 g 5-nitroindazole 0.4 g Starter solution (for 1 liter finishing) Glacial acetic acid 120 g potassium bromide 225 g water To make 1000 ml.

(Preparation of developer)
t-A and Part-B were added at the same time, water was added while stirring and dissolving to make up to 10 liters, and pH was adjusted to 1 with glacial acetic acid.
Adjusted to 0.5 to obtain a developer. 20 ml of a starter solution was added per liter of the developer, and the pH was adjusted.
Was adjusted to 10.4 to obtain a working solution.

(Fixing Solution Formulation) Part-A (for finishing 18 liters) Ammonium thiosulfate (70 g / L) 6000 g Sodium sulfite 110 g Sodium acetate trihydrate 450 g Sodium citrate 50 g Sodium gluconate 3 g 1- (N, N-) 18 g of dimethylamino) -ethyl-5-mercaptotetrazole Water is added to make up to 8000 ml.

Part-B 800 g of aluminum sulfate (Preparation of fixing solution) Part-A and P were added to about 5 liters of water.
Simultaneously add art-B, add water while stirring and dissolving to make up to 18 liters, adjust the pH to 4.4 with sulfuric acid and sodium hydroxide, and use this as a fixer solution and fixer replenisher. And

The processing temperature was 35 ° C. for development and 33 ° for fixing.
° C, washing at 20 ° C, and drying at 45 ° C. <High-moisture sticking> After the sample was spread at 23 ° C and 80% RH for 2 hours, three identical samples cut to 10 cm x 10 cm were stacked, and an acrylic plate of 10 cm x 10 cm (5 mm thick) was placed on top. Then, a weight of 1 kg is placed thereon and left for 24 hours. The three stacked samples are peeled off, and the level of sticking is visually evaluated.

Evaluation Criteria No sticking 4. 2. Slightly sticky but not noticeable There is sticking, but practically acceptable. There are many sticks and it is not practical 1. <Sucker transportability> Hollow hemispherical soft polyurethane made with a 2.7 cm diameter opening in a hole with a diameter of about 9 mm at the center of the suction cup made of hard plastic with a diameter of about 9 mm and a length of about 14 cm Insert a cylindrical bar. When the suction cup is pressed against the sample by holding the cylindrical rod, the suction cup is deformed and becomes flat, the air inside is eliminated, and the sample is adhered in vacuum. Prepare three samples of 18cm × 30cm, and repeat the suction and forced peeling 200 times while changing the front and back of two of them, then measure the holding time until another sample is vacuum adhered and falls naturally. The evaluation was made to evaluate the sucker transportability. The evaluation was performed in an atmosphere of 23 ° C. and 55% RH.

Evaluation criteria: 91 seconds or more: good holding time and sufficient margin 46 to 90 seconds: holding time is practically acceptable level 16 to 45 seconds: holding time is slightly short and impractical 15 seconds or less: clearly holding Short time Example 2 The same sample as in Example 1 was prepared except that the protective layer of Example 1 was changed as described below, and the contact angle, processing unevenness, high-moisture sticking, and suction cup transferability were evaluated. . In order to reduce the contact angle, surfactant 2-2 or comparative compound A was added to the protective layer. Table 3 shows the evaluation results.

[Third Layer: Protective Layer] Amount added per side Inert ossein gelatin 0.70 g / m ² sodium-i-amyl-n-decylsulfosuccinate 13 mg / m ² 1,2-bis (vinylsulfonylacetamide) ) Ethane 50 mg / m ² Preservative 1 mg / m ² Matting agent Table 3 Surfactant 2-2 Table 3 Comparison A: (C ₉ H ₁₉ ) ₂ C ₆ H ₃ —O— (CH ₂ CH ₂ O) ₁₂ SO ₃ Na listed in Table 3

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[Table 3]

Example 3 The sample prepared in Example 1 was subjected to the above-mentioned development processing and development processing using a fixing solution containing 3.1 g / L of boric acid to evaluate processing unevenness. Table 4 shows the evaluation results.

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[Table 4]

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According to the present invention, it is possible to provide a silver halide photographic material maintaining good transportability without deteriorating processing unevenness in rapid processing, and to provide a processing method for developing with a boron-free fixing solution. can do.

Claims (6)

[Claims] A kinetic coefficient of friction on the side having a light-sensitive silver halide emulsion layer is 0.2 to 0.5 and a matte degree is 6
A silver halide photographic light-sensitive material, wherein the pressure is 20 to 20 kPa. 2. The method according to claim 1, further comprising a matting agent having a hydrophilic group on the side having the photosensitive silver halide emulsion layer, wherein a contact angle of water on the surface having the emulsion layer is 40 ° or less. Silver halide photographic light-sensitive material. 3. The method according to claim 1, wherein the coefficient of kinetic friction on the side having the photosensitive silver halide emulsion layer is 0.2 to 0.5, and the matting agent on the side having the emulsion layer contains a hydrophilic group. Silver halide photographic light-sensitive material. 4. The silver halide photographic light-sensitive material according to claim 3, wherein the contact angle with water on the surface having the photosensitive silver halide emulsion layer is 40 ° or less. 5. The silver halide photographic material according to claim 3, wherein the matting degree on the side having the photosensitive silver halide emulsion layer is 6 to 20 kPa. 6. A processing method comprising developing the silver halide photographic light-sensitive material according to claim 1 with a fixing agent containing no boron.