JPH0934059A - Method for processing silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a silver halide photographic sensitive material prevented from occurrence of static marks in a rapid processing and peeling of film after processing and to provide its processing method. SOLUTION: This silver halide photographic sensitive material is processed in an automatic developing machine provided with a drying device using heat rollers and a surface electric resistivity is <=1×10<12> Ω/cm (23 deg.C and 55% releative humidity) after the processing, and it is preferred that the photosensitive material contains at least one kind of conductive polymer and conductive metal oxide particles and their colloid.

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 light-sensitive material, and more specifically, it is free from static marks and peels off a processed film in an automatic processor having a drying device with a heat roller. The present invention relates to a good silver halide photographic light-sensitive material having no film and a film, and a processing method thereof.

[0002]

2. Description of the Related Art In recent years, rapid processing has become widespread in silver halide photographic light-sensitive materials and it has become possible to shorten the processing time. In reality, it is required to have a quick processability.

As a means for accelerating the developability and dryness of the light-sensitive material, for example, it is known to reduce the amount of binder of silver halide grains to reduce the load of development and drying.

Further, in order to improve the drying property of the silver halide photographic light-sensitive material, for example, JP-A-6-273899 or 6-
No. 250350 discloses a processing method using an automatic processor having a drying device using a heat roller.

However, as a matter of course, the reduction of the binder amount is not preferable because the physical properties of the film are deteriorated, and especially when the treatment is rapidly performed by an automatic processor having a drying device with a heat roller, the drying efficiency is improved. However, there is a problem that the processed film is peeled off due to contact with the heat roller.

On the other hand, a silver halide photographic light-sensitive material is easily charged under low humidity, and when it is discharged, fog called a static mark is generated. For medical films,
Antistatic is considered to be an important elemental technology because static marks can cause misdiagnosis. Many proposals have been made for this antistatic method, for example, polyalkylene oxide-based surfactants are well known.

However, most of the polyalkylene oxide-based surfactants have the drawback that when added to an amount having an antistatic ability, the physical properties of the film deteriorate and the film peels off when dried with a heat roller as described above. Was there.

Further, in recent years, a method for processing a silver halide photographic light-sensitive material using reductones as a developing agent which replaces hydroquinone from the environment has been described, for example, in US Pat.
No. 323, European Patent No. 9,202,849 and the like. However, the silver halide photographic light-sensitive material produced by the processing method has a problem that film peeling is likely to occur when dried with a heat roller as in the above.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide a silver halide photographic light-sensitive material in which static marks are not generated and a processed film does not peel off, and a processing method thereof.

[0010]

The objects of the present invention have been solved by the following.

(1) In the processing method of a silver halide photographic light-sensitive material processed by an automatic processor having a drying device with a heat roller, the surface electric resistance value of the silver halide photographic light-sensitive material after processing is 1 × 10. ¹² Ω / cm (23 ° C, 5
5% RH) or less, a method for processing a silver halide photographic light-sensitive material.

(2) The silver halide photographic material according to item (1), characterized in that the silver halide photographic light-sensitive material contains at least one selected from a conductive polymer, conductive metal oxide particles or a colloid thereof. Method of processing photosensitive material.

(3) A method of processing a silver halide photographic light-sensitive material, which is processed with a developer containing a reductone,
The surface electric resistance value after the treatment is 1 × 10 ¹² Ω / cm (23
C., 55% RH) or less, a method for processing a silver halide photographic light-sensitive material.

(4) The silver halide photographic material according to item (3), wherein the silver halide photographic light-sensitive material contains at least one kind selected from conductive polymers, conductive metal oxide particles or colloids thereof. Method of processing photosensitive material.

(5) The method for processing a silver halide photographic light-sensitive material as described in the above item (3) or (4), wherein the processing is carried out by an automatic processor having a drying device using a heat roller.

Hereinafter, the present invention will be described in detail.

The present invention relates to a silver halide photographic light-sensitive material processed by an automatic processor having a heat roller drying device.

The heat roller is a metal having good heat conductivity (for example, aluminum, stainless steel, iron) equipped with a heat source (for example, a metal resistance heating element, a halogen lamp, etc.) capable of controlling the temperature for heating the outer peripheral portion in the central portion. , Copper or the like) or a plastic material (for example, Bakelite or the like), the outermost peripheral portion of which is covered with Teflon or silicone rubber and the outer periphery is appropriately heated.

Particularly preferred is Teflon.

The transport roller having the heat source of the present invention inside the roller has a diameter of 12 to 80 mm and a length of 30 to 110.
cm is preferably used.

The surface temperature of the heat roller is preferably 60 to 150 ° C, more preferably 80 to 120.
° C.

The conveying roller having a heat source inside the roller of the present invention may be a staggered type or an opposing type, but an opposing type is particularly preferable.

As the drying method, a method using a heat roller and an infrared radiation drying method may be used in combination. Further, both drying methods may be combined with a conventional drying method of blowing hot air.

The heat roller referred to in the present invention refers to the roller shown by 3 in the side sectional view of the automatic processor shown in FIG. 1, and the film after washing is quickly dried by heating this roller. Is.

In the present invention, the present invention can be applied to any automatic developing machine having a drying device with at least one heat roller, such as a heat roller and a warm air drying device or a heat roller and an infrared radiation drying device. The present invention can be applied to a case where the above are combined and dried. The surface temperature of the heat roller is preferably between 60 ° C and 90 ° C.

The silver halide photographic light-sensitive material of the present invention contains at least one selected from conductive polymers, conductive metal oxide particles or colloids thereof. The layer to be contained may be a silver halide photographic light-sensitive material constituent layer, preferably a subbing layer on the surface of the support or a hydrophilic layer on the subbing layer, for example a gelatin layer, a silver halide emulsion layer or a backing. A layer, a protective layer, etc. are mentioned.

Next, the conductive polymer used in the present invention will be described. Examples of the conductive polymer of the present invention include water-soluble polymers having at least one conductive group selected from a sulfonic acid group, a sulfuric acid ester group, a tertiary ammonium salt, a quaternary ammonium salt, a carboxyl group and a polyethylene oxide group. Among these groups, a sulfonic acid group, a sulfate group, and a quaternary ammonium base are preferable. The conductive groups require at least 5% by weight per polymer molecule.

Specific examples of compounds of the water-soluble conductive polymer used in the present invention will be given below. In addition to the following, specific compounds include P-10 to P-37 described in JP-A No. 4-80744 by the same applicant as the present invention, and likewise used preferably.

[0029]

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[0030]

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In the above P-1 to P-9, x,
y and z represent the mol% of each monomer component, and M represents the average molecular weight (in the present specification, the average molecular weight refers to the number average molecular weight).

Next, the conductive metal oxide particles or colloids thereof that can be used in the present invention will be described.

The conductive metal oxide generally has high conductivity when the crystallinity is high, but it is necessary to consider the particle size and the ratio of particle / binder for light scattering, and the silver halide emulsion. Metal oxide fine particles having low crystallinity are preferred because they often cause problems in terms of processability such as fogging of the toner and difficulty of uniform dispersion. Examples of the metal oxide fine particles include ZnO and Ti
O ₂ , SnO ₂ , Al ₂ O ₃ , In ₂ O ₃ , SiO ₂ , Mg
O, BaO, good MoO like, in particular ZnO, TiO ₂ and SnO ₂ are preferred, SnO ₂ are particularly preferred. Further, as an example in which a heteroatom is doped, Al, In, etc. for ZnO, Nb, Ta, etc. for TiO ₂ , S
Examples of nO ₂ include Nb, Sb, and halogen elements.

The metal oxide colloid used in the present invention, particularly the colloidal SnO ₂ sol comprising stannic oxide, can be prepared by dispersing ultrafine SnO ₂ particles in a suitable solvent, or by using a solvent. Any method such as a method of producing from a decomposition reaction of a soluble Sn compound in a solvent may be used.

Regarding the method for producing SnO ₂ ultrafine particles,
Especially the temperature condition is important, and the method involving high temperature heat treatment is
When the heat treatment is unavoidably required because the growth of primary particles and the phenomenon that the crystallinity increases, the heat treatment should be performed at 300 ° C. or lower, preferably 200 ° C. or lower, and more preferably 150 ° C. or lower. However, 25 ℃
Heating from to 150 ° C. is a means preferably selected when dispersion in a binder is considered.

Further, due to recent advances in powder manufacturing technology, in manufacturing ultrafine particles, a method of spraying a compound manufactured by a wet method into an electric furnace, a high temperature thermal decomposition method of an organometallic compound, etc. have been developed. However, it is economically not preferable to redisperse ultrafine particles produced by such a method in a solvent, and it causes serious defects as a photographic light-sensitive material such as generation of aggregated particles. there is a possibility. For this reason, the method of redispersing in a solvent after the production process in which only the metal oxide is isolated is not adopted in the present invention which is used as a photographic antistatic agent.
However, when the compatibility between the binder and the solvent of the SnO ₂ sol is poor, it is necessary to replace the solvent. In such a case, another compound having good compatibility with the solvent of the SnO ₂ sol or good dispersion stability should be used. Add an appropriate amount of SnO ₂ sol to S
nO ₂ ultrafine particles and a compound added in an appropriate amount are 300 ° C. or less, preferably 200 ° C. or less, more preferably 150 ° C.
After being dried and separated by the following heating, it is redispersed in another solvent.

A method for producing a Sn compound soluble in a solvent from a decomposition reaction in the solvent will be described below. The solvent-soluble Sn compound is a compound containing an oxo anion such as K ₂ SnO ₃ .3H ₂ O, a water-soluble halide such as SnCl ₄ , R ′ ₂ SnR ₂ , R ₃ SnX, R ₂ Sn
A compound having a structure of X ₂ (wherein R and R ′ represent an alkyl group), for example, (CH ₃ ) ₃ SnCl. (Pyridine), (C ₄ H ₉ ) ₂ Sn (O ₂ CC ₂ H ₅ ) _{2 and} other organic metal compounds, and oxo salts such as Sn (SO ₄ ) ₂ .2H ₂ O. As a method for producing a SnO ₂ sol using these Sn compounds soluble in a solvent, a physical method such as heating and pressurizing, a chemical method such as oxidation, reduction and hydrolysis after dissolution in a solvent, or After passing through the intermediate, Sn
There is a method for producing an O ₂ sol. As an example
The method for producing SnO ₂ sol described in No. 5-6616 is described. SnCl ₄ is dissolved in 100 times volume of distilled water to form a precipitate of stannic hydroxide as an intermediate. Ammonia water is added to this stannic hydroxide to make it slightly alkaline and dissolve. Then, the mixture is heated until the smell of ammonia disappears, whereby a colloidal SnO ₂ sol is obtained. In this example,
Water was used as the solvent, but alcohol solvents such as methanol, ethanol, and isopropanol; ether solvents such as tetrahydrofuran, dioxane and diethyl ether; aliphatic organic solvents such as hexane and heptane; aromatic organic solvents such as benzene and pyridine; Various solvents can be used depending on the compound, and the present invention has no particular limitation on the solvent. Preferably, solvents such as water and alcohols are selected.

In the method of producing from a decomposition reaction of a solvent-soluble Sn compound in a solvent, a compound containing an element other than Sn which is soluble in the solvent may be added during the process. For example, adding a fluorine-containing compound soluble in a solvent,
This is the addition of a metal compound that can take a trivalent or pentavalent coordination number that is soluble in a solvent.

The solvent-soluble fluorine-containing compound may be either an ionic fluoride or a covalent fluoride. For example,
HF, or metal fluorides such as KHF ₂ , SbF ₃ and MoF ₆ , compounds that generate fluoro complex anions such as NH ₄ MnF ₃ and NH ₄ BiF ₄ , inorganic molecular substances such as BrF ₃ , SF ₄ and SF ₆ Fluoride, CF ₃ I, CF ₃ COOH, P
An organic fluorine compound such as (CF ₃ ) ₃ can be used, but when the solvent is water, a combination of a fluorine-containing compound and a non-volatile acid can be used, such as a combination of CaF ₂ and sulfuric acid. .

The compound of a metal soluble in a solvent and capable of having a trivalent or pentavalent coordination number means a group III element such as Al, Ga, In and Tl or a V such as P, As, Sb and Bi.
Group elements, Nb, which can have a trivalent or pentavalent coordination number,
It is a group of compounds containing transition metals such as V, Ti, Cr, Mo, Fe, Co, and Ni.

The conductive polymer contained in the silver halide photographic light-sensitive material of the present invention is preferably added in an amount of 0.001 to 10 g per unit m ^{2 in} terms of solid content.
It is particularly preferable to add 0.05 to 5 g.

The conductive metal oxide particles or colloids thereof used in the silver halide photographic light-sensitive material of the present invention are contained in an amount of 0.05 to ² .
It is preferable to add 0 g, particularly preferably 0.1 to 1
It is to add 0 g. Among the conductive metal oxide particles or colloids thereof, particularly preferred is a colloid of conductive metal oxide particles.

These conductive materials may be used alone or in combination, and further different conductive materials may be used in different layers.

The silver halide photographic light-sensitive material of the present invention has a surface electric resistance of 1 × 10 ¹² Ω / cm (23
C., 55% RH) or less. It is preferable that the surface electric resistance value is 1 × 10 ¹⁰ Ω / cm or less so that the object effect of the present invention can be more favorably achieved. In addition, the measuring method of the surface electric resistance is a teraohm meter V manufactured by Kawaguchi Electric Co., Ltd.
Using E-30, applied voltage 100v, 23 ° C., RH55
%.

When the silver halide photographic light-sensitive material of the present invention is treated with a developer containing a reductone as a developing agent, the surface electric resistance value after treatment is 1 × 10 ¹² Ω / cm.
(23 ° C., 55% RH) or less.

The reductone of the developing agent used here is ascorbic acid or its derivative and can be represented by the following general formula (A).

[0047]

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In the formula, R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted amino group,
It represents a substituted or unsubstituted alkylthio group, and R ₁ and R ₂ may combine with each other to form a ring. k represents 0 or 1, and when k is 1, X represents a -CO- or -CS- group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

Among the compounds represented by the general formula (A), a compound represented by the following general formula (Aa) in which R ₁ and R ₂ are bonded to each other to form a ring is particularly preferable.

[0050]

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In the formula, R ₃ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a sulfo group, a carboxyl group, It represents an amide group or a sulfonamide group, Y ₁ represents O or S, and Y ₂ represents O, S or NR ₄ . R ₄ represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. M ₁ and M ₂ each represent a hydrogen atom or an alkali metal atom.

The above general formula (A) or general formula (Aa)
Examples of compounds represented by are shown below, but the present invention is not limited thereto.

[0053]

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[0054]

[Chemical 6]

Typical of these compounds is L-ascorbic acid or its derivative, which is commercially available or can be easily synthesized by a known synthesis method. The amount of reductone used may be 1 to 100 g per liter of the developer.

The silver halide composition of the silver halide emulsion used in the silver halide photographic light-sensitive material of the present invention may be arbitrary, for example, any of silver chloride, silver bromide, silver iodobromide, silver chloroiodobromide and the like. You may use the silver halide of. A preferred silver halide composition is a silver iodobromide emulsion containing 30 mol% or less of silver iodide.

If the halogenated particles have the constitution of the present invention,
It may be of any crystal type, for example a cube,
It may be a single crystal such as an octahedron or a tetrahedron, or may be polytwin particles having various shapes.

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 (1
(Dec. 1978), pp. 22-23, "Emulsion".
Preparation and Types ”, 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, for example, T.I. H. By James “The
Theory of the Photographi
C. Process "4th edition, published by Macmillan (1977), pages 38-104, GF.
Duffin's "Photographic Emul"
"Sion Chemistry", Focal Pre
ss (1966), P. "Chimie et Physique Photo by Glafkids
published by graphique "Paul Montel Inc. (1
967) or V.S. L. "Mak" by Zelikman et al.
ing And Coating Photograph
Hic Emulsion "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,
The particles can be produced using particle preparation conditions such as a conversion method and a core / shell method, and 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 monodisperse emulsions having a narrow grain size distribution or polydisperse emulsions having a wide grain size distribution. Good. Here, the monodisperse emulsion means a silver halide emulsion having a variation coefficient of 0.20 or less in terms of grain size as defined in JP-A-60-162244, for example.

The monodisperse emulsion has an average grain size of 0.1 μm.
silver halide grains larger than m, at least 95
Emulsions are included in which the wt% of the grains are within ± 40% of the average grain diameter. Also, the average particle size is 0.25 to 2 μm.
At least 95 wt% or at least 95% in quantity
Also, a silver halide emulsion in which the above silver halide grains have a mean grain size of ± 20% is included.

The method for producing the above-mentioned monodisperse emulsion is known, and is described in, for example, J. Photo. Sci, 12.242-251, (19
63), JP-A-48-36890, and JP-A-52-1636.
No. 4, No. 55-142329, No. 58-49938
No. 1,413,748, U.S. Pat.
No. 4,628, 3,655,394 and the like.

For the emulsion used in the silver halide photographic light-sensitive material of the present invention, a seed crystal is used as a method for obtaining the above monodisperse emulsion, and a silver ion and a halide ion are supplied using this seed crystal as a growth nucleus. A grown emulsion 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).
May be 2 or more tabular grains.

Preferred tabular grains have an aspect ratio of 3 or more and 50 or less, and more preferably 3 or more and 20 or less. In addition, the spherical equivalent spherical diameter of the particles is 0.2 to 30 μm.
m, and more preferably 0.4 to 10 μm. Further, the thickness of the particles is preferably 0.5 μm or less, more preferably 0.3 μm 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 2,112,157.
Nos. 4,414,310 and 4,434,2
No. 26, etc., and emulsions 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. The emulsion as a particularly preferred embodiment is a silver halide grain having substantially two distinct layered structures (core / shell structure) composed 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 40 mol%.
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. The silver halide other than the 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.

The method for producing the above-mentioned core / shell type emulsion is known, and is described in, for example, J. Photo. Sci, 24.198. (1
976), U.S. Pat. Nos. 2,592,250 and 3,50
5,068, 4,210,450, 4,44
4,877 or JP-A-60-143331 can be referred to.

The emulsion may be subjected to a Nudel washing method, a flocculation sedimentation method or the like in order to remove soluble salts. Preferred washing methods include, for example, Japanese Patent Publication No. 35-16.
No. 086, which uses a sulfo group-containing aromatic hydrocarbon-based aldehyde resin, or JP-A-2-7037, which describes a desalting method using a polymer flocculant G-3, G-8, etc. be able to.

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) N
o. 17643 (December 1978), (RD) No.
18716 (November 1979) and (RD) No. 3
Various compounds described in 08119 (December 1989) can be used. These three (RD)
The types and locations of the compounds described in 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 IVA Desensitizing dye 23 IV 998 IVB Dye 25 -26 VIII 649-650 1003 VIII Development accelerator 29 XXI 648 Upper right fog inhibitor / stabilizer 24 IV 649 Upper right 1006-7 VI Whitening agent 24 V 998 V Hardener 26 X 651 Left 1004-5 X Surfactant 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 halogenation of the present invention The support used for the silver photographic light-sensitive material is described in RD above. Examples of suitable supports include polyethylene terephthalate film and the like, and the surface of the support is provided with an undercoat layer to improve the adhesiveness of the coating layer, corona discharge or ultraviolet irradiation. Good.

The hydrophilic colloid layer of the silver halide photographic light-sensitive material according to the present invention specifically 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, an antihalation layer and a backing layer.

For the hydrophilic colloid layer, 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. Examples of synthetic polymers other than gelatin include cellulose derivatives such as hydroxyethyl cellulose,
A homo- or copolymer such as polyvinyl alcohol, polyvinyl alcohol partial acetal, poly-N-vinyl pyrrolidone, polyacrylic acid and polyacrylamide can be used.

The photographic processing of the light-sensitive material of the present invention is carried out, for example, by the processing solutions described in RD-17643, XX to XXI, pages 29 to 30 or 308119, XX to XXI, 1011 to 1012. May be processed. This process may be either a monochrome photographic process for forming a silver image or a color photographic process for forming a dye image. The processing temperature is usually in the range of 18 ° C to 50 ° C.

For the developing solution, known agents such as preservatives, alkali agents, pH buffers, antifoggants, hardeners, development accelerators, surfactants, defoamers, toning agents, and water softeners can be used. A solubilizing agent, a viscosity imparting agent, etc. may be used as necessary.

A fixing agent such as thiosulfate or thiocyanate is used in the fixing solution, and a water-soluble aluminum salt such as aluminum sulfate or potassium alum may be contained as a hardening agent. In addition, it may contain a preservative, a pH adjuster, a water softener and the like.

[0083]

The present invention will be further described with reference to the following examples, but the present invention is not limited thereto.

Example 1 (Preparation 1 of Conductive Metal Oxide Colloid Solution) 65 g of stannic chloride hydrate was mixed with 2000 cc of water / ethanol mixed solution.
To obtain a homogeneous solution. Then, this was boiled to obtain a coprecipitate. The resulting precipitate is removed by decantation, and the precipitate is washed with distilled water many times. Silver nitrate was dropped into distilled water after washing the precipitate, and after confirming that there was no reaction of chlorine ions, 1000 cc of distilled water was added to bring the total amount to 2000.
cc. Add 40cc of 30% ammonia water,
It was heated in a water bath to obtain a colloidal gel dispersion. This colloidal gel dispersion is designated as dispersion A-1.

(Preparation of Conductive Metal Oxide Colloid Solution 2) 65 g of stannic chloride hydrate and antimony trichloride 1.
0 g was dissolved in 2000 cc of water / ethanol mixed solution to obtain a uniform solution. Then, this was boiled to obtain a coprecipitate. The resulting precipitate is removed by decantation, and the precipitate is washed with distilled water many times. Silver nitrate is dropped into distilled water from which the precipitate has been washed, and after confirming that there is no reaction of chloride ions, 1000 cc of distilled water is added to bring the total amount to 2000 cc. Further, 40 cc of 30% ammonia water was added and heated in a water bath to obtain a colloidal gel dispersion. This colloidal gel dispersion is designated as dispersion (A-2).

(Preparation of conductive metal oxide fine particle powder) Stannous chloride hydrate (65 g) and antimony trichloride (1.5 g) were dissolved in ethanol (1000 g) to obtain a uniform solution. 1N aqueous sodium hydroxide solution was added to this solution to adjust the pH of the solution to 3
Was added dropwise to obtain a coprecipitate of colloidal stannic oxide and antimony oxide. The coprecipitate obtained is heated to 50 ° C. for 24 hours.
After standing for a time, a reddish brown colloidal precipitate was obtained.

The reddish brown colloidal precipitate was separated by centrifugation. Water was added to the precipitate to remove excess ions, and the precipitate was washed with water by centrifugation. This operation was repeated three times to remove excess ions. 100 g of colloidal precipitate from which excess ions were removed was mixed with 50 g of barium sulfate having an average particle size of 0.3 μm and 1000 g of water and sprayed in a firing furnace heated to 900 ° C. to obtain a bluish average particle size of 0.1 μm. A powder mixture (A-3) consisting of tin and barium sulfate was obtained.

(Preparation of support) After biaxial stretching and heat setting, a polyethylene terephthalate film colored in blue with a thickness of 175 μm and a concentration of 0.15 was subjected to a corona discharge treatment of 8 W / m ² · min for both sides, Undercoat coating solution B having the following composition
-1 was applied as an undercoat layer B-1 to a dry film thickness of 0.8 μm, and dried at 100 ° C. for 1 minute.

<Undercoating first layer> Undercoating coating solution B-1 Copolymer latex liquid containing 30% by weight of butyl acrylate, 20% by weight of t-butyl acrylate, 25% by weight of styrene and 25% by weight of 2-hydroxyethyl acrylate. (Solid 30%) 270 g Compound (C-1) 0.6 g Hexamethylene-1,6-bis (ethylene urea) 0.8 g Finish with 1 liter of water.

<Undercoating second layer> Further, a corona discharge treatment of 8 W / m ² · min was applied on the above-mentioned undercoating layer B-1, and a dry film was formed with an undercoating coating solution B-2 having the following composition on both sides. It was applied to a thickness of 0.1 μm and dried at 100 ° C. for 1 minute.

Subbing coating liquid B-2 Gelatin 10 g Compound (C-1) 0.4 g Compound (C-2) 0.1 g Silica particles having an average particle diameter of 3 μm 0.1 g Conductive compound shown in Table 1 Finish with 1 liter of water.

[0092]

[Chemical 7]

(Preparation of silver halide emulsion) 4.5 g of potassium bromide, 20.6 g of gelatin, and 1 liter of water containing 2.5 cc of a 5% aqueous solution of thioether were stirred into a reaction vessel kept at 60 ° C. Meanwhile, 37 cc of an aqueous solution containing 3.43 g of silver nitrate and 33 cc of an aqueous solution containing 2.97 g of potassium bromide and 0.363 g of potassium iodide were added by the double jet method for 37 seconds. Next 0.9 g of potassium bromide
Was added to the solution, and the temperature was raised to 70 ° C. to obtain silver nitrate 4.9.
53 cc of an aqueous solution containing 0 g was added over 13 minutes. Further, 15 cc of 25% aqueous ammonia solution was added, and after physically aging for 20 minutes while maintaining the temperature, 14 cc of 100% acetic acid solution was added. Subsequently, an aqueous solution containing 133.3 g of silver nitrate and an aqueous solution of potassium bromide were added by the controlled double jet method for 35 seconds while keeping the pAg at 8.5.

After the addition was completed, the temperature was lowered to 35 ° C. to remove soluble salts by the precipitation method, and then the temperature was raised to 40 ° C., 35 g of gelatin, 2.5 g of phenoxyethanol and a thickening agent were added, and caustic soda and bromide were added. The pH was adjusted to 6.1 and pAg 8.3 with an aqueous potassium and silver nitrate solution. Emulsion Em-1 was thus prepared.

In the obtained emulsion, 93% of the total projected area of all grains was composed of grains having an aspect ratio of 3 or more, and the average projected area diameter of all grains having an aspect ratio of 3 or more was 1.4 μm. The aspect ratio was 7.

Preparation, processing and evaluation of sample To the obtained silver halide emulsion of Em-1 was added pure water so that the volume per mol of silver was 300 ml, and then 55 ° C.
Then, the total amount of the spectral sensitizing dyes A and B described below was added at a weight ratio of 100: 1 (540 mg per mol of silver halide).

After 10 minutes, ammonium thiocyanate was added in an amount of 2 × 10 ^-3 mol per mol of silver, and appropriate amounts of chloroauric acid, hypo and triphenylphosphine selenide were added to start chemical ripening. The pH at this time is 6.1.
5. The silver potential was 50 mv.

70 minutes before the end of chemical ripening, 4.0 g was added per mol of silver iodide fine grain silver, and then 4-hydroxy-
6-Methyl-1,3,3a, 7-tetrazaindene was added to complete the chemical ripening.

The following additives for emulsion were added to the obtained emulsion to prepare a preparation liquid. The pH of the photographic emulsion coating solution after preparation was 6.20, and the silver potential was adjusted to 80 mV (35 ° C.) using sodium carbonate and potassium bromide solution.

Using this emulsion coating solution, a sample was prepared as follows. That is, the photographic emulsion layer had a silver equivalent of 2.0 g / m ² per side and a gelatin amount of 2.0 g / m ² per side.

A protective layer solution was prepared using the additives described below. The protective layer is coated with gelatin on one side of 0.9 g / m 2.
^{The two} layers were simultaneously coated on the support at a speed of 80 m / min using two slide hopper type coaters together with the emulsion layer prepared above so as to obtain 2, and dried for 2 minutes and 20 seconds to obtain a sample. The emulsion was spectrally sensitized with an appropriate amount of the following two sensitizing dyes.

Spectral sensitizing dye A 5,5'-dichloro-9-ethyl-3,3'-di- (3
-Sulfopropyl) -oxacarbocyanine sodium salt anhydride Spectral sensitizing dye B 5,5'-di- (butoxycarbonyl) -1,1'-diethyl-3,3'-di- (4-sulfobutyl)- Anhydrous benzimidazolocarbocyanine sodium salt The additives used for the emulsion are as follows. The amount of addition is shown in an amount per mole of silver halide.

1,1-Dimethylol-1-bromo-1-nitromethane 10 mg t-butyl-catechol 70 mg Polyvinylpyrrolidone (molecular weight 10,000) 1.0 g Styrene-maleic anhydride copolymer 2.0 g Nitrophenyl-triphenyl Phosphonium chloride 5.0 mg 1,3-Dihydroxybenzene-4-sulfonic acid ammonium 2.0 g 2-Mercaptobenzimidazole-5-sulfonic acid sodium salt 1.5 mg C ₄ H ₉ OCH ₂ CH (OH) CH ₂ N (CH ₂ COOH) ₂ 1.5 g 1-phenyl-5-mercaptotetrazole 15 mg Methacrylic acid-ethyl acrylate copolymer 18 g

[0104]

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Next, the additives used in the protective layer liquid are shown. The stated weight is shown in the amount per liter of the coating solution.

Lime-treated inert gelatin 58 g Acid-treated gelatin 2 g Sodium-i-amyl-n-decylsulfosuccinate 1.0 g Polymethyl methacrylate, area average particle diameter 3.5 μm matting agent 0.4 g Silicon dioxide particles, area average Matting agent having a particle size of 1.2 μm 0.7 g Ludox AM (manufactured by DuPont) (colloidal silica) 3.0 g The following surfactants (a), (b) and (c) and a hardener are added. (A), (b), (c) are sample No. Add to only a few

[0107]

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For the development, the automatic developing machine shown in FIG. 1 was used with a developing solution and a fixing solution having the following composition. The developing temperature was 35 ° C., the fixing temperature was 33 ° C., and the washing water was at a temperature of 18 ° C. Was supplied.

As for the drying temperature, the surface temperature of the heat roller according to the present invention was 100 ° C., and all the treatment steps were conducted in the 30 second mode.

Processing Step Processing Temperature (° C.) Processing Time (sec) Replenishment Amount Insertion-0.8 Development + Transfer 35 9.7 220 ml / m ² Fixing + Transport 33 5.5 370 ml / m ² Washing + Transfer 184 2.8 5.0 l / min Squeeze 40 3.8 Drying * 50 5.4 Total-30.0 * Drying conditions are heat roller coated with Teflon on an aluminum roller (a halogen heater is used as a heat source) according to the present invention. Using.

Developer formulation Part-A (for finishing 15 liters) Potassium hydroxide 470 g Potassium sulfite (50% solution) 3000 g Sodium hydrogencarbonate 150 g Diethylenetriamine pentaacetic acid 5 sodium salt 45 g 5-Methylbenzotriazole 2.0 g 1-phenyl-5 -Mercaptotetrazole 0.2 g hydroquinone 390 g Part-B (for 15 liter finishing) glacial acetic acid 220 g triethylene glycol 200 g 1-phenyl-3-pyrazolidone 27 g 5-nitroindazole 0.45 g n-acetyl-DL-penicillamine 0.15 g fixing Liquid formulation Part-A (for finishing 19 liters) Ammonium thiosulfate (70 wt / vol%) 4000 g Sodium sulfite 175 g Sodium acetate trihydrate 400 g Quent Sodium 50g Gluconic acid 38g Boric acid 30g Glacial acetic acid 140g Part-B (for 19 liter finishing) Aluminum sulfate (anhydrous salt conversion) 65g Sulfuric acid (50wt%) 105g <Measurement of antistatic performance (static mark resistance)> Unexposed After conditioning the sample for 2 hours at 23 ° C. and 20% RH,
After rubbing the sample with a rubber roller and a nylon roller in a dark room under the same conditions, the same treatment as described above was performed to examine the degree of generation of static marks. As the antistatic performance, static marks were visually evaluated according to the following criteria.

A: Not generated B: Occurred in an area of less than 3% C: Occurred in an area of 3% or more and less than 10% D: Occurred in an area of 10% or more <Measurement of surface electric resistance> Kawaguchi Using a teraohm meter VE-30 manufactured by Denki Co., applied voltage 100V, 23 ° C., RH
It was measured under the condition of 55%.

<Peeling off of film> The developed blackened film processed with the automatic processor shown in FIG.
After conditioning the humidity at 60% H for 2 hours, apply a sapphire needle of 0.3 mmφ at a load of 500 g and a speed of 30 cm / Sec for 20 minutes.
The length of cm was rubbed 10 times. The film peeling of the emulsion film was evaluated relative to the scratches by the following 5 grades.

A: No scratches at all B: Invisible to the naked eye but detected with a 10 times magnifying glass C: Slightly detected with the naked eye D: Clearly film peeling and scratches are a problematic level E : Table 1 below shows the results above the level at which the scratches were generated and were unusable.

[0115]

[Table 1]

*: Poor drying occurred in the treatment of 20 consecutive samples (other samples had good dryness) ★★: As a result of confirming the transparency (haze) by developing the unexposed sample, the sample No. 11 and 12 were slightly inferior to the other samples.

As can be seen from the table, the samples according to the invention are
It can be seen that there is no generation of static marks in the rapid processing, and there is little peeling of the processed film.

Example 2 Preparation of emulsion 16 g of gelatin was dissolved in 1 liter of water, and 0.4 g of potassium bromide and 6 parts of sodium chloride were placed in a container heated at 53 ° C.
g and 0.8 ml of a 10% ethanol solution of polyisoprene polyoxyethylene disuccinic acid sodium salt were added, and then 600 ml of an aqueous solution containing 100 g of silver nitrate, an aqueous solution containing 56 g of potassium bromide and 7 g of sodium chloride 60
20 ml of silver chloride was added by the double jet method with 0 ml.
An aqueous solution containing 500 ml of an aqueous solution containing 100 g of silver nitrate, 40 g of potassium bromide, 14 g of sodium chloride, and 0.7 mole of potassium hexachloroiridium (III) at a molar ratio to silver of 500% to form a core portion having a mole% of 100%.
ml and a double jet method to form a shell portion of 40 mol% of silver chloride, and a cubic monodispersed silver chlorobromide emulsion Em having a silver chloride content of 30 mol% and an average particle diameter of 0.35 μm.
-2 was prepared. Then, the emulsion is desalted and then gelatin 3
0 g was added and the temperature was kept at 55 ° C. As a sensitizing dye, 5,5′-dimethoxy-3,3′-di- (3-sulfopropyl) -9 was used.
-Ethyl-thiacarbocyanine-triethylamine salt was added in a molar ratio to silver of 100 mg, and then gold chloride and sodium thiosulfate were added for chemical sensitization, and then 4-hydroxy-6-methyl-1,3,3a. , 7-Tetrazaindene was added for stabilization.

<Backing layer> Backing lower layer coating solution Gelatin 400 g i-amine-n-decylsulfosuccinate sodium 0.4 g Antihalation dye (1) 10 g Diethylene glycol 5.0 g Glyoxal 40% aqueous solution (hardener) 5.0 ml

[0120]

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Finish with water to 7 liters <Backing upper layer coating liquid> Gelatin 400 g i-amine-n-decylsulfosuccinate sodium 10 g Antihalation dye (1) 10 g Polymethylmethacrylate 12 g Surfactant (a) 3.0 g Interface Activator (b) 0.75 g Glyoxal 40% aqueous solution (hardener) 34.0 ml Make up to 7 liters with water.

<Silver Halide Emulsion Layer Coating Solution> Samples shown in Table 2 were prepared using the above emulsion Em-2.
The following additives were added per mol of silver halide to prepare a coating solution.

Trimethylolpropane 10 g Nitrophenyl-triphenylphosphonium chloride 50 mg 1,3-Dihydroxybenzene-4-ammonium sulfonate 1 g 2-Mercaptobenzimidazole-5-sodium sulfonate 10 mg 1,1-Dimethylol-1-bromo- 1-nitromethane 10mg

[0124]

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<Emulsion side protective layer coating liquid> The addition amount is shown as the amount per liter of coating liquid.

Lime-treated inert gelatin 68 g Acid-treated gelatin 2 g i-amine-n-decylsulfosuccinate sodium 1.4 g Polymethylmethacrylate (particle size 4 μm) 0.15 g Silicon dioxide particles (area average particle size 1.2 μm) 0 0.5 g Ludox AM (colloidal silica [manufactured by DuPont]) 30 g Topside 300 (manufactured by Permchem Asia Ltd.) 45 mg Surfactants (a) (b) (C) and addition of a hardener (emulsion protective layer of Example 1) The same amount, except that the surfactants (a), (b) and (c) are added only to sample Nos. 22 and 23).

[0127]

[Chemical 12]

<Coating of Sample> The same support as used in Example 1 was coated with a silver halide emulsion and an emulsion protective layer solution. The backing lower layer and the upper layer were coated on the opposite surface side.

The amount of gelatin in the backing layer was 3.
Simultaneous coating was performed by the slide hopper method at a speed of 90 m / min so that the upper layer was 0 g / m ² and the upper layer was 1.2 g / m ² . The amount of gelatin and the amount of silver in the emulsion layer are 2.0 g / m ² and 2.5 g, respectively.
A sample was obtained by coating so as to be / m ² . The amount of gelatin in the protective layer was 0.9 g / m ² .

The same evaluation as in Example 1 was conducted using the obtained sample except that a developer having the following composition using ascorbic acid, which is a reductone of the present invention, was used as a developer formulation.
Table 2 shows the results.

Developer composition (for finishing 15 liters) Sodium sulfite 240 g L-ascorbic acid 900 g 1-phenyl-4-hydroxymethyl-4-methyl-3-pyrazolidone 100 g potassium carbonate 420 g 1-phenyl-5-mercaptotetrazole 0. 45 g potassium hydroxide 130 g Adjust the pH to 10.3.

[0132]

[Table 2]

★: Sample developed with the developer of Example 1 ★★: As a result of confirming the transparency (haze) by developing the unexposed sample, the sample No. 30 and 31 were slightly inferior to the other samples.

As is apparent from the table, even when the sample of the present invention was treated with the developing solution containing L-ascorbic acid, the sample of the present invention did not generate static marks in the rapid processing, and the treated film had no halogen peeling. A silver halide photographic light-sensitive material was obtained.

[0135]

As demonstrated in the examples, according to the present invention, a silver halide photographic light-sensitive material and a processing method therefor in which a static film is not generated by rapid processing and the processed film is not peeled off. Was obtained.

[Brief description of drawings]

FIG. 1 is a side sectional view of an automatic processor used in an example.

[Explanation of symbols]

 1 Film Detecting Section 2 Squeeze 3 Heat Roller 4 Drying Fan 5 Development 6 Fixing 7 Washing 8 Waste Cock 9 Replenishing Pump 10 Processing Agent Bottle Storage 11 Chemical Mixer

Claims (5)

[Claims] 1. A method of processing a silver halide photographic light-sensitive material, which is processed by an automatic processor having a drying device with a heat roller, wherein the surface electric resistance value of the silver halide photographic light-sensitive material after processing is 1 × 10 ^12. Ω / cm (23 ° C, 55%
RH) or less, a method of processing a silver halide photographic light-sensitive material. 2. The silver halide photographic light-sensitive material according to claim 1, wherein the silver halide photographic light-sensitive material contains at least one kind selected from conductive polymers, conductive metal oxide particles or colloids thereof. Processing method. 3. A method of processing a silver halide photographic light-sensitive material, which is processed with a developer containing a reductone, wherein the surface electric resistance value after processing is 1 × 10 ¹² Ω / cm (23 ° C., 5
5% RH) or less, a method for processing a silver halide photographic light-sensitive material. 4. The silver halide photographic light-sensitive material according to claim 3, wherein the silver halide photographic light-sensitive material contains at least one selected from a conductive polymer, conductive metal oxide particles or colloids thereof. Processing method. 5. The method of processing a silver halide photographic light-sensitive material according to claim 3, wherein the processing is carried out by an automatic processor having a drying device using a heat roller.