JPH0497344A - Silver halide photographic sensitive material treated for antistatic processing method therefor - Google Patents

Abstract

PURPOSE:To lessen the deterioration in surface specific resistance after processing and to suppress the generation of static electricity as well as to prevent static charge during high-speed transportation by processing the above photosensitive material at >=1500mm/min transporting speed for <=19 second fixing time by using a fixer having >=0.1 and <=1.0mol/l Al content. CONSTITUTION:This photosensitive material is processed at >=1500mm/min transporting speed for <=19 second fixing time by using the fixer having >=0.1 and <=1.0mol/l Al content. The pH of the fixer is more preferably 3.9 to 6.5. The more preferable pH of the liquid is 4.2 to 5.3. The fixing processing conditions are preferably <=18 second, more particularly preferably <=15 fixing time. Further, the fixing temp. is preferably >=20 deg.C, more particularly preferably >=25 deg.C. The total processing time (Dry to Dry) by an automatic developing machine is preferably confined to <=60 seconds. The deterioration in the specific surface resistance after the processing is lessened in this way and the static charge during the high-speed transporting is prevented. In addition, the generation of the static electricity is suppressed.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to a silver halide photographic material for printing plate making and a processing method thereof, and more specifically to a plastic film support that has extremely excellent antistatic properties even after processing. The present invention relates to a photosensitive material having the following properties and a processing method thereof.

[Prior Art] Plastic film supports generally have strong electrostatic properties, and this often imposes many restrictions on their use. For example, when polyethylene terephthalate is used as a support for a silver halide photographic light-sensitive material, it is extremely susceptible to charging, especially under low humidity conditions such as in winter.

Various problems occur when photosensitive materials are charged. For example, the discharge may cause electrostatic shock to the operator, static marks may be generated on the photosensitive material, and pinholes may be formed due to adhesion of foreign matter such as dust, resulting in a significant deterioration of quality. It takes a lot of time to correct it, which is a big problem in terms of work environment and work efficiency. Also, recently, high-sensitivity photographic emulsions are coated at high speed,
Antistatic measures are especially important when exposing highly sensitive photosensitive materials in large quantities using an automatic printer or the like.

[Problems to be Solved by the Invention] For this purpose, a method of providing an antistatic layer is generally known as described in Japanese Patent Application No. 1-228763, P, 3-4.

Also known is a method of using a conductive metal oxide such as tin oxide or indium oxide doped with antimony or phosphorus for the antistatic layer. However, with these methods, deterioration of the surface resistivity after treatment was unavoidable. The deterioration of the surface resistivity is thought to be mainly due to the counterion exchange reaction of the water-soluble conductive polymer during the fixing process or the outflow of the dope component of the conductive metal oxide. Therefore, when fixing time was shortened to reduce these adverse effects, sufficient fixing was not achieved.

Furthermore, as a recent trend, there has been a demand for shorter development processing times in order to improve work efficiency, and for this reason, it has become desirable to increase the transport speed of the film. However, when the conveyance speed of an automatic processor was increased, the dried film came into contact with many rollers at high speed during the drying process, making it extremely susceptible to electrostatic charge and electrostatic shock.

The present invention has been made to solve the above problems, and a first object of the present invention is to provide a photosensitive material with less deterioration in surface resistivity after processing, and to provide a processing method therefor. There is a particular thing.

A second object of the present invention is to provide a photosensitive material that is not easily charged even when transported at high speeds by not only leaking generated static electricity but also suppressing the generation of static electricity itself.

[Means for Solving the Problems] An object of the present invention is to form at least one antistatic layer on a support.
In a method for processing a silver halide photographic material having more than one layer, the transport speed is 1500 mm/min or more, and the fixing time is 19 seconds or less using a fixing solution with an Ai content of 0.01 mol/l or more and 10 mol/y or less. This can be achieved by a method for processing a silver halide photographic light-sensitive material, which is characterized by processing the material, and by a silver halide photographic light-sensitive material processed by the above-mentioned processing method.

The present invention will be explained in more detail below.

One of the causes of the deterioration of the surface resistivity after processing is considered to be the influence of aluminum ions in the fixing solution during the fixing process. In the present invention, in order to reduce this influence, to! Using a fixing solution with a content of 0.01 mol/f or more and 10 mol/ρ or less, a fixing time of 19 seconds or less, and a transport speed of 1500 m.
It has been found that by processing at a speed of m/min or higher, deterioration of surface resistivity can be prevented without impairing fixing properties.

The fixer used in the present invention is A
It is necessary to contain 0.01 to 1.0 mol/2 of 2.

Examples of the A2 compound include chromium alum, potassium alum, and other A2 compounds.

In addition to the above, the fixer may contain various acids, salts, fixing accelerators, wetting agents, surfactants, chelating agents, hardeners, etc. in addition to thiosulfates and sulfites. For example, thiosulfates and sulfites include the potassium, sodium, and ammonium salts of these acids; acids include sulfuric acid, hydrochloric acid, nitric acid, halic acid, formic acid, acetic acid, propionic acid, oxalic acid, tartaric acid; Examples include citric acid, malic acid, phthalic acid, etc. Salts include potassium, sodium,
Examples include salts such as ammonium. As the fixing accelerator, Japanese Patent Publication No. 45-35754, Japanese Patent Application Laid-Open No. 58-12253
No. 5, thiourea derivatives described in No. 58-122536,
Alcohol with triple viscosity in the molecule, US Patent 4.1
Examples include thioethers described in No. 26.459, cyclodextran ethers that free anions, crown ethers, diazabicycloundecene, di(hydroxyethyl)butamine, and the like. Examples of wetting agents include alkanolamine alkylene glycol and the like.

Examples of the chelating agent include aminonitride acids such as nitrilotriacetic acid and EDTΔ.

The preferred concentration of sulfite contained in the fixer is 0.03 to 0.04 mol/l, more preferably 0.04 to 0.03 mol/l.

The preferred pH of the fixer is 39-65. The most preferred liquid pI is 42 to 5.3.

The fixing processing conditions in the present invention include a fixing time of 18
The time is preferably at most seconds, and particularly preferably at most 15 seconds.

Further, the fixing temperature is preferably 20°C or higher, more preferably 25°C.
The above is particularly preferable.

The effectiveness of conveyance speed in the present invention is interpreted as follows (
This is not to deny that the effects of the present invention are due to effects other than the principles described herein.)

As mentioned above, in order to improve the fixing performance within the limited fixer temperature and time, it is necessary to increase the agitation amount of the fixer relative to the emulsion surface (hereinafter simply referred to as the emulsion surface) of the photosensitive material. is valid.

However, increasing the amount of agitation of the fixer itself is less effective at the center of the emulsion surface in the mid-direction of conveyance, and at the edges, the amount of agitation becomes more than necessary, which tends to waste energy. Therefore, in order to utilize energy effectively and to exhibit the effect over the entire emulsion surface, it is thought that it is better to transport the photosensitive dye through the fixer solution more quickly.

In the present invention, in order to minimize the deterioration of surface resistivity, the total processing time (Dry to
It is particularly preferable that the drying time be 60 seconds or less.

In addition, increasing the transport speed tends to generate static electricity, so
In the present invention, the antistatic layer is provided to leak the generated static electricity and reduce the surface smoother value of the photographic material to 35 mmHg.
It is preferable to suppress the generation of static electricity by doing the above. This is because when the surface smoother value is 35 mmT-Ig or more, the surface roughness of the photosensitive material greatly reduces the contact area with rollers and the like, making it possible to effectively suppress the generation of static electricity.

In order to make the surface smoother value 35 mmHg or more, a matting agent can be used, or laser treatment, high voltage discharge treatment, etc. can be performed, but it is preferable to use a matting agent in the present invention.

As the matting agent used in the present invention, any known matting agent can be used. For example, the silica described in Swiss Patent No. 330,158, French Patent No. 1,296
, 995, British Patent No. 1.173,1
Inorganic particles such as alkaline earth metals or carbonates such as cadmium and zinc as described in US Pat.
037, starch derivatives described in Belgian Patent No. 625.451 or British Patent Nos. 981 and 198, polyvinyl alcohol described in Japanese Patent Publication No. 44-3643, and polystyrene described in Swiss Patent No. 330,158. or polymethyl methacrylate, polyacrylonitrile as described in U.S. Pat. No. 3,079,257;
Mention may be made of organic particles such as the polycarbonate described in US Pat. No. 3,022,169.

In the present invention, these matting agents may be used alone or in combination. The matting agent used in the present invention may be of fixed or irregular shape.

A part of the above-mentioned matting agent may be contained in at least one outermost layer, and may be contained in layers other than the outermost layer.

In order to fulfill its basic function as a matting agent, it is desirable that at least a portion of the matting agent be exposed on the surface.

In the present invention, the matting agent can be added by dispersing it in the coating solution in advance, or by spraying the matting agent after the coating solution of the layer to which the matting agent is added is applied and before drying is completed. etc. When adding two or more types of matting agents, these methods may be used in combination.

If a matting agent with a large grain size is used on the silver halide emulsion layer side, matte pinholes are likely to occur, but if the average grain size is 0.
When silver halide grains of 16 μm or less are used, the occurrence of matte pinholes can be significantly suppressed.

In the present invention, the coating is generally dried by blowing drying air, but drying may also be performed using far infrared rays, microwaves, or the like. In the present invention, when coating the outermost layer on the emulsion layer side, the weight ratio of water to binder is 80% for the entire coating solution of one layer or multiple layers to be coated.
The coating surface temperature at 0% to 200% is 19°C or less,
Moreover, it is preferable that it takes 35 seconds or more for the weight ratio of water and binder to go from 800% to 200%.

The silver halide photographic material of the present invention has at least one antistatic layer. The antistatic layer contains at least a conductive substance, and examples of the conductive substance include water-soluble conductive polymers, conductive metal oxides, and the like.

When a water-soluble conductive polymer is used as a conductive material,
The antistatic layer preferably also contains at least a hydrophobic polymer and a curing agent.

Examples of the water-soluble conductive polymer include polymers having at least one conductive group such as a sulfonic acid group, a sulfuric acid ester group, a quaternary ammonium salt, a tertiary ammonium salt, and a carboxyl group. It is preferable that the conductive group is contained in an amount of 5% by weight or more per polymer molecule. The water-soluble conductive polymer may contain a hydroxyl group, an amino group, an epoxy group, an aziridine group, an active methylene group, a sulfinic acid group, an aldehyde group, and a vinyl sulfone group.

The molecular weight of the polymer is 3000 to tooooo,
Preferably it is 3500-50000.

In the present invention, the amount of water-soluble conductive polymer added is 1
0mg/rrr ~1000mg/tT? is preferable, more preferably 100mg/nr to 1000mg/r
rr is particularly preferred.

Examples of water-soluble conductive polymer compounds used in the present invention are listed below, but the present invention is not limited thereto.

Margin below Exemplary compound CH.

CI-1.

A~7 A-10 Dexto Funsal 7 Eight Substitution degree 3.0 Mn=5000008-18 Dexto Funsal 7 Eight Substitution degree 2.0 Mn-100000Δ-21 Δ-14 Cl-1.

C11.

In ``Neshang,'' 2 Δ-1 to A-21, the stone has an average molecule f
f1 (in this specification, average molecular weight indicates number average molecular weight), GP expressed in terms of polyethylene glycol
This is based on the measured value by C.

Water-soluble conductive polymers tend to crack due to slight fluctuations in drying conditions, and to prevent this, hydrophobic polymer particles can be contained.

The hydrophobic polymer particles contained in the water-soluble conductive polymer layer are composed of so-called latex, which is substantially insoluble in water. This hydrophobic polymer includes styrene, styrene derivatives, alkyl acrylates, alkyl methacrylates, olefin derivatives, halogenated ethylene derivatives,
It is obtained by polymerizing monomers selected from vinyl ester derivatives, acrylonitrile, etc. in any combination.

In particular, it is preferable that at least 30 mol% of styrene derivatives, alkyl acrylates, and alkyl methacrylates are contained. Particularly preferred is 50 mol% or more.

There are two methods to make a hydrophobic polymer into a latex: emulsion polymerization, or dissolving a solid polymer in a low boiling point solvent, finely dispersing it, and then eluting the solvent. Emulsion polymerization is preferable because a complete product can be produced.

The molecular weight of the hydrophobic polymer may be 3000 or more,
There is almost no difference in transparency depending on molecular weight.

In the present invention, the amount of hydrophobic polymer used is 1 mg.
/rd to 500mg/rrr is preferable, and 10mg/d to 500mg/rrr is particularly preferable.

Specific examples of hydrophobic polymers used in the present invention will be given below.

Exemplary compound CH.

Margin below.

CI+.

Below, it is preferable to use an epoxy compound as the curing agent described in 4;

As the epoxy compound, those containing a hydroxyl group or an ether bond are preferred.

Specific examples of the epoxy compound used in the present invention are listed below.

(A) :[::I:= In the present invention, the amount of curing agent used is 1 mg/rr? ~
100mg/rr? It is preferable that the distance is 5 m.
g/resistance ~100mg/rr? It is particularly preferable that

When the antistatic layer contains a water-soluble polymer, the surface pH of the antistatic layer is preferably 8.0 or less, but if it is too low, it is not preferable from the viewpoint of film stability. A particularly preferred range is 3.0 to 7.5.

As the conductive metal oxide, any one of indium oxide, tin oxide, metal oxide doped with antimony atoms or phosphorus atoms, or a combination thereof can be used. In this case, the amount added is 0.01 to 10g/
rrr, preferably 0.1 to Ig/ba.

As indium oxide, indium oxide (In2
o) and indium oxide (InaOs) are known, but in the present invention, it is preferable to use indium oxide.

Further, as tin oxide, stannous oxide (Sno) and stannic oxide (SnOs) are known, but stannous oxide is preferably used in the present invention. Specific examples of metal oxides doped with antimony atoms or phosphorus atoms include tin oxide and indium oxide. The metal oxide can be doped with antimony or phosphorus by mixing a tin or indium halide, alkoxy compound, or nitrate compound with an antimony or phosphorus halide, alkoxy compound, or nitrate compound, and oxidizing and calcining the mixture. . These metal compounds can be easily obtained from metal compound manufacturers such as Nippon Yztrium Co., Ltd., for example. In addition, the preferred content rate when doping antimony or phosphorus is
It is preferably 05 to 10% by weight based on tin and indium. It is preferable to add these inorganic compounds by dispersing them in a hydrophilic colloid such as gelatin, or by dispersing them in a polymeric compound such as acrylic acid or maleic acid.

The loading ratio per binder is preferably 1 to 100% by weight.

Further, in the present invention, a curing agent can be used together with the conductive metal oxide. The curing agent used can be the same as the curing agent described above.

The antistatic layer according to the present invention is preferably coated on a transparent support. As the transparent support, any photographic support can be used, but polyethylene terephthalate or cellulose triacetate, which is made to transmit 90% or more of visible light, is preferred.

These transparent supports are prepared by methods well known to those skilled in the art, but in some cases, a slight amount of dye may be added to give them a blue tint so as not to substantially inhibit light transmission. good.

The support used in the present invention may be coated with a subbing layer containing a latex polymer after being subjected to a corona discharge treatment. Corona discharge treatment has an energy value of 1mW.
~IKW/rrrmin is particularly preferably applied. Particularly preferably, corona discharge treatment is performed again after coating the latex subbing layer and before coating the antistatic layer.

The present invention can be applied to photosensitive materials formed on a support. For example, silver halide color photosensitive materials,
These include photosensitive materials for X-rays and photosensitive materials for plate making.

The light-sensitive material of the present invention has at least one silver halide emulsion layer. A tetrazolium compound or a hydrazine compound can be added as a contrast enhancer to the silver halide emulsion contained in the silver halide emulsion layer. In the present invention, the above-mentioned tetrazolium compound or hydrazine compound may be added to a layer adjacent to the emulsion layer.

The hydrazine compound used in the present invention is preferably a compound represented by the following formula [1-1].

- Drinking price [H] In the formula, R represents a monovalent organic residue, R7 represents a hydrogen atom or a monovalent organic residue, Q and Q are a hydrogen atom,
Alkylsulfonyl group (including those with substituents),
It represents an arylsulfonyl group (including one having a substituent), and X□ represents an oxygen atom or a sulfur atom. -Among the compounds represented by [H], compounds in which X is an oxygen atom and R2 is a hydrogen atom are more preferred.

The monovalent organic residues for R1 and R2 include aromatic residues, heterocyclic residues, and aliphatic residues.

Aromatic residues include phenyl groups, naphthyl groups, and substituents thereof (e.g., alkyl groups, alkokene groups, acylhydrazino groups, dialkylamino groups, alkoxycarbonyl groups, cyano groups, carboxy groups, nitro groups, alkylthio groups, hydroxyl groups) , sulfonyl group, carbamoyl group, halogen atom, acylamino group, sulfonamide F group, urea group, thiourea group, etc.).

Specific examples of those with substituents include 4-methylphenyl group, 4-ethylphenyl group, 4-oxyethylphenyl group, 4-dodecylphenyl group, 4-carboxyphenyl group, 4-diethylaminophenyl group, -octylaminophenyl group, 4-benzylaminophenyl group, 4-acetamido-2-methylphenyl group, 4-(
3-ethylthioureido) phenyl group, 4-[2-(
2゜4-di-tert-butylphenoxy)butyramido]phenyl group, 4-[2-(2,4-di-tert
-butylphenoxy)butyramido]phenyl group, and the like.

The heterocyclic residue is a three- or six-membered monocyclic or fused ring having at least one of oxygen, nitrogen, sulfur, or selenium atoms, and may have a substituent.

Specifically, for example, pyrroline ring, pyridine ring, quinoline ring, indole ring, oxazole ring, benzoxazole ring, naphthoxazole ring, imidazole ring, benzimidazole ring, thiazoline ring, thiazole ring, benzothiazole ring, naphthothiazole ring, selenazole ring,
Examples include residues such as a benzoselenazole ring and a naphthoselenazole ring.

These heterocycles have 1 to 4 carbon atoms, such as methyl group and ethyl group.
Alkyl group, methoxy group, ethoxy group etc. carbon number 1-4
may be substituted with an alkoxy group, an aryl group having 6 to 18 carbon atoms such as a phenyl group, a halogen atom such as chloro or bromine, an alkoxycarbonyl group, a cyano group, an amino group, or the like.

Aliphatic residues include linear and branched alkyl groups, cycloalkyl groups, and those with substituents, as well as alkenyl groups and alkynyl groups.

Straight-chain and branched alkyl groups include, for example, those having 1 to 1 carbon atoms.
18, preferably 1 to 8 alkyl groups, and specific examples include methyl group, ethyl group, isobutyl group, and 1-octyl group.

Examples of the cycloalkyl group include those having 3 to 10 carbon atoms, such as a cyclopropyl group, a cyclohexyl group, and an adamantyl group. Substituents for alkyl groups and cycloalkyl groups include alkoxy groups (e.g. methoxy, ethoxy, propoxy, butoxy, etc.), alkoxycarbonyl groups, carbamoyl groups, hydroxy groups, alkylthio groups, amide groups, acyloxy groups,
Cyano group, sulfonyl group, halogen atom (e.g. chlorine,
bromine, fluorine, iodine, etc.), aryl groups (for example, phenyl groups, halogen-substituted phenyl groups, alkyl-substituted phenyl groups), etc. Specific examples of substituted groups include 3
-methoxypropyl group, ethoxycarbonylmethyl group,
Examples include 4-chlorocyclohexyl group, benzyl group, p-methylbenzyl group, and p-chlorobenzyl group.

Further, as an alkenyl group, for example, allyl
) group and an alkynyl group include, for example, a propargyl group.

Preferred specific examples of the hydrazine compound used in the present invention are shown below, but the present invention is not limited thereto.

J-1 Margin below ;+, +-','J H-16 H-17 Kyoto -NHNIICOCH, OCH.

Shiyama H-35 H-37 Addition of hydrazine compound represented by general formula [11] m
is preferably 10-6 to 10-' mol/silver 1 mol, more preferably 10-4 to 10-2 mol/silver 1 mol.

Next, the tetrazolium compound used in the present invention will be explained.

Tetrazolium compounds can be represented by the following - drinking cost.

General formula [T] In the formula, R1+ Rs and Rs each independently represent a phenyl group or a substituted phenyl group, Xe represents an anion,
n represents 2. The substituent is preferably a hydrogen atom or one having a negative or positive Hammett's sigma value (σP), which indicates the degree of electron attraction. In particular, negative ones are preferred.

Hammett's sigma values for phenyl substitution are found in many publications, such as the Journal of Medical Chemistry (
Journal of Medical Chemistry
try) Volume 20, page 304, 1977, C. Hansch (C.

A particularly preferable group having a negative sigma value is, for example, a methyl group (σP=-0.17 or less, all numbers in parentheses are σ
P value), ethyl group (-0,15), cyclopropyl group (-0,21), n-propyl group (-0,13), 1
so-propyl group (-0,15), cyclobutyl group (
-0,15), n-butyl group (-0,16), 1s
o-butyl group (-0,20), n-pentyl group (-0
,15), cyclohexyl group (-0,22), amino group (-0,66), acetylamino group (-0,15)
), hydroxyl group (-0,37), methoxy group (
-0,27), ethoxy group (-0,24), propoxy group (-0,25), butoxy group (-0,32)
, pentoxy group (-0,34), etc., and these are all useful as substituents of the compound represented by -drinkage [T].

Specific examples of compounds represented by the general formula [T] used in the present invention will be listed below, but the compounds of the present invention are not limited to these.

(Exemplary Compounds) T-10 T-11 -14 The following margins The tetrazolium compounds used in the present invention are described in, for example, Chemical Review.
s) It can be synthesized in 8 cases according to the method described in Vol. 55, pp. 335-483.

The tetrazolium compound according to the present invention is preferably used in an amount of about 1 mg to about 10 g, preferably about 10 mg to about 2 g, per mole of silver halide contained in the silver halide photographic material of the present invention. .

The silver halide emulsion used in the light-sensitive material of the present invention includes:
As the silver halide, any silver halide used in ordinary silver halide emulsions, such as silver bromide, silver chloride, silver iodobromide, silver chlorobromide, and silver chloroiodobromide, can be used. Further, the silver halide grains may be obtained by any of the acid method, neutral method, and ammonia method.

Silver halide grains may have a uniform silver halide composition distribution within the grain, or may be core/shell grains in which the silver halide composition differs between the inside and surface layer of the grain, and the latent image is mainly on the surface. It may be a particle that is formed inside the particle, or it may be a particle that is formed mainly inside the particle.

The silver halide emulsion used in the present invention is, for example, US Pat. No. 2,444,607, US Pat. No. 2,716,062, US Pat.
No. 89,380, No. 2,058,626, No. 2,
118,411, Japanese Patent Publication No. 43-4133, U.S. Patent No. 3,342,596, Japanese Patent Publication No. 4417-1987, West German Publication No. 2,149,789, Japanese Patent Publication No. 39-2
Compounds described in specifications or publications such as No. 825 and Japanese Patent Publication No. 49-13566, preferably, for example, 5°6-drimethylene-7-hydroxyne-s-triazolo(1,5-a)pyrimidine,5. 6-Titramethylene-7-hydroxy-5-t-riazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy-5-t-riazolo(1,5-a)pyrimidine, 5-methyl-7-hydroxy- 8-triazolo(1,5-a) pyrimidine, 7
-hydroxyne-5-) riazolone (1,5-a) pyrimidine, 5-methyl-6-promorph-hydroxy-S
- triazolo(1,5-a)pyrimidine, gallic acid ester (e.g. isoamyl gallate, dodecyl gallate,
propyl gallate, sodium gallate), mercaptans (1-phenyl-5-mercaptotetrazole, 2
-mercaptobenzthiazole), benzotriazoles (5-bromobenztriazole, 5-methylbenztriazole), henraimidazoles (6-nidropenzimidazole), and the like.

The silver halide emulsion used in the present invention may further contain various known additives depending on the purpose. Further, the emulsion used in the present invention can be chemically sensitized by conventional methods, and can be optically sensitized to a desired wavelength range using a sensitizing dye.

Gelatin is preferred as the hydrophilic colloid used in the present invention, but other hydrophilic colloids can also be used.

Gelatin preferably used in the present invention includes alkali-treated gelatin and acid-treated gelatin. When using ossein gelatin, it is preferable to remove calcium or iron. The iron content is 001-5
Preferably 0 ppm, more preferably 0.1 to 10 ppm
It is m. The amount of calcium and iron can be adjusted in this way by passing an aqueous gelatin solution through an ion exchange device.

The photosensitive material can be provided with auxiliary layers such as a filter layer, an antihalation layer, an antiirradiation layer, and a backing layer.

In the present invention, the silver halide photographic material and/or developer may contain an amino compound.

Further, in order to improve the developability, a developing agent such as phenidone or hydroquinone or an inhibitor such as benzotriazole may be contained in the emulsion. Alternatively, in order to increase the processing ability of the processing solution, the backing layer may contain a developing agent or an inhibitor.

The developing agents used in developing the silver halide photographic material of the present invention include catechol, pyrogallol and its derivatives, ascorbic acid, chlorohydroquinone,
Bromohydroquinone, methylhydroquinone, 2.3
-dibromohydroquinone, 2,5-diethylhydroquinone, catechol, 4-chlorocatechol, 4-phenylcatechol, 3-methoxy-catechol, 4-acetyl-pyrogallol, sodium ascorbate and the like.

In addition, typical examples of ICL-(CH=CH), -NH, type developers include ortho and rose aminophenols, such as 4-aminophenol, 2-amino-6-phenylphenol, 2-amino-4-chloro-
Examples include 6-phenylphenol and N-methyl-p-aminophenol. Furthermore, H2N-(CH=CH)n-N
Examples of the H2 type developer include 4-amino-2-methyl-
N,N-diethylaniline, 2,4-diamino-N,N
-diethylaniline, N-(4-amino-3-methylphenyl)-morpholine, p-phenylenediamine, and the like.

Examples of petrocyclic type developers include 3-pyrazolidone, 1-phenyl-3-pyrazolidone, 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone. -pyrazolidones,
Examples include 1-phenyl-4-amino-5-pyrazolone and 5-aminolaucil.

The Theory of the Photographic Process, 4th Edition, by T. H. James.
of the Photographic Process
ss Fourth Edition) No. 291-334
Pages and Journal of the American Chemical
Society (Journal of the Ameri)
Developers such as those described in Can Chemical Society, Volume 73, Page 3.100 (1951) can be effectively used in the present invention. These developers may be used alone or in combination of two or more types, but it is preferable to use two or more types in combination. In addition, sulfites such as sodium sulfite and potassium sulfite can be used as preservatives in the developer used for developing the photosensitive material of the present invention. Further, as a preservative, hydroxylamine or a hydrazide compound can be used, and in this case, the amount used is preferably 5 to 500 g, more preferably 20 to 200 g per 12 of the developer.

Further, the developer may contain glycols as an organic solvent, and such glycols include ethylene glycol, diethylene glycol, propylene glycol, triethylene glycol, 1,4-butanediol,
Among them, diethylene glycol is preferably used. The amount of these glycols used is preferably 5 to 500 g, more preferably 20 to 200 g per developer. These organic solvents can be used alone or in combination.

The silver halide photographic light-sensitive material of the present invention can be developed with a developer containing the above-mentioned development inhibitor to obtain a light-sensitive material with extremely excellent storage stability.

The pH value of the developer having the above composition is preferably 9 to 13, and more preferably the pH value is in the range of 10 to 12 from the viewpoint of stability and photographic properties. Regarding cations in the developer,
It is preferable that the ratio of potassium ions is higher than that of sodium because the activity of the developer can be increased.

The silver halide photographic material of the present invention can be processed under various conditions. For example, the developing temperature is preferably 50°C or lower, particularly preferably around 25°C to 40°C, and the developing time is generally completed within 2 minutes, but particularly preferably 10 seconds to 50 seconds is effective. often brings. Furthermore, it is optional to employ treatment steps other than development, such as washing with water, stopping, stabilizing, and further, if necessary, pre-hardening, neutralization, etc., and these can be omitted as appropriate. Furthermore, these treatments may be so-called manual development such as plate development or frame ring development, or mechanical development such as roller development or hanger development.

[Example] EXAMPLES The present invention will be specifically explained below with reference to Examples.

It should be noted that, as a matter of course, the present invention is not limited to the embodiments described below.

Example 1 A negative silver halide photosensitive material was prepared as a photosensitive abrasive material for bright room reversal in the following manner.

(Preparation of emulsion) A silver chlorobromide emulsion having a silver bromide content of 2 mol % was prepared as described below.

An aqueous solution containing 23.9 mg of pentabromorodium potassium salt, sodium chloride, and potassium bromide per 60 g of silver nitrate and an aqueous silver nitrate solution were stirred into an aqueous gelatin solution and mixed at 40°C for 20 minutes to obtain an average particle size of 016μ.
m silver chlorobromide emulsions were prepared.

This emulsion was added with 6-methyl-4-hydroxy- as a stabilizer.
After adding 200 mg of 1,3,3a,7-chitrazaindene, the mixture was washed with water and desalted.

To this was added 20 mg of 6-methyl-4-hydroxy-13,
After adding 3a,7-chitrazaindene, sulfur sensitization was performed. After sulfur sensitization, add the required amount of gelatin and use 6-methyl-4hydroxy-1,3,3 as a stabilizer.
a, Add 7-chitrazaindene, then add water to 260
A finished emulsion was prepared in 1p.

(Preparation of latex (L) for emulsion addition) Add 0.25 kg of KMDS (dextran sulfate ester sodium salt) manufactured by Meito Sangyo Co., Ltd. and 0.05 kg of ammonium persulfate to 40 liters of water.
4.51 kg of n-butyl acrylate and 5.4 kg of styrene were added to the liquid under a nitrogen atmosphere while stirring at a liquid temperature of 81°C.
A mixture of 9 kg of acrylic acid and 0.1 kg of acrylic acid was added over 1 hour, and then 0.005 kg of ammonium persulfate was added.
After further stirring for 1.5 hours, the mixture was cooled and the pH was adjusted to 6 with aqueous ammonia.

The obtained latex liquid was filtered using a GF/D filter manufactured by Whoman and made up to 50.5 kg with water to prepare a monodisperse latex (L) with an average particle size of 025 μm.

The following additives were added to the emulsion and latex for emulsion addition (L) to prepare a coating solution for a silver halide emulsion layer as described below.

(Preparation of coating solution for emulsion layer) After adding 9 mg of compound (A) as a bactericide to the emulsion solution, the pH was adjusted to 65 using 0.5N sodium hydroxide solution, and then the following tetrazolium compound (T ) to 36
Added 0 mg and further saponin 2 per mole of silver halide.
Add 51 g of 0% aqueous solution, 180 mg of sodium dodecylbenzenesulfonate, 80 mg of 5-methylbenzene-riazole, 431Q of the above emulsion addition latex (L), 60 mg of compound (M), and styrene as a thickener. Maleic acid copolymer water-based polymer 2
80 mg were added one after another and finished up to 4751 g with water to prepare a coating solution for an emulsion layer.

Next, an emulsion protective film coating solution was prepared as follows.

(Preparation of emulsion protective film coating solutions P-1, P-2, and P-3) Add 800 cc of pure water to 50 g of gelatin, and after swelling, dissolve at 40°C. Then, as a coating aid, the following compound (Z
), 12.5 g of the following compound (N) and 3 g of the following compound (D) as a filter dye.
were added sequentially, and further adjusted to p)T6.0 with citric acid solution.

In this liquid, as shown in Table 1, the average particle size was 3 μm and 7 μm.
After adding amorphous silica, it was finished to 1000 cc to prepare emulsion protective film coating solutions P-1, P-2, and P-3, respectively.

Table-1 Compound (T) (Exemplary Compound T-2) Compound (Z) Compound (M) Compound (N) Compound (A> Add 5g of Compound (D) and add the following compound (C) as a methanol solution.
-5) was added in an amount of 63 mg. Add 800 g of a water-soluble styrene-maleic acid copolymer as a binder to this solution and the viscosity is 1 second! E. Black 1 was prepared, the pH was adjusted to 5.4 using citric acid aqueous solution, and glyoxal was added to 144 m
g, the above epoxy curing agent (exemplified compound E-5)
．． Add 0g and finish to 960g with water to make I3C monk cloth 11
k I3-1 was prepared.

Compound (c-i> Next, a backing layer coating solution used for coating a backing lower layer was prepared as follows.

(Preparation of backing layer coating solution B-1) Swell 36 g of gelatin in water, heat and dissolve, then add 1.6 g of the following compound (C-1) as a dye, (C-2)
Add 310 mg of (C-3), 1.9 g of (C-3), and 29 g of the above compound (N), and then add 1.9 g of a 20% aqueous solution of saponin.
1, ρ, the following compound (C-4) as a physical property modifier] Compound * (C-2> Compound (C-3) Compound (C-4) Compound (C-5) Next, the protective film of the backing layer Protective film coating lr for layer
uB-2 was prepared as follows.

(Preparation of backing layer protective film coating solution B-2) Gelatin 5
0 g was swollen in water and dissolved by heating, followed by adding 340 mg of 2-sulfonate-succinic acid bis(2-ethylhexyl) ester sodium salt, 34 g of sodium salt, and further adding 11 g of glyoxal and 540 mg of mucochloric acid. To this was added spherical polymethyl methacrylate-1 with an average particle size of 4 μm as a matting agent at a concentration of 40 mg/rd, and the mixture was finished with water to a concentration of 1000 rd to prepare a protective film coating solution B-2.

[Creation of support having antistatic layer] After corona discharge was performed on a subbed-treated polyethylene terephthalate film (thickness 100 μm) at an energy of 50 W/tri min, a coating solution for an antistatic IL layer having the following composition was applied to the undercoated polyethylene terephthalate film (thickness 100 μm). The coating was applied using a roll-fit coating pan and an air knife at a speed of 30 m/min so as to achieve the desired coating amount.

Water-soluble t1 conductive polymer (A-12) 0.6g/
Hydrophobic polymer particles (13-14) 0.3g/
Hardener (E-5) 0.15g,
/Awakened nonionic surfactant HO (CI-12c lI20) 36HO, 06g/
After drying, dry at 90℃ for 2 minutes, then dry at 140℃ for 9 minutes.
A support having an antistatic layer was prepared by heat treatment for 0 seconds.

[Preparation of evaluation sample] On the side of the support having the antistatic layer, backing layer coating liquid B-1 and backing layer protective film coating liquid 13 were prepared.
-2 was applied simultaneously.

Next, coat the emulsion layer coating solution and the emulsion protective film coating solution (P-1, P-2 or P-3) on the opposite side of each support.
Simultaneous multilayer coating, drying and evaluation samples No. 1 to No. 017
It was created. During drying, the average temperature of the coating surface was 17° C. when the weight ratio of water and gelatin in the coating solution ranged from 800% to 200%, and the drying time was 40 seconds.

At that time, the amount of gelatin applied was 20g/20g for the backing layer.
Resistant to dusting, protective layer 1.5g/rrf, emulsion layer 20g
/ clear, emulsion protective layer 1.0g/m, silver amount 35g/m
It was durable.

Evaluation-i (I1) was developed using a processing solution with the following formulation.

[Developer prescription] (Composition Δ) Pure water (ion-exchanged water)
55% W/V aqueous solution) 100d potassium carbonate
50 g hydroquinone
15 g5-Methylbenzotriazole 200g 1-phenyl-5-mercaptotetrazole 0mg Potassium hydroxide Adjust the pH of the solution to 109 Nailized potassium 4.5g (composition) Pure water (ion-exchanged water) 3g Diethylene glycol 50 g Ethyleneaminetetraacetic acid disodium salt 5 mg Acetic acid (90% aqueous solution) 03 5-, :, l-0 Indazole l l
0mg1-phenyl-3-pyrazolidone 500
When using a mg developer, the above composition Δ was dissolved in the order of the composition Δ in 500 g of water, and the final solution was used.

[Fixer formulation] Fixer F-1 (Composition Δ-1) Ammonium thiosulfate (725% W/V aqueous solution) 230, Q 9.5 g 59g 6.7 g g 8.1d Sodium sulfite Sodium acetate trihydrate Sodium boric acid citrate/dihydrate acetic acid (90% W/W aqueous solution) (Composition-1) Pure water (ion exchange water) Sulfuric acid (50% W/W aqueous solution) 17g 5.8 g Aluminum sulfate (8% 208 equivalent nail included is 81% W/W
When using a 26.5 g fixing lfk (ytJ2), the above composition Δ-1 and composition 13-1 were dissolved in 500 d of water in this order, and the composition was made into one solution.

The pH of this fixing llkF-1 was about 43.

Fixer F-2 was prepared in the same manner as fixer F-1 except that aluminum sulfate was omitted from Composition-1.

[Development processing conditions] Development was carried out under the conditions shown in Table-2. However, each process time also includes the so-called wading conveyance time up to the next process.

Table 2 Test 1 Old ■ value (scratching property) A scratching test was conducted on the backing layer side after the fixing process using a surface property testing device manufactured by Shinto Scientific Co., Ltd. The results were expressed as the load (g) at which scratches began to appear.

(Smoothster value) The smoothster value was measured using 5M-6B+ manufactured by Toei Electronics Co., Ltd. in the same environment after processing the sample under the conditions shown in Table 2 without exposing it to light, then conditioning the humidity with 236C 48% RH for 2 hours. .

(Fixing Properties) After each treatment under the conditions shown in Table 2, the samples were visually observed and evaluated as x if silver halide remained and ○ if no silver halide remained.

(Peeling electrification property) In order to investigate the ease with which static electricity occurs, a 15 cm x 15
10cm x 1 to the processed evaluation sample cut into cm size
The operation of bringing a 0 cm size neoprene rubber sheet into contact and peeling it off was repeated 10 times, and the amount of charge immediately after that was measured.

Show the above results Shown in 3.

Blank space below 1 Example 2 Instead of the water-soluble conductive polymer used as the conductive material in Example 1, stannic oxide doped with 1% antimony atoms as a metal oxide was used for the antistatic layer, and this was coated with an alkali. Dispersed in treated gelatin, the amount of tin oxide added is O
, Ig/rrr, and gelatin were coated in an amount of 1g/7m to form an antistatic layer. Other than this, the same evaluation as in Example 1 was carried out in the same manner as in Example 1, and the same results as in Example 1 were obtained.

Example 3 Tetrazolium compound ('
Samples were prepared and evaluated in the same manner as in Example 2, except that the following hydrazine compound (HD) was used as a contrast enhancer instead of ")".

As a result, the same results as in Example 1 could be obtained.

Incidentally, a developer having the composition shown below was used, and the development conditions were 38° C. and 20 seconds.

Human ranane compound (Hr)) (Exemplary compound 1-1-8
) [Developer B cohytroquinone 45.0 gN
-Methyl p-aminophenol 1/2 sulfate sulfur hydroxide
・Rium 150 potassium hydroxide
5505 Sulfosalicylic acid
450 boric acid 3
50 Potassium sulfite 1100 Ethylenediaminetetraacetic acid disodium salt Potassium bromide 5-Methylbenzotri-n-butyl diethano water added 1.0 g 6.0 g Azole 0.6 g Luamine 15.0 g 1! (pII = 11.6) Example 4 A negative film for darkroom photography was prepared as follows.

In Example 1, the pentabromorodium potassium salt used in emulsion preparation was 25 μg per 60 g of silver nitrate, the silver bromide content was silver chlorobromide with a silver bromide content of 25 mol%, and the following sensitizing dye (C) was used during chemical sensitization. An emulsion was prepared. Using this emulsion, Sample 1 was prepared and evaluated in the same manner as in Example 1. As a result, the same results as in Example 1 could be obtained.

Sensitizing dye (C) CI-12CH, CN CzH, SO, Na Example 5 A high-sensitivity negative film for bright room use was prepared as follows.

(Preparation of sample) In an acidic atmosphere with nitric acid at pH 3.0, while maintaining the silver potential (EAg) at 170 mV, add [solution B] to [solution A] below.
] was added and EAg was controlled by NaCβ in IN and mixed by Chondrold double jet method, and [solution C
] was added at the same reaction temperature and addition flow rate as [solution B] until the addition time was 2 minutes, and then the EAg in [solution B] was added at the same reaction temperature and addition flow rate as [solution B].
A silver halide emulsion was prepared by adding at a flow rate of 099 times the addition flow rate controlled by aC, (.).The average grain size of the obtained silver halide grains was 0.08 μm.

[Solution Δ] Gelatin 5.6 g Polyisopropylene-polyethylene oxydisuccinic acid ester sodium salt 10% ethanol solution
0.56mQ sodium chloride
0.12 g concentrated nitric acid
0431 Di-distilled water 44
5 mJ2 [Solution i (1: B) Silver nitrate 60 g Concentrated nitric acid 0.208 d Distilled water [Solution i (l C) Gelatin polyisopropylene-polyethylene oxydisuccinic acid-
Ester sodium salt 10% ethanol solution Potassium bromide sodium chloride Na, Rh (4° distilled water [Solution D] Gelatin 1.4 g Polyisopropylene-polyethyleneoxydisuccinic acid-ester sodium salt 10% methanol solution
0.14d distilled water
48.81p Each silver halide grain had a silver chloride content of 90 mol%, a rhodium content of 2 x 10-' mol per mol of silver halide, and a degree of monodispersity of 8 to 15%.

To measure the EAg value, a metal silver electrode and a double diagonal 85.2d 0.3,9 4.2 g 18.6 g 0.021Q 81.319 1% aqueous solution A reference electrode was used for junction type saturated Ag/AgC.

(The structure of the electrode used the double junction disclosed in Japanese Patent Application Laid-Open No. 57-197534.)
], [Solution C] was added using a variable flow rate roller tube metering pump.

During the addition, the emulsion was sampled and observed using an electron microscope to ensure that no new grains were generated, thereby confirming that the amount added did not exceed the critical growth rate in the system.

Each emulsion prepared in this way was added with 6-methyl-
200 mg of 4-hydroxy-13,3a,7-chitrazaindene per mole of silver halide was added, the pH was adjusted to 5.7 with sodium carbonate, and then [Solution lt&D] was added. Thereafter, each silver halide emulsion was washed with water and desalted in a conventional manner, and then 58 mg of 6
After adding -methyl-4-hydroxy-1,3,3a,7-chitrazaindene and 150 mg of potassium bromide,
Sulfur sensitized.

After sulfur sensitization, 570 mg of 6-methyl-4-hydroxy-1,3,3a,7-chitrazaindene per mole of silver halide and 25 g of gelatin were added as stabilizers. Furthermore, the following additives were added to prepare an emulsion layer coating solution, and Example 1
The same emulsion protective film coating solution, backing layer coating solution,
A sample was prepared in the same manner as in Example 1 using the protective film coating solution for the backing layer.

[Heavy liquid additive for emulsion layer Cosaponin 100mg/Potassium bromide 3mg/Desensitizing dye (
DS-1) 1mg/sodium hydroxide resistance 10mg/mThe above tetrazolium compound (T) 45mg/mSodium dodecylbenzenesulfonate 21mg/butyl acrylate-styrene-acrylic acid copolymer latex 1g7m5-methylbenzotriazole 10mg/i5-phenyl- 1-mercaptotetrazole 11, 5 mg/rd 2-mercaptobenzimidazole 5-sulfonic acid 1 mg/bopendyl triphenylphosphonium chloride
5mg/resistant to the above compound (M)
5.8 mg 1rd desensitizing dye (DS-1) The same results as in Example 1 were obtained by processing and evaluating in the same manner as in Example 1.

[Effects of the Invention] As is clear from Examples 1 to 5, the present invention provides a photosensitive material that exhibits little deterioration in surface resistivity even after processing, and further suppresses the generation of static electricity itself even when transported at high speeds and is less likely to be charged. We were able to. Furthermore, we were able to provide a processing method for this purpose.

Claims (5)

[Claims] (1) In a method for processing a silver halide photographic material having at least one antistatic layer on a support, the transport speed is 1500 mm/min or more and the Al content is 0.0.
1. A method for processing a silver halide photographic light-sensitive material, which comprises processing using a fixing solution of 1 mol/l or more and 1.0 mol/l or less for a fixing time of 19 seconds or less. (2) A silver halide photographic material processed by the processing method according to claim 1. (3) The silver halide photographic material according to claim 2, which has a surface smoother value of at least 35 mmHg or more. (4) The silver halide photographic material according to claim 2 or 3, wherein the antistatic layer contains a water-soluble conductive polymer. (5) The silver halide photographic material according to claim 2 or 3, wherein the antistatic layer contains a conductive metal oxide.