JP2663043B2 - Silver halide photographic material - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a silver halide photographic light-sensitive material, and more particularly to a silver halide photographic light-sensitive material used in graphic arts fields and micro fields.

(Prior art and its problems) In the field of graphic arts, with the variety and complexity of printed matter, the photoengraving process is often a more complicated process, and improvements such as rationalization of work and labor saving are required. Have been. In particular, electrostatic charge accumulates due to contact friction or peeling between photosensitive materials or the surface of different kinds of materials when performing line drawing and halftone photography using ultra-high contrast photosensitive material or performing close contact exposure. Then, due to dust that has randomly adhered to the photosensitive material or the original film, the mark remains as a pinhole after the development processing, and a great deal of labor has to be spent on correcting or redoing the exposure. There was a problem. In order to solve such problems, techniques for improving the charging characteristics of the photosensitive material with a surfactant or the like have been introduced. However, it is still not sufficient, and particularly, the charging property is lost due to development processing. However, when this film is used as a document, there is a drawback that the pinhole is hardly improved, and there has been a strong demand for the development of a photosensitive material with less occurrence of the pinhole.

Also, in the micro field, with the rapid development of the information society, the enormous records that have been accumulated over the past many months can be copied quickly and accurately, and the enormous amount of data generated in daily economic activities. The importance of high-speed recording of important information (output information from a computer) is increasing. In order to satisfy these needs, there is a strong demand for speeding up automatic conveyance of an automatic exposure apparatus and an automatic development processing apparatus. Increasing the speed increases the accumulation of electrostatic charges, causing a problem of generating static marks due to discharge light. In order to improve this, it is essential to prevent the photosensitive material from being charged, and the improvement has been strongly demanded.

Japanese Patent Application No. 63-162146 discloses a method for improving these disadvantages.
No. 63-169316, JP-A-63-63035, Japanese Patent Application No. 63-2
There is a method using a conductive metal oxide or a conductive polymer compound described in 63257 and # 63-325385.

However, when a conductive layer containing a conductive metal oxide is used, a failure occurs in which the coating layer is disturbed due to agglomeration of the metal oxide in multi-layer simultaneous coating. To achieve stable production, it has been strongly desired to improve this disadvantage.

(Object of the Invention) An object of the present invention is to stably produce and provide a silver halide photographic light-sensitive material having an antistatic property.

(Constitution of the Invention) An object of the present invention is to provide a silver halide photographic light-sensitive material having at least one layer containing a conductive metal oxide and another hydrophilic colloid layer on a support, containing a conductive metal oxide. This was achieved by reducing the concentration of alkaline earth metal atoms in the adjacent layer of the layer to be formed to 1500 ppm or less with respect to the amount of the binder in the adjacent layer.

Crystalline metal oxide particles are preferred as the conductive metal oxide used in the present invention, but those containing oxygen vacancies and those containing a small amount of heteroatoms forming donors for the metal oxide used, etc. Is generally preferred because of its high conductivity, and the latter is particularly preferred because it does not give fog to the silver halide emulsion. Examples of metal oxide include ZnO _{is, TiO 2, SnO 2, Al} 2 O 3, In 2 O 3, SiO 2, MgO,
BaO, MoO ₃ , V ₂ O _{5 and the} like, or composite oxides thereof are preferable, and ZnO, TiO ₂ and SnO ₂ are particularly preferable. Examples of including heteroatoms include, for example, the addition of Al, In, etc. to ZnO,
Addition of Sb, Nb, halogen element, etc. to nO ₂ or T
Addition of Nb, Ta or the like is effective for iO ₂ . The addition amount of these different atoms is preferably in the range of 0.01 mol% to 30 mol%, and particularly preferably 0.1 mol% to 10 mol%.

The metal oxide fine particles of the present invention have conductivity, and their volume resistivity is preferably 10 ⁷ Ω-cm or less, particularly preferably 10 ⁵ Ω-cm or less.

These oxides are described in JP-A-56-143431 and JP-A-56-143431.
-120519 and 58-62647.

Further, as described in JP-B-59-6235, a conductive material in which the above-mentioned metal oxide is adhered to other crystalline metal oxide particles or fibrous materials (for example, titanium oxide) may be used. .

The available particle size is preferably 10μ or less, but 2μ
When it is less than the above, it is easy to use with good stability after dispersion. Use of conductive particles having a particle size of 0.5 μm or less to minimize the light scattering property is very preferable because a transparent photosensitive material can be formed.

When the conductive material is needle-like or fibrous, the length is preferably 30 μm or less and the diameter is preferably 2 μm or less, particularly preferably the length is 25 μm or less and the diameter is 0.5 μm or less, and the length / diameter ratio is 3 or more.

The conductive metal oxide of the present invention is used by being dispersed in a binder.

The binder is not particularly limited as long as it has a film-forming ability, for example, gelatin, proteins such as casein, carboxymethyl cellulose, hydroxyethyl cellulose, acetyl cellulose, diacetyl cellulose, cellulose compounds such as triacetyl cellulose, Dextran, agar, sodium alginate, starch derivatives, polyvinyl alcohol,
Polyvinyl acetate, polyacrylate, polymethacrylate, polystyrene, polyacrylamide,
Examples thereof include synthetic polymers such as poly-N-vinylpyrrolidone, polyester, polyvinyl chloride, and polyacrylic acid.

Particularly, gelatin (lime-treated gelatin, acid-treated gelatin, oxygen-decomposed gelatin, phthalated gelatin, acetylated gelatin, etc.), acetylcellulose, diacetylcellulose, triacetylcellulose, polyvinyl acetate, polyvinyl alcohol, polybutyl acrylate, polyacrylamide And dextran are preferred.

In order to more effectively use the conductive metal oxide of the present invention to lower the resistance of the conductive layer, it is preferable that the volume content of the conductive substance in the conductive layer is higher, but the strength as a layer is sufficiently high. Since a binder of at least about 5% is required to have the conductive metal oxide, the volume content of the conductive metal oxide is 5 to 95%.
% Is desirable.

The amount of the conductive metal oxide of the present invention is preferably 0.05 to 20 g per square meter of the photographic light-sensitive material, and more preferably 0.1 to 20 g.
10 g is preferred. The surface resistivity of the conductive layer of the present invention is 25 ° C. 25
In an atmosphere of% RH, the resistance is 10 ¹² Ω or less, preferably 10 ¹¹ Ω or less. Thereby, good antistatic properties can be obtained.

At least one conductive layer containing the conductive metal oxide of the present invention is provided as a constituent layer of a photographic light-sensitive material. For example, any of a protective layer, a back layer, an intermediate layer, an undercoat layer and the like may be used, but two or more layers may be provided as necessary.

In the present invention, the alkaline earth metal atom is an element belonging to Group II of the periodic table, and as typical ones, Ca, Mg,
Ba, etc. When these atoms combine with other atoms, they become divalent cations and often form compounds having strong ionic bonding properties.

In general, gelatin used as a binder in photographic light-sensitive materials contains a considerable amount of calcium salt which enters from raw material bone and the like. In the case of lime-processed gelatin, the calcium content in the gelatin is 2000 ppm or more. When gelatin having a high calcium content is used for an adjacent layer of a layer containing a conductive metal oxide, the conductive metal oxide is formed at the interface where the layer of the conductive metal oxide and the adjacent layer come into contact in the simultaneous multi-layer coating. Agglomerates and disturbs the coating layer. As a result of intensive studies to solve this problem, it was found that aggregation could be prevented by reducing the calcium content of the adjacent layer to 15,000 ppm or less based on the amount of gelatin. Although this phenomenon is very difficult to predict, it is presumed that aggregation is caused by the interaction between the divalent cation (Ca ⁺⁺ ) and the conductive metal oxide.

In the present invention, the content of the alkaline earth metal atom in the adjacent layer is 1500 ppm or less, preferably 1200 ppm or less, based on the binder amount.

The adjacent layer in the present invention means an upper layer and a lower layer of a layer containing a conductive metal oxide.

In the present invention, the concentration of the alkaline earth metal atoms in at least one of the adjacent layers is reduced. However, when the adjacent layer is present in both the upper layer and the lower layer, the alkaline earth metal in any of the adjacent layers is reduced. It is preferable to reduce the concentration of metal atoms. The binder amount of the adjacent layer is 0.1 g / m ² -1
It is a 0g / m ^2. The binder is not particularly limited as long as it has a film forming ability, and the same binder as that used for the layer containing the conductive metal oxide is used.

In the present invention, the content of the alkaline earth metal atom is 15
In order to reduce the content to 00 ppm or less, for example, in the case of gelatin having a high Ca ⁺⁺ content, the
A so-called deionized gelatin having a low Ca ⁺⁺ content (100 ppm or less) can be obtained. The quantification of the alkaline earth metal atom can be easily determined by a generally known atomic absorption method.

The layer containing the conductive metal oxide of the present invention and the adjacent layer may contain a chelate compound.

The stability constant of the chelate compound used in the present invention is:
6.0 or more, preferably 7 to 11
Is used.

The stability constant of the chelate compound used in the present invention is:
It is defined in Ueno Keihei, "Chelate Titration Method" (Revised, 17th edition, 18 pages (1979) Nankodo). Dortite reagent
Stability constants of various chelate compounds used in the present invention are described in the 12th edition of the General Catalog (Showa 55), Dojin Chemical Laboratory.

Examples of specific chelate compounds used in the present invention include alkali metal salts of the following compounds,
It is not limited to these.

logK _ML 1) trans-1,2-cyclohexanediamine-N, N,
N ', N'-tetraacetic acid (CYDTA) 10.3 2) 1,2-diaminopropane-N, N, N', N'-tetraacetic acid (methyl EDTA) 8.8 3) Ethylenediaminetetraacetic acid (EDTA) 8.7 4) Tri Ethylenetetramine-N, N, N ', N ", N, N-
Hexacetic acid (TTHA) 8.1 5) Diethylenetriamine-N, N, N ', N ", N" -pentaacetic acid (DTPA) 9.3 The addition amount of the chelate compound is 1 ×
It is 10 ^-8 mol or more and can be added up to the solubility of the compound.

In the present invention, a better antistatic property can be obtained by further using a fluorine-containing surfactant in addition to the conductive substance.

Preferred fluorine-containing surfactants used in the present invention include a fluoro-alkyl group, an alkenyl group, or an aryl group having 4 or more carbon atoms and an anionic group (sulfonic acid (salt), sulfuric acid (salt) as an ionic group. ) Carboxylic acid (salt),
Phosphoric acid (salt)), cationic group (amino salt, ammonium salt, aromatic amine salt, sulfonium salt, phosphonium salt), betaine salt (carboxyamine salt, carboxyammonium salt, sulfoamine salt, sulfoammonium salt, phosphoammonium salt) Or a surfactant having a nonionic group (substituted or unsubstituted polyoxyalkylene group, polyglyceryl group or sorbitan residue).

These fluorine-containing surfactants are disclosed in JP-A-49-10722, British Patent No. 1,330,356, U.S. Patent Nos. 4,335,201 and 4,34.
No. 7,308, UK Patent No. 1,417,915, JP-A-55-149938
No. 58-196544 and British Patent No. 1,439,402.

 Some of these specific examples are described below.

F-1 C ₈ F ₁₇ SO ₃ K The layer to which the fluorine-containing surfactant of the present invention is added is not particularly limited as long as it is at least one layer of a photographic material, and examples thereof include a surface protective layer, an emulsion layer, an intermediate layer, an undercoat layer, and a back layer. Can be. Among them, a preferable addition site is the surface protective layer, and either one of the emulsion layer side and the back layer side may be used. However, the case where it is added to both surface protective layers is more preferable.

When the surface protective layer is composed of two or more layers, any layer may be used, and the surface protective layer may be further overcoated on the surface protective layer.

The amount of the fluorinated surfactant of the present invention may be 0.0001 to 1 g per square meter of the photographic light-sensitive material, more preferably 0.0002 to 0.25 g, and particularly preferably 0.0003 to 1 g.
~ 0.1g.

Further, two or more kinds of the fluorinated surfactants of the present invention may be mixed.

Next, another antistatic agent can be used in combination with the layer containing the fluorine-containing surfactant of the present invention or another layer, whereby a more favorable antistatic effect can be obtained.

In the photographic emulsion layer and the non-photosensitive hydrophilic colloid layer of the present invention, a water-soluble dye (oxonol dye,
Hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. ) May be contained.

The photographic emulsion layer and the non-photosensitive hydrophilic colloid layer of the present invention may contain an inorganic or organic gelatin hardener. For example, active vinyl compounds (1,3,5-triacryloyl-hexahydro-s-triazine, bis (vinylsulfonyl) methyl ether, N, N'-methylenebis- [β- (vinylsulfonyl) propionamide], etc.), active halogen Compounds (such as 2,4-dichloro-6-hydroxy-s-triazine), mucohalic acids (such as mucochloric acid), N-carbamoylpyridinium salts (such as (1-morpholy, carbonyl-3-pyridinio) methanesulfonate), Haloamidinium salts (1-
(1-chloro-1-pyridinomethylene) pyrrolidinium, 2-naphthalene sulfonate, etc.) can be used alone or in combination. Above all, JP-A-53-4122
0, 53-57257, 59-162546, 60-80846 and the active halides described in U.S. Pat. No. 3,325,287 are preferred.

The silver halide emulsion used in the present invention may have any composition such as silver chloride, silver chlorobromide, silver iodobromide and silver iodochlorobromide.

The average grain size of the silver halide used in the present invention is preferably fine grains (for example, 0.7 μm or less), particularly 0.5 μm.
The following is preferred. The particle size distribution is basically not limited, but is preferably monodispersed. The term “monodisperse” as used herein means that at least 95% by weight or the number of particles is composed of a group of particles having a size within ± 40% of the average particle size.

The silver halide grains in the photographic emulsion may have regular crystals such as cubic and octahedral,
In addition, those having irregular crystals such as spheres and plates, or those having a complex form of these crystal forms may be used.

In the silver halide grains, the inside and the surface layer may be composed of a uniform phase or may be composed of different phases. Two or more kinds of silver halide emulsions formed separately may be used as a mixture.

The silver halide emulsion used in the present invention contains a cadmium salt during the formation or physical ripening of silver halide grains.
A sulfite, a lead salt, a thallium salt, a rhodium salt or a complex salt thereof, an iridium salt or a complex salt thereof, and the like may coexist.

The silver halide emulsion used in the method of the present invention may not be chemically sensitized, but may be. As methods of chemical sensitization of silver halide emulsions, sulfur sensitization, reduction sensitization and noble metal sensitization are known, and any of these can be used alone or in combination with chemical sensitization. Is also good.

Gelatin is advantageously used as a binder or protective colloid of the photographic emulsion, but other hydrophilic colloids can also be used. For example, cellulose derivatives such as hydroxyethylcellulose, carboxymethylcellulose, etc., sugar derivatives such as starch derivatives, polyvinyl alcohol, polyvinyl alcohol partial acetal,
A synthetic hydrophilic polymer material of a metal such as a single or copolymer such as poly-N-vinylpyrrolidone, polyacrylic acid, polymethacrylic acid, and polyacrylamide can be used.

As gelatin, in addition to lime-processed gelatin, acid-processed gelatin may be used, and gelatin hydrolyzate and gelatin oxygen-decomposed product can also be used.

A known spectral sensitizing dye may be added to the silver halide emulsion layer used in the present invention.

The photographic emulsion used in the present invention can contain various compounds for the purpose of preventing fog during the production process, storage or photographic processing of the light-sensitive material, or stabilizing photographic performance. That is, azoles such as benzothiazolium salts, nitroisodazoles, triazoles, benzotriazoles, benzimidazoles (particularly nitro- or halogen-substituted); heterocyclic mercapto compounds such as mercaptothiazoles, mercaptobenzothiazoles, Mercaptobenzimidazoles, mercaptothiadiazoles, mercaptotetrazoles (especially 1-phenyl-5-mercaptotetrazole), mercaptopyrimidines; the above heterocyclic mercapto compounds having a water-soluble group such as a carboxyl group or a sulfone group; thioketo compounds, for example Oxazolinethione; azeindenes such as tetraazeindenes (especially 4-hydroxy-substituted (1,3,3a, 7) tetraazaindenes); benzenethiosulfonic acids; Nsurufin acid, can be added to many of the compounds known to the antifoggants or stabilizers, such as hydroquinones.

The photographic emulsion layer or other hydrophilic colloid layer of the light-sensitive material prepared by using the present invention may have coating aids, antistatic, slipperiness improvement, emulsification / dispersion, adhesion prevention and photographic property improvement (eg, development acceleration, high contrast For various purposes such as sensitization), various surfactants may be contained.

For example, saponins (steroids), alkylene oxide derivatives (eg, polyethylene glycol, polyethylene glycol / polypropylene glycol condensate, polyethylene glycol alkyl ethers or polyethylene glycol alkyl aryl ethers, polyethylene glycol esters, polyethylene glycol sorbitan esters, polyalkylene glycol) Nonionic surfactants such as alkylamines or amides, polyethylene oxide adducts of silicone, glycidol derivatives (eg, alkenyl succinic acid polyglycerides, alkylphenol polyglycerides), fatty acid esters of polyhydric alcohols, and alkyl esters of sugars. Agent: alkyl carboxylate, alkyl sulfonate, alkyl benzene sulfo Acid salts, alkyl naphthalene sulfonates, alkyl sulfates, alkyl phosphates, N-acyl-N-alkyl taurines, sulfosuccinates, sulfoalkyl polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl phosphorus Anionic surfactants containing an acidic group such as a carboxy group, a sulfo group, a phospho group, a sulfate group, and a phosphate group such as acid esters; amino acids, aminoalkyl sulfonic acids, aminoalkyl sulfate or phosphoric acid Amphoteric surfactants such as esters, alkylbetaines and amine oxides; alkylamine salts;
Cationic surfactants such as aliphatic or aromatic quaternary ammonium salts, heterocyclic quaternary ammonium salts such as pyridinium and imidazolium, and phosphonium or sulfonium salts containing aliphatic or heterocyclic rings can be used.

Particularly, surfactants preferably used in the present invention are polyalkylene oxides having a molecular weight of 600 or more described in JP-B-58-9412. Further, a polymer latex such as polyalkyl acrylate can be contained for dimensional stability.

Further, for the purpose of preventing adhesion or improving the brushability of the light-sensitive materials, improving the vacuum adhesion, spherical particles such as polymethyl methacrylate or amorphous particles such as silicon dioxide and barium sulfate-strontium may be contained as a matting agent. it can. The average particle size is from 0.1μ to 10μ, preferably from 1 to 5μ.

As a support of the light-sensitive material of the present invention, cellulose triacetate, cellulose diacetate, nitrocellulose, polystyrene, polyethylene terephthalate and the like can be used. Further, a steam barrier layer made of a vinylidene chloride copolymer or the like may be provided on both surfaces of the support.

Examples of development accelerators suitable for use in the present invention or accelerators for developing nucleation transmission include JP-A-53-77616 and JP-A-54-77616.
7732, 53-137133, 60-140340, 60-1495
In addition to the compounds disclosed in No. 9, various compounds containing an N or S atom are effective.

To obtain ultra-high contrast photographic characteristics using the silver halide light-sensitive material of the present invention, a conventional infectious developer or U.S. Pat.
It is not necessary to use an alkaline developer close to pH 123 described in JP-A-975, and a stable developer can be used.

That is, the silver halide light-sensitive material of the present invention contains 0.15 mol / or more of sulfite ion as a preservative, and has a pH of 10.5
With a developer having a pH of from 12.3 to 12.3, particularly from 11.0 to 12.0, a negative image having a sufficiently high contrast can be obtained.

There is no particular limitation on the developing agents that can be used in the method of the present invention, and examples thereof include hydroxybenzenes (eg, hydroquinone) and 3-pyrazolidones (eg, 1-phenyl-3-pyrazolidone, 4,4-dimethyl-1-phenyl-).
3-pyrazolidone), aminophenols (for example, N-
Methyl-p-aminophenol) or the like can be used alone or in combination.

The silver halide light-sensitive material of the present invention particularly contains dihydroxybenzenes as a main developing agent and 3
-Suitable for processing with a developer containing pyrazolidones or aminophenols. Preferably, the developer contains 0.05 to 0.5 mol / dihydroxybenzenes / mol.
, 3-pyrazolidones or aminophenols are 0.
It is used in the range of 06 mol / or less.

Also, as described in U.S. Pat.No.4,269,929,
By adding amines to the developer, the development speed can be increased and the development time can be shortened.

Other developers include pH buffers such as sulfites, carbonates, borates and phosphates of alkali metals, bromides,
It can contain a development inhibitor such as iodide and an organic antifoggant (particularly preferably nitroindazoles or benzotriazoles) or an antifoggant. Also, if necessary, a water softener, a dissolution aid, a color tone agent,
It may contain a development accelerator, a surfactant (especially preferably the above-mentioned polyalkylene oxides), an antifoaming agent, a hardening agent, and a silver stain inhibitor (for example, 2-mercaptobenzimidazole sulfonic acids) of the film.

The development temperature and time are preferably from about 13 ° C to about 50 ° C for 5 seconds to 1 minute.

On the other hand, the fixing solution is an aqueous solution containing a thiosulfate, a water-soluble aluminum compound, acetic acid and a dibasic acid (for example, tartaric acid, citric acid or a salt thereof), and has a pH of 4.4 or more, preferably 4.6 to 5.4, more preferably 4.6 to 5.0.

The pH of the fixer changes the swelling of the film and has a significant effect on residual color. That is, if the pH exceeds 5.4, even if a predetermined hardener is introduced, the swelling of the film is large, poor drying, transport trouble such as poor passage occurs, and when a large amount of hardener is introduced to prevent it, Film contamination occurs due to deposition of a hardener. On the other hand, when the pH is 4.4 or less, a problem such as residual color occurs, and when the pH is 4.0 or less, problems such as poor fixing occur. However, in the above-mentioned pH range and the amount of the hardener according to the present invention, it becomes possible to quickly obtain a film with less residual color.

The fixing agent contains thiosulfate such as sodium thiosulfate and ammonium thiosulfate as an essential component, and ammonium thiosulfate is particularly preferable from the viewpoint of fixing speed. The amount of the fixing agent used can be appropriately changed, and is generally about 0.1 to
About 5 mol /.

Examples of the acidic hardener in the fixing solution of the present invention include a water-soluble aluminum salt, a chromium salt, and an ethylenediaminetetraacetic acid complex using a trivalent iron compound as an oxidizing agent. Preferred compounds are water-soluble aluminum salts, such as aluminum chloride, aluminum sulfate and potassium alum. A preferable addition amount is 0.01 mol to 0.2 mol /, more preferably 0.03 to 0.08 mol /.

Tartaric acid or a derivative thereof as the aforementioned dibasic acid,
Citric acid or a derivative thereof can be used alone or in combination of two or more. These compounds are used in Fixer 1
Is effective in containing 0.005 mol or more, particularly 0.01 mol / to 0.03 mol /.

Specifically, tartaric acid, potassium tartrate, sodium tartrate, potassium hydrogen tartrate, sodium hydrogen tartrate, potassium sodium tartrate, ammonium tartrate, ammonium potassium tartrate, aluminum potassium tartrate,
Antimonyl potassium tartrate, sodium antimonyl tartrate, lithium hydrogen tartrate, lithium tartrate, magnesium hydrogen tartrate, potassium potassium tartrate, potassium lithium tartrate and the like.

Examples of citric acid or derivatives thereof effective in the present invention include citric acid, sodium citrate, potassium citrate, lithium citrate, ammonium citrate, and the like.

The fixer may optionally contain a preservative (eg, sulfite, bisulfite), a pH buffer (eg, acetic acid, boric acid), a pH adjuster (eg, sulfuric acid), and a chelating agent (described above). . Here, the pH buffer is 10 to 10 because the pH of the developer is high.
The amount is about 40 g /, more preferably about 18 to 35 g /.

Fixing temperature and time are the same as for development, about 18 ° C
5 seconds to 1 minute at ~ 50 ° C is preferred.

According to the method of the present invention, the developed and fixed photographic material is washed and dried. The water washing is performed to almost completely remove the silver salt dissolved by the fixing.
Seconds to 3 minutes are preferred. Drying is performed at about 40 ° C. to about 100 ° C., and the drying time can be appropriately changed depending on the surrounding conditions.
Usually, it may be about 5 seconds to 3 minutes 30 seconds.

US Patent No. 30 for roller transport type automatic developing machine
No. 25779, No. 3,554,971 and the like, and are simply referred to as a roller transport type processor in this specification. The roller transport type processor has four steps of development, fixing, washing and drying, and the method of the present invention does not exclude other steps (for example, a stop step), but most of these steps follow the steps. preferable.

Development and fixing temperatures are typically between 18 ° C and 50 ° C
And more preferably from 25 ° C to 43 ° C.

The developing method of the present invention is particularly suitable for rapid processing using an automatic developing machine. Roller transport type automatic developing machine,
Any of belt conveyance and others can be used. The processing time may be short, within 2 minutes in total, especially 100 seconds or less, in which the time allocated to development is 5 seconds to 60 seconds, or the fixing time is 5 seconds to 40 seconds, and the washing time is 5 seconds to 60 seconds. It is fully effective for rapid processing.

The developer of the present invention is disclosed in JP-A-56-24 as a silver stain inhibitor.
The compound described in No. 347 can be used. Compounds described in JP-A-61-267759 can be used as a dissolution aid added to the developer. Further pH used for developer
As the buffer, compounds described in JP-A-60-93433 or compounds described in JP-A-62-186256 can be used.

In the photographic processing of the photosensitive material for micros of the present invention, any of the known developing methods for forming a positive silver image by reversal development can be used. Known treatment liquids can be used. The processing temperature is usually selected between 18 ° C and 65 ° C, but may be lower than 18 ° C or higher than 65 ° C.

 The reversal development process usually comprises the following steps.

First development-Washing-Bleaching-Washing-Overall exposure-Second development-
Fixing-washing-drying.

The developer used in the black-and-white photographic processing of the first development can contain a known developing agent. As a developing agent,
Dihydroxybenzenes (eg hydroquinone),
3-Pyrazolidones (e.g., 1-phenyl-3-pyrazolidone), aminophenols (e.g., N-methyl-p-aminophenol), 1-phenyl-3-pyrazolines, ascorbic acid, and those described in U.S. Pat. No. 4,067,872. Heterocyclic compounds such as a condensed 1,2,3,4-tetrahydroquinoline ring and an indolene ring can be used alone or in combination. In particular, it is preferable to use pyrazolidones and / or aminophenols together with dihydroxybenzenes. The developer generally contains other known preservatives, alkali agents, pH buffers, antifoggants and the like, and further, if necessary, a dissolution aid, a color tone agent, a development accelerator, a surfactant, an antifoaming agent, It may contain a water softener, a hardener, a viscosity imparting agent and the like. The light-sensitive material of the present invention usually contains 0.15 mol / l of a sulfite ion as a preservative.
It is processed with the developer contained above.

The pH is preferably 9 to 11, particularly preferably 9.5 to 10.5.

The first developer contains a silver halide solvent such as NaSCN of 0.5 to
6g / used.

As the second developer, a general black-and-white developing solution can be used. That is, it has a composition obtained by removing the silver halide solvent from the first developer. The pH of the second developer is 9
-11 is preferred, and pH 9.5-10.5 is particularly preferred.

A bleaching agent such as potassium dichromate or cerium sulfate is used in the bleaching solution.

Thiosulfate and thiocyanate are preferably used for the fixing solution, and may contain a water-soluble aluminum salt as necessary.

(Effect of the Invention) According to the present invention, a silver halide photographic light-sensitive material having excellent antistatic properties can be stably manufactured and provided.

 Hereinafter, the present invention will be described in detail with reference to Examples.

Example-1 The following undercoating- (1) first undercoat layer and the undercoating- (2) undercoat second layer were sequentially applied to both surfaces of a biaxially stretched 100 μm thick polyethylene terephthalate support.

Formulation- (1) First layer of undercoat Vinylidene chloride latex (core-shell type latex aqueous dispersion core 90% by weight, shell 10% by weight) 15 parts by weight Core vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (93:
3: 3: 0.9: 9.1) Shell part Vinylidene chloride: methyl acrylate: methyl methacrylate: acrylonitrile: acrylic acid (9
0: 3: 3: 2: 2) 2,4-Dichloro-6-hydroxy-s-triazine 0.25 parts by weight Polystyrene fine particles (average particle size 3 μm) 0.05 100 Add distilled water 100 〃 Further, 10% by weight of KOH To adjust the pH to 6 ± 0.3.

This coating solution was applied at a temperature of 10 ° C. and a drying temperature of 180 ° C. for 2 minutes so as to have a dry film thickness of 1 μm.

Formulation - (2) second subbing layer of gelatin (Ca ⁺⁺ content 2500 ppm) 1 part by weight of methylcellulose 0.05 〃 compounds - 0.02 〃 _{C 12 H 25 O (CH 2} CH 2 O) 10 H 0.03 〃 compound - 3.5 × 10 ^{- 3} 〃 Acetic acid 0.2 100 Add water to 100 〃 Apply this coating solution at 170 ° C for 2 minutes and dry film thickness 0.1
It was applied to a thickness of μm.

On one side of the support thus obtained, two layers of a conductive layer and a back layer having the following formulations-(3) and-(4) were simultaneously coated.

The gelatins of formulas (3) and (4) are prepared by subjecting lime-processed gelatin to cation exchange treatment to prepare gelatin from which alkaline earth metal atoms have been removed, and adding CaCl ₂ .2 to the back layer of formula (4).
H ₂ O, MgCl ₂ .6H ₂ O, and BaCl ₂ .2H ₂ O were added, respectively, to prepare the contents shown in Table 1.

Formulation (3) Conductive layer SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25μ) 300 mg / m ² gelatin (Ca ⁺⁺ content 30 ppm) 170 化合物 Compound-7 〃 Dodecylbenzenesulfonic acid sodium salt 10 〃 Dihexyl-α-sulfosuccinate sodium salt 40 〃 Polystyrene sulfonic acid sodium salt 9 〃 Formulation-(4) Back layer gelatin 2.9 g / m ² compound-300 mg / m ² compound-50 化合物 Compound-50 化合物 Compound -10 Dodecylbenzenesulfonic acid sodium salt 70 〃 Dibenzyl-α-sulfosuccinate sodium salt 15 mg / m ² 1,1'-bis (vinylsulfonyl) methane 150 エ チ ル Ethyl acrylate latex (average particle size 0.05μ) 500 パ ー Perfluorooctane sulfone Lithium acid salt 10 ケ イ 素 Silicon dioxide fine powder particles 35 〃 (average particle size 4μ, pore diameter 17Å, surface area 300m ² / g) Furthermore, the following prescription- (5),
(6), (7) and (8) silver halide emulsion layers-1,-
2, protective layers -2 and -3 were sequentially applied.

Formulation- (5) Silver halide emulsion layer-1 Solution I; 300 ml of water, 9 g of gelatin II solution; 100 g of AgNO ₃ , 400 ml of water III solution: 37 g of NaCl, 1.1 ml of (NH ₄ ) ₃ RhCl ₆ , 400 ml of water The solution II and the solution III were simultaneously added to the kept solution I at a constant rate. After removing soluble salts from this emulsion by a conventional method well known to those skilled in the art, gelatin was added, and 6-methyl-4-hydroxy-1,3,3a, 7-tetrazaindene was added as a stabilizer. The average grain size of this emulsion is 0.20μ
And the amount of gelatin per 1 kg of the emulsion was 60 g.

 The following compounds were added to the emulsion thus obtained.

Compound - 6 × 10 ^-3 mol / Ag1 mol of the compound - 60 mg / m ² Compound - 9 mg / m ² Compound - 10 mg / m ² of polystyrene sulphonic acid sodium salt 40 mg / m ² N-oleoyl -N- methyl taurine sodium salt 50mg
/ m ² 1,1'-bis (vinylsulfonyl) methane 70 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² Ethyl acrylate latex (average particle size 0.05μ) 0.46 g / m ² The applied coating solution was applied so that the applied silver amount was 1.3 g / m ² .

Of (5) - NaCl 37g, ( NH 4) 3 RhCl 6 2.2mg, water 400ml formulation; - Formulation silver halide emulsion layer -2 I solution; water 300 ml, gelatin 9 g II solution; AgNO ₃ 100 g, water 400ml III solution In the same manner as the emulsion, the solution I and the solution II
The emulsion was prepared by simultaneously adding the solution I. This emulsion was a monodisperse emulsion having an average grain size of 0.20μ.

 The following compounds were added to the emulsion thus obtained.

Emulsified dispersion of hydrazine derivative Compound 5 × 10 ⁻³ mol / Ag 1 mol Compound − 60 mg / m ² compound − 9 mg / m ² compound − 10 mg / m ² Polystyrene sulfonate sodium salt 50 mg / m ² N-oleoyl − N-methyltaurine sodium salt 40 mg / m ² 1,1′-bis (vinylsulfonyl) methane 80 mg / m ² 1-phenyl-5-mercaptotetrazole 3 mg / m ² Ethyl acrylate latex (average particle size 0.05 μ) 0.40 g / m ² The coating solution thus obtained was applied so that the coated silver amount was 1.3 g / m ² .

Formulation - (7) protective layer-2 Gelatin 1.0 g / m ² lipoic acid 5 mg / m ² sodium dodecylbenzenesulfonate 5 mg / m ² Compound - 20 mg / m ² of polystyrene sulphonic acid sodium salt 10 mg / m ² Compound - 20 mg / m ² of ethyl acrylate latex (average particle size 0.05 .mu.m) 200 mg / m ² formulation - (8) protective layer -3 gelatin 1.0 g / m ² of silicon dioxide fine powder particles (average particle size 3.5 [mu], pore diameter 25
Å, surface area 700 m ² / g) 50 mg / m ² sodium dodecylbenzenesulfonate 20 mg / m ² potassium perfluorooctanesulfonate 10 mg / m ² N-perfluorooctanesulfonyl-N-propylglycinepotadium salt 3 mg / m ² Sodium salt of polystyrene sulfonic acid 2 mg / m ² Sulfate sodium salt of poly (degree of polymerization 5) oxyethylene nonylphenyl ether 20 mg / m ² <Preparation method of emulsified dispersion of hydrazine derivative> The mixture was heated to 65 ° C. and uniformly dissolved to obtain a solution I.

The solution was heated to 65 ° C. and uniformly dissolved to obtain a solution II.

The liquids I and II were mixed and stirred at a high speed with a homogenizer (manufactured by Nippon Seiki Seisakusho) to obtain a fine particle emulsified dispersion. This emulsion was heated under reduced pressure to remove ethyl acetate, and then water was added to make 250 g. The residual ethyl acetate was 0.2%.

The number of aggregates of conductive metal oxides (SnO ₂ / Sb) generated in Samples 1 to 19 thus obtained was examined. Table 1 shows the results.

As is clear from Table 1, the sample of the present invention shows no generation of aggregates.

Example-2 In Samples-2 to 7 of Example-1, simultaneous application was performed with the back layer of formulation- (4) as the lower layer and the conductive layer of formulation- (3) as the upper layer. In the same way as -1,
Samples -20 to 25 were prepared, and the occurrence of aggregates was examined in the same manner as in Example-1. Table 2 shows the results.

As is evident from Table 2, it can be seen that Samples -21 to 25 of the present invention have no generation of aggregates.

Example-3 Gelatin 14 mg / m ^{2 on} both sides of a biaxially stretched 100 μ thick bluish dyed polyethylene terephthalate support, 9 mg / m ² of a reaction product of a polyamide comprising diethylenetriamine and adipic acid and epichlorohydridine. Was coated with an undercoat layer. On one side of this support the following formulation:
The three layers (9), (10), and (11) of the conductive layer, the back layer, and the back protective layer were simultaneously coated in a multilayer manner.

Formulation (9) Conductive layer SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 400 mg / m ² gelatin (Ca ⁺⁺ content 30 ppm) 220 化合物 Compound-1 〃 Dodecylbenzenesulfonic acid sodium salt 25 〃 dihexyl -α- sulfosuccinates sodium salt 45 〃 polystyrene sulfonic acid sodium salt 9 〃 formulation - (10) back layer gelatin (Ca ⁺⁺ content 30 ppm) 4.7 mg / m ² compound - 10 mg / m ² compound - 40 〃 Compound-65-Compound-85-5-Methylbenzotriazole 9-Dodecylbenzenesulfonic acid sodium salt 70-Polystyrenesulfonic acid sodium salt 10-1,2-bis (vinylsulfonylacetamide) ethane 160-Formula-(11) Back protection Layer Gelatin (Ca ⁺⁺ content 30 ppm) 1.2 mg / m ² Polymethyl methacrylate fine particles (average particle size 2.5 μm) 30 バ Barium sulfate-strontium fine particles (average particle size 1.0 μm)
m) 100 化合物 Compound-3 Ｎ N-perfluorooctanesulfonyl-N-propylglycine potadium salt 3 mg / m ² Sodium chloride 30 化合物 Compound 30 In addition, the following formula-(12), (1
3), (14) and (15) silver halide emulsion layers-1,-
2, -3 and a protective layer were applied.

Formulation- (12) Silver halide emulsion layer-1 An aqueous solution of potassium bromide and an aqueous solution of silver nitrate are simultaneously added to an aqueous gelatin solution at 40 ° C. for about 20 minutes while being vigorously stirred, and silver bromide having an average particle diameter of 0.08 μm is added. An emulsion was obtained. 580 mg of sodium thiosulfate and chloroauric acid (tetrahydrate) were added to each of the emulsions per mol of Ag, and the emulsion was heated at 75 ° C. for 80 minutes to perform chemical sensitization. Using the silver bromide grain emulsion thus obtained as a core, grains are grown in the same manner as in the first precipitation environment, except that the pAg of the solution is controlled to be 7.90, and finally the average grain size is 0.18 μm. Of a core / shell type monodispersed silver bromide emulsion was obtained. After washing and desalting, 6.2 mg of sodium thiosulfate and 1 mg of chloroauric acid (tetrahydrate) were added to each of the emulsions per 1 mol of Ag, and heated at 65 ° C. for 60 minutes to perform chemical sensitization to prepare emulsions. . Anhydro-2- [3- (phenylhydrazolo) is used as a fogging agent on this emulsion.
Butyl] -3- (3-sulfopropyl) benzothiazolium hydroxide as a compound as a sensitizing dye
Was added in an amount of 257 mg and 140 mg, respectively, per mole of Ag. Further, 10 mg / m ^{2 of} sodium dodecylbenzenesulfonate was added as a coating aid, and 20 mg / m ^{2 of} sodium polystyrenesulfonate was added as a thickener, and coating was performed so that the applied silver amount was 1.0 g / m ² .

Formulation- (13) Silver halide emulsion layer-2 An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous gelatin solution at 45 ° C. for about 40 minutes while being vigorously stirred, and the average particle diameter was 0.2 μm. To obtain a silver bromide emulsion.
The emulsion was subjected to chemical sensitization by adding 5 mg of sodium thiosulfate and 1 mol of silver chloroaurate (tetrahydrate) per mol of silver and heating at 75 ° C. for 80 minutes.

The silver bromide particles thus obtained were used as a core to further grow by further treating in the same precipitation environment for 40 minutes, and finally an octahedral monodispersed core / shell silver bromide emulsion having an average particle diameter of 0.35 μm was obtained. I got This emulsion was further divided into two equal parts, and the following amounts of sodium thiosulfate and chloroauric acid (tetrahydrate) were added, and the mixture was heated at 65 ° C. for 60 minutes to carry out a chemical sensitization treatment. A silver halide emulsion was obtained.

The fogging agent and the sensitizing dye used in Formulation- (12) were added to the emulsion at 257 mg and 200 mg, respectively, per mole of Ag. Further, add 3m each of the coating aid and thickener used in formula (12).
g / m ² and 4 mg / m ^2, as a hardener, 1,3-vinylsulfonyl-2-propanol 62 mg / m ² In addition, the amount of coated silver is 0.8 g /
It was coated so as to become a m ^2.

Formulation- (14) Silver halide emulsion layer-3 An aqueous solution of potassium bromide and an aqueous solution of silver nitrate were simultaneously added to an aqueous gelatin solution at 75 ° C. for about 40 minutes while being vigorously stirred, and the average particle diameter was 0.4 μm. To obtain a silver bromide emulsion.
The emulsion was subjected to chemical sensitization by adding 4 mg of sodium thiosulfate and 1 mol of silver chloroaurate (tetrahydrate) per mol of silver and heating at 75 ° C. for 80 minutes.

The silver bromide particles thus obtained are used as a core to further grow by further treating in the same precipitation environment for 40 minutes, and finally an octahedral monodispersed core / shell silver bromide emulsion having an average particle diameter of 0.6 μm. I got After washing with water and desalting, 0.9 mg of sodium thiosulfate per mole of silver was added to the emulsion, and the mixture was added
The mixture was heated for 0 minutes to perform a chemical sensitization treatment to obtain an internal latent image type silver halide emulsion.

The fogging agent and the sensitizing dye used in Formulation- (12) were added to the emulsion at 257 mg and 200 mg, respectively, per mole of Ag. Further, add 3m each of the coating aid and thickener used in formula (12).
g / m ² and 4 mg / m ² , and Compound- 10 mg / m ² were added, and the mixture was coated so that the coated silver amount became 1.5 g / m ² .

Formulation - (15) Protective layer Gelatin 1.7 g / m ² Barium sulfate - strontium particles (average particle size 1.0μ
m) 85 mg / m ² sodium dodecylbenzenesulfonate 45 〃 N-perfluorooctanesulfonyl-N-propylglycine potadium salt 2 ナ ト リ ウ ム sodium polystyrenesulfonate 10 〃 1,3-divinylsulfonyl-2-propanol 53 比較 comparison As a sample, a sample was prepared by changing only the gelatin of the formulas (9), (10) and (11) to the one having a Ca ⁺⁺ content of 2700 ppm, and using the same other components. As a result, agglomerates of the comparative sample Ca occurrence of (SnO ₂ / Sb) is to 55 / m ^{2 ++}
The sample of the present invention using gelatin having a content of 30 ppm was satisfactory without generation of aggregates. The conductivity of both the sample of the present invention and the comparative sample was 3 × 10 ¹⁰ Ω (10% RH at 25 ° C.).

Example-4 On one side of a biaxially stretched polyethylene terephthalate (175 μm thick) support having an undercoat layer on both sides, two layers of a conductive layer and a back layer of the following formulas (16) and (17) were provided. At the same time, multi-layer coating was performed.

Formulation (16) Conductive layer SnO ₂ / Sb (9/1 weight ratio, average particle size 0.25 μm) 300 mg / m ² gelatin (Ca ⁺⁺ content 30 ppm) 170 〃 Proxel 7 ナ ト リ ウ ム Sodium dodecylbenzenesulfonate 10 〃 Dihexyl-α-sulfone succinate sodium 40 ナ ト リ ウ ム Sodium polystyrene sulfonate 9 処方 Prescription-(17) Back layer Gelatin (Ca ⁺⁺ content 30 ppm) 1580 mg / m ² compound-72 バ Barium sulfate-strontium (average particle size 1.5 μm ) 50 mg / m ² liquid paraffin 60 〃 N-perfluorooctanesulfonyl-N-propylglycine potassium 5 ス ル ホ ン sodium dodecylbenzenesulfonate 9 〃 dihexyl-α-sulfone succinate 34 〃 sodium polystyrene sulfonate 4 〃 proxel 5 〃 Further, an emulsion layer and a protective layer of the following formulas (18) and (19) were coated on the opposite surface.

Formulation-(18) Emulsion layer Solution II and Solution III were simultaneously added to Solution I for 5 minutes, and when octahedral particles having an average particle size of 0.10 μm were formed, the addition of Solution II and Solution III was suspended, and 1 mole of silver was added. Sodium thiosulfate and chloroauric acid tetrahydrate
115 mg each was added, followed by a chemical sensitization treatment at 75 ° C. for 60 minutes. The solution was added to the chemically sensitized core particles thus obtained again.
Simultaneous addition of II and solution III was continued, and solution IV was added over 5 minutes 5 minutes after resuming addition of solution II, and the pAg value of the mixture was reduced.
Adjust the addition rate of Solution III to 7.50,
Solution II was added at 40 ° C. for 40 minutes. After the completion of the addition of the solution II, the resultant was washed with water and desalted by a sedimentation method, and then dispersed in an aqueous solution containing 100 g of inert gelatin. To this emulsion were added sodium thiosulfate and chloroauric acid tetrahydrate per mole of silver.
Add 34 mg each, and adjust the pH and pAg values to 8.9 and 7.0 (40
° C), and then subjected to a chemical sensitization treatment at 75 ° C for 60 minutes.

Thus, an internal latent image type cubic core / shell emulsion whose surface was chemically sensitized and having an average particle size of 0.28 μm was finally obtained. The following compounds were added to this emulsion, and the coated silver amount was 1.7 g / m
² was applied.

Nucleating agent (compound-) 0.04 mg / m ² Sensitizing dye (compound-) 24 〃 5-methylbenzotriazole 4.1 ナ ト リ ウ ム sodium dodecylbenzenesulfonate 5 〃 1,3-divinylsulfonyl-2-propanol 56 〃 polystyrene sulfonic acid Sodium 35 〃 Formula-(19) <Protective layer> Inert gelatin 1300 mg / m ² Colloidal silica 249 〃 Liquid paraffin 60 バ Barium strontium sulfate (average particle size 1.5 μm) 32 〃 Proxel 4.3 〃 N-perfluorooctanesulfonyl- N- propyl-glycine Potassium nitrosium salt 5.0 mg / m ² 1,3-divinyl-sulfonyl-2-propanol 56 mg / m ² compound - 30 mg / m ² As a comparative sample, a sample was prepared by changing only the gelatin of the formulas (16) and (17) to that having a Ca ⁺⁺ content of 2700 ppm and using the same other components. As a result, the generation of aggregates (SnO ₂ / Sb) of the comparative sample was 45 pieces / m ² and the Ca ⁺⁺ content was 30
The sample of the present invention using ppm gelatin was satisfactory without generation of aggregates.

The conductivity is 3.3 × 10 ¹⁰ Ω for both the sample of the present invention and the comparative sample.
(25 ° C., 10% RH).

Claims (1)

(57) [Claims] 1. A silver halide photographic material having at least one layer containing a conductive metal oxide and another hydrophilic colloid layer on a support, a layer adjacent to a layer containing a conductive metal oxide. Silver halide photographic light-sensitive material, wherein the concentration of the alkaline earth metal atoms is 1500 ppm or less based on the amount of the binder in the adjacent layer.