JPH10282619A - Silver halide photographic sensitive material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide the silver halide photographic sensitive material stabilized and enhanced in antistatic property independent of humidity by forming a layer containing carbon black and an amphoteric surfactant. SOLUTION: The antistatic layer to be formed contains the carbon black and the amphoteric surfactant, thus permitting the obtained antistatic performance to be independent of humidity and as superior as conductive metal oxides and high in cost performance and not to be deteriorated by photographic processing conditions and to exhibit excellent antistaticness. In this case the combined use of the carbon black and the amphoteric surfactant permits the carbon black to be enhanced in dispersibility in a gelatin solution and the amphoteric surfactant to enhance synergistically the intrinsic conductivity of the carbon back.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a silver halide photographic material having excellent antistatic properties, and more particularly to a lithographic printing material utilizing a silver complex salt diffusion transfer method.

[0002]

2. Description of the Related Art A silver halide photographic material uses a film or a resin-coated paper as a support, but these materials have low conductivity and cause various problems.

One of these problems is that films,
When a coating solution containing silver halide is applied at high speed to a support such as resin-coated paper, the support is charged while being rubbed and rubbed by a roller, and when the support is discharged, the silver halide is fogged ( (Electrostatic fog). This problem can be avoided before or simultaneously with the application of the coating solution containing silver halide, if the antistatic layer is applied.

Secondly, when a user uses photosensitive materials, they are charged and dust and dust adhere to the photosensitive materials, and undesired images such as pinholes are formed during exposure and photographic processing. However, there is a problem that the workability is poor due to the overlapping of the photosensitive materials. What is important in these problems is that the antistatic properties must be good before and after the processing of development, fixing, and washing, even under low humidity conditions.

[0005] In order to solve these problems, as an antistatic method closest to the present invention, a conductive carbon black is used to secure the antistatic property of JP-A-4-26444.
No. 3, but conductive carbon black has poor dispersion stability, the amount of use is limited, and the conductivity of the coating solution is significantly deteriorated with the lapse of time. The dispersion stability of not only conductive carbon black but also a layer containing carbon black is high. And the stability of the coating solution over time and the coating properties were poor.

Conventionally, there has been proposed a method for improving the conductivity of a support or a coated surface of a photographic light-sensitive material, and attempts have been made to utilize various hygroscopic substances, water-soluble inorganic salts, certain surfactants, polymers and the like. Have been. For example, US Pat. No. 2,882,
157, 2,972,535, 3,062,7
No. 85, No. 3,262,807, No. 3,514,29
Nos. 1, 3,938,999, and JP-A-2-20865.
No. 1, No. 5,202,333, U.S. Pat. Nos. 2,982,651, 3,428,456, 3,552,972, and 3,655. , 387, etc. are known.

However, they are effective in certain film supports and photographic materials, but adversely affect the photographic properties of other photographic materials, lose their antistatic action during photographic processing, and are subject to low humidity conditions. In some cases, there was no antistatic effect at all.

US Pat. Nos. 3,753,716 and 4,266,015 disclose the antistatic effect of a fluorine-containing polymer due to the effect of lowering the friction coefficient. In order to obtain antistatic properties on both front and back surfaces of the photosensitive material, the fluorine-containing polymer must be contained in the uppermost layer on both the front and back surfaces, and the fluorine-containing polymer must be contained in the upper layer of the photosensitive layer of the photographic material. become. Most fluorine-containing polymers have a water-repellent property, and when such antistatic properties are obtained on both front and back surfaces, the fluorine-containing polymer-containing layer provided on the uppermost layer is repellent in the development of a photographic material. In some cases, this may cause a development hindrance in hydration and adversely affect photographic properties.

As antistatic methods having no humidity dependency, Japanese Patent Application Laid-Open Nos. Sho 56-143431 and 63-98656 describe the same.
A method using a conductive metal oxide is described in, for example, Japanese Patent Application Laid-Open No. H10-260, 1988. These are used by coating the fine particles of the conductive metal oxide by itself or with fibrous potassium titanate. These common drawbacks include the possibility of agglomeration of the particles during application in the product manufacturing process and soiling of the applied material.
Further, the conductive metal oxide is very expensive, which leads to a considerable increase in cost.

On the other hand, a lithographic printing material to which a silver complex salt diffusion transfer method (DTR method) is applied is known. This lithographic printing material has an undercoat layer, a silver halide emulsion layer and a physical development nucleus layer on a support, and is disclosed in U.S. Pat. No. 3,721,559.
No. 3,490,905, No. 3,385,70
No. 1, No. 3,814,603, No. 3,454,3
No. 98, No. 3,764, 323, No. 3,099,
No. 209, JP-B-44-27242, 48-305
No. 62, JP-A-53-9603 and JP-A-53-21602.
Nos. 54-103104 and 56-9750.

According to a typical silver complex salt diffusion transfer method suitable for the method of making a lithographic printing plate, an undercoat layer which also prevents halation, a silver halide emulsion layer, a physical development nucleus is provided on a support. When the photosensitive material comprising the layers is subjected to image exposure and development processing, the silver halide on which the latent image is formed becomes blackened silver in the emulsion. At the same time, the silver halide having no latent image formed thereon is dissolved by the action of the silver halide solvent contained in the developing solution and diffuses to the surface of the photosensitive material. The dissolved and diffused silver complex is deposited as image silver on the physical development nuclei of the surface layer by the reducing action of the developing agent.

These lithographic printing materials have the advantage that they can be made directly from a plate making camera or laser output machine.
It is widely used because of its simplicity. These lithographic printing plates are required to have a high resolution, and have an undercoat layer also serving as an antihalation layer as described above. Conventionally, carbon black has been used as an antihalation agent, and it would be advantageous if an excellent antistatic performance could be imparted by utilizing the conductivity of the carbon black.

[0013]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a silver halide photographic light-sensitive material having a stable antistatic property independent of humidity. Another object of the present invention is to provide a lithographic printing material to which a silver complex salt diffusion transfer method having excellent antistatic properties is applied.

[0014]

According to the present invention, at least one antistatic layer containing carbon black and an amphoteric surfactant is provided.
This is achieved by providing layers.

By using carbon black and an amphoteric surfactant, it has the same antistatic performance as a conductive metal oxide having no humidity dependency, and is excellent in cost performance.
In addition, it has been found that, depending on the photographic processing conditions, excellent antistatic performance without deteriorating the antistatic performance is exhibited.

The present invention is the result of research on how to effectively apply the conductivity of carbon black to photographic materials.
It succeeded in improving the dispersion stability of carbon black in a water-soluble colloid such as gelatin, and attaining a high level of antistatic performance when a carbon black-containing layer was applied and dried.

That is, by using a combination of carbon black and an amphoteric surfactant, the dispersibility of the carbon black in the gelatin solution is enhanced, and the amphoteric surfactant synergistically enhances the inherent conductivity of the carbon black. I found something.

Accordingly, the carbon black used in the present invention is not limited to the highly conductive carbon black described in JP-A-4-264443, but may be any of the commonly used carbon blacks. ,
In each case, high conductivity is obtained.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The carbon black used in the present invention is not particularly specified, and those having good dispersibility and low specific gravity are desirable.
It is known that the conductivity is caused by the contact between the conductive powders, and the conductivity depends on the volume% of the conductive powder. This is an advantage that the required amount of black is small. The carbon black of the present invention is SD-9134 (conductive carbon black) manufactured by Dainippon Ink and S
D-9139, SD-9020, etc. can be obtained from the manufacturer.

The carbon black of the present invention is pulverized carbon obtained by incomplete combustion or pyrolysis of natural gas, petroleum, etc., and there are three types of production methods, high content of low PH volatile substances, There are channel black, which has a small size and is mainly used as a reinforcing agent for natural rubber, thermal black which has a coarse particle size and is used as a pigment, and furnace black which is made from natural gas and has a medium particle size. When the raw material is injected into a preheated reactor to cause thermal decomposition, the furnace temperature rises, and then the decomposition reaction is automatically performed. Compounding is also possible, and the particle size is preferably 100 μm or less, particularly preferably 0.01 to 2 μm. Particle size is 1
When the thickness is more than 00 μm, the coating material is stained when a coating liquid is applied during the production of a photographic light-sensitive material, and carbon black cannot be uniformly contained without sufficient dispersion, thereby losing commercial value.

The carbon black-containing layer may also serve as a backing layer, an undercoat layer, an antihalation layer, an anti-curl layer, an adhesive layer, and the like, and further, various hardening agents and matting agents used in the art. Additives such as a dispersant, an adhesive, an antifoggant, and a stabilizer, and a surfactant other than the amphoteric surfactant of the present invention may be used in combination, if necessary.

The carbon black-containing layer containing carbon black and an amphoteric surfactant used in the present invention can be used in combination with other antistatic agents, for example, as described in JP-A-64-69621.
No. 2-2644
2. Thermosetting conductive polymer described in No. 2, JP-A-56-14
No. 3431 and JP-A-63-98656.

By using the carbon black of the present invention and an amphoteric surfactant, the coating solution has good stability over time, good coatability, and anti-static properties independent of humidity can be obtained. It was unexpected that a photographic light-sensitive material with antistatic properties could be produced.

The amphoteric surfactant of the present invention generally contains an anionic group and a cationic group in one molecule, and is disclosed in US Pat. No. 3,843,368 and JP-A-59-49535.
And JP-A-61-236546 describe the use of amphoteric surfactants in photosensitive materials and the like. However, by using these amphoteric surfactants in combination with carbon black, stable antistatic treatment can be achieved. It does not suggest that sex can be obtained. The amphoteric surfactant is an amphoteric compound containing an alkyl, aryl group or aralkyl group as a lipophilic atomic group in the molecule, or a hydrophilic atomic group, and other surfactants such as an oil-soluble surfactant and an anionic compound. It can be used in combination with a surfactant, a nonionic surfactant and the like. Specifically, the structural formulas are shown below in Chemical Formulas 1 to 8 of the amphoteric surfactant, but the present invention is not limited thereto. In addition, it can be obtained from Nikko Chemical Co., Ltd., Toho Chemical Industry Co., Ltd. Asahi Glass Co., Ltd., and Ajinomoto Co., Ltd. Among the following examples, sulfobetaine-type amphoteric surfactants are particularly preferable.

[0025]

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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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Examples of the support used in the present invention include a cellulose nitrate film, a cellulose acetate film, a cellulose acetate butyrate film, a cellulose acetate propionate film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film, and a laminate of these. There are things. Further, paper coated with a baryta or an α-olefin polymer, particularly a polymer of an α-olefin having 2 to 10 carbon atoms such as polyethylene, polypropylene, ethylene butene copolymer or the like can be used.

In the present invention, another antistatic agent can be used in combination with the protective layer or other layers of the photographic light-sensitive material, whereby a more favorable antistatic property can be obtained.
U.S. Pat. No. 2,882,882 discloses such an antistatic agent.
No. 157, No. 2,972,535, No. 2,982,6
No. 51, 3,062,785, 3,262,80
No. 7, 3,428, 456, 3, 457, 076
Nos. 3,454,625 and 3,514,291
Nos. 3,552,972, 3,615,531
Nos. 3,655,387 and 3,753,716
Nos. 3,938,999 and 4,070,189
Nos. 4,266,015 and 4,891,306.

The silver halide photographic material according to the present invention will be described. Examples of binders for the photographic component layer include gelatin, proteins such as casein, carboxymethyl cellulose, hydroxyethyl cellulose, cellulose compounds such as dextran, agar, sodium alginate, sugar derivatives such as starch derivatives, synthetic hydrophilic colloids such as polyvinyl alcohol and poly-N-. Vinyl vilolidone, polyacrylic acid copolymer, polyacrylamide, or derivatives or partial hydrolysis thereof can also be used in combination.
Among them, gelatin is preferred. The gelatin described herein refers to lime-treated gelatin, acid-treated gelatin, enzyme-treated gelatin, and the like.

The carbon black-containing layer of the present invention mainly comprises the above-mentioned binder, carbon black and an amphoteric surfactant. Although the content of carbon black can be used in a wide range, it is about 0.05 to 10 g / m ² , preferably about 0.1 to 5 g / m ² , and more preferably 0.3 to 5 g / m ^2. It is. The amount of gelatin relative to the amount of carbon black in the carbon black-containing layer is 1
More than twice is common.

The carbon black of the present invention is black and has an antihalation effect, and can be used more effectively by including it in an antihalation layer of a photographic light-sensitive material. On the other hand, a small amount of carbon black to obtain transparency,
For example, when good conductivity is exhibited with a carbon black content of 0.3 g / m ² or less, the carbon black / binder weight ratio of the carbon black-containing layer is preferably set to 1/1 or more. More preferably from 1.5 / 1 to
5/1. However, in this case, in order to protect and stabilize the carbon black-containing layer, it is preferable to provide an adjacent layer containing a binder with respect to the carbon black-containing layer, and the amount of the binder in the adjacent layer is 1 g / m ^2. Above, preferably about 1.5 to 6 g / m ² is required. This adjacent layer may be a lower layer, an upper layer, or an upper or lower layer of the carbon black-containing layer with respect to the support.

On the other hand, the amphoteric surfactant is preferably used in an amount of about 0.1 to 10% by weight, more preferably 1 to 5% by weight, based on the carbon black used in combination. At most or at least, the antistatic performance is inferior, and when it is too large, the stability of the coating solution, bubbling during manufacturing, coating failure, deterioration of coating film physical properties, and in some cases, aggregation of carbon black may be caused and conductivity may be lost. .

As the light-sensitive silver halide emulsion layer, any of those known in the art can be used, but preferably a high-sensitivity silver halide light-sensitive material, an emulsion layer used in a silver halide light-sensitive material for high-temperature rapid processing, etc. In some cases, an electrophotographic master using toner or a direct drawing master
It is also possible to use the antistatic layer of the present invention for such purposes.

In the photographic light-sensitive material of the present invention, the composition of a photographic processing solution such as a developing solution, a development stopping solution, a fixing solution, etc., can be a composition known to those skilled in the art depending on the purpose and type of the photographic material. .

The present invention is particularly suitable for a lithographic printing material having a subbing layer, a silver halide emulsion layer and a physical development nucleus layer in this order on a support. The layer containing carbon black is an undercoat layer and / or a back coat layer.

The amount of the binder in the undercoat layer is 0.5 to 8 g.
/ M ² , preferably 1 to 5 g / m ² . The undercoat layer preferably contains carbon black for the purpose of preventing halation as described above, and further contains the amphoteric surfactant. Solid powder (for example, silica particles) having an average particle size of 0.1 to 10 microns for improving printing durability
May be included. Further, a photographic additive such as a developing agent can be included. The undercoat layer is disclosed in JP-A-48-5503,
As described in JP-A-48-100203 and JP-A-49-16507.

The silver halide emulsion layer includes, for example, silver chloride,
It consists of silver bromide, silver chlorobromide, and those containing silver iodide. The silver halide crystal may contain a heavy metal salt such as a rhodium salt, an iridium salt, a palladium salt, a ruthenium salt, a nickel salt, a platinum salt, and the like, in an amount of 10 ^-8 to 10 ^-3 per mol of silver halide. Is a mole. The crystal form of the silver halide is not particularly limited, and may be cubic to tetradecahedral grains, or core-shell or tabular grains. The silver halide crystal may be a monodisperse or polydisperse crystal,
Its average particle size is in the range of 0.2-0.8 μm. One preferred example is a monodispersed or polydispersed crystal containing 70 mol% or more of silver chloride containing a rhodium salt or an iridium salt or both.

The silver halide emulsion can be sensitized in various ways as it is manufactured or coated. It is preferred to chemically sensitize by methods well known in the art such as, for example, with sodium thiosulfate, alkyl thioureas, or with gold compounds such as rhodium gold, gold chloride, or a combination of both. Silver halide emulsions can also be sensitized or desensitized positively or negatively by dyes such as cyanine, merocyanine and the like. There is no particular limitation on the wavelength range in which the sensitization or desensitization can be performed. Therefore, orthosensitization, panchromatic sensitization, helium-neon laser sensitization, argon laser sensitization, LED sensitization, and semiconductor laser sensitization can be performed, and UV sensitization and visible light reduction for a bright room can be performed. You can feel it.

The surface layer present above the silver halide emulsion layer contains physical development nuclei. As physical development nuclei, silver, antimony, bismuth, cadmium, cobalt, lead, nickel, palladium, rhodium, gold, platinum and other metal colloid fine particles, and sulfides, polysulfides, selenides of these metals, or those It may be a mixture or a mixed crystal. The physical development nucleus may or may not contain a hydrophilic binder, but gelatin, starch, dialdehyde starch, carboxymethylcellulose, gum arabic, sodium alginate, hydroxyethylcellulose, polystyrene sulfonic acid, vinyl imidazole and acrylamide It may contain a polymer, a hydrophilic polymer such as polyvinyl alcohol or an oligomer thereof, and the content thereof is 0.5 g / m ^2.
The following is preferred. In addition, the physical development nucleus layer
It may contain a developing agent such as hydroquinone, methylhydroquinone, or catechol, or a known hardener such as formalin or dichloro-s-triazine.

As the support of the lithographic printing material of the present invention,
Paper, a synthetic or semi-synthetic polymer film, a metal plate of aluminum, iron, or the like can be used as long as it can withstand lithographic printing. One or both surfaces of the support may be coated with one or more polymer films or metal thin films. The surface of these supports can be subjected to a surface treatment in order to improve the adhesion to the coating layer.

Particularly preferably used supports are paper coated on both sides or one side with a polyolefin polymer, a polyester film, a polyester film having a hydrophilic surface, an aluminum plate having been subjected to a surface treatment, and the like.
These supports may contain pigments for preventing halation and solid fine particles for improving the surface properties. Further, the support may be light-transmissive so that backside exposure is possible.

The lithographic printing material of the present invention is preferably provided with a backing layer for the purpose of preventing curling and the like. It is preferable that the backcoat layer contains carbon black for preventing halation and further contains the amphoteric surfactant. The binder amount of the backing layer is about 1 to 6 g / m ² , preferably 2 to 5 g / m 2.
g / m ² .

The lithographic printing material of the present invention preferably contains gelatin as a binder. The containing layer is a backing layer, an undercoat layer, an emulsion layer, and may be a physical development nucleus layer. These gelatin-containing layers can be hardened with a gelatin hardener. Examples of the gelatin hardener include inorganic compounds such as chrome alum, aldehydes such as formalin, glyoxal, malealdehyde and glutaraldehyde, and N such as urea and ethylene urea.
Aldehydes such as methylol compounds, mucochloric acid, 2,3-dihydroxy-1,4-dioxane, 2,4
-Dichloro-6-hydroxy-S-triazine salt,
Compounds having an active halogen, such as 2,4-dihydroxy-6-chloro-triazine salt, divinyl sulfone,
Divinyl ketone, N, N, N-triacroylhexahydrotriazine, compounds having two or more active three-membered ethyleneimino groups or epoxy groups in the molecule, dialdehyde starch as a polymer hardener And the like, or one or more of various compounds.

The hardener can be added to all layers or to some or only one layer.
Of course, in the case of two-layer simultaneous application, the diffusible hardener can be added to only one of the layers. The addition method can be added at the time of emulsion production or in-line at the time of coating.

The developing solution used in the lithographic printing material of the present invention includes alkaline substances such as sodium hydroxide, potassium hydroxide, lithium hydroxide and sodium tertiary phosphate, such as sulfites and halogens as preservatives. Silver halide solvents, for example, thiosulfate, thiocyanate, cyclic imide, 2-mercaptobenzoic acid, amines, etc., thickeners, for example, hydroxyethylcellulose, carboxymethylcellulose, etc., antifoggants, for example, potassium bromide, -262
The compounds described in JP-A No. 01-001 can contain a developing agent such as hydroquinone, catechol, 1-phenyl-3-pyrazolidone and the like, and a development modifier such as polyoxyalkylene compound and onium compound. Further, as the developing solution, a compound or the like described in U.S. Pat. No. 3,776,728 which improves the ink running of the surface silver layer can be used.

In carrying out the silver complex salt diffusion transfer method in the present invention, for example, British Patent No. 1,000,11
No. 5, No. 1,012,476, No. 1,042,477
As described in the specification of Japanese Patent Application Laid-Open No. H10-163, a developer is mixed in a silver halide emulsion layer and / or an image receiving layer or another water-permeable layer adjacent thereto. Therefore, in such a material, the processing solution used in the development stage may be a desired "alkaline activating solution" containing no developer.

The surface silver layer after development of the lithographic printing plate of the present invention can be converted to ink receptivity or enhanced in receptivity with any known surface treating agent. Examples of such a processing solution include JP-B-48-29723 and U.S. Pat.
721, 559 and the like. The printing method, the desensitizing solution, the humidifying solution, and the like to be used can be a commonly known method.

[0054]

EXAMPLES The present invention will be illustrated below by way of examples, but the present invention is not limited thereto.

Example 1 For the purpose of hydrophilization, an undercoating composition containing an epoxy compound as disclosed in JP-A-60-213942 was used as a backing layer on a polyester film support which had been subjected to aqueous undercoating. Apply antistatic layer as above.

<Method of preparing antistatic coating liquid> Gelatin 60 g Water 500 ml Various carbon black dispersions (manufactured by Dainippon Ink and Chemicals, Inc.) Xg (solid content) 10% Various surfactants ym 2,4- Dichloro-6-hydroxy-S-triazine salt (10% aqueous solution) 50 ml 1000 ml by adding water The types and amounts of carbon black and surfactant used here are shown in Table 1.

The coating solution immediately after the above coating solution and aged at 36 ° C. for 24 hours were applied at a moisture application amount of 50 ml / m ² . On the opposite side of the support, a silver halide emulsion layer spectrally sensitized to a red wavelength region for a helium / neon laser (silver content: 3.5 g / g)
m ² , the amount of gelatin is 2 g / m ² ) and the protective layer (the amount of gelatin is 1
g / m ² ) to prepare each sample. Thereafter, each sample was heated at 40 ° C. for 6 days.

The heated sample was cut and developed. The developer was MRA-CD401 manufactured by Mitsubishi Paper Mills, Ltd.
At 38 ° C for 20 seconds.
The substrate was treated with F-901 at 35 ° C. for 20 seconds, and then washed with water for 30 seconds. All the processes were performed manually.

The antistatic ability of the sample before and after the treatment was left for 2 hours in an atmosphere of 25 ° C. and 20% RH (relative humidity) in order to examine the humidity dependency. The surface resistance was measured using a surface resistance meter model HT-210. As the surface resistance is lower, the antistatic property is better. Table 2 shows the results.

The carbon blacks used in Table 1 are of three types, each of which can be classified as follows. SD9020: Pigment using polyacrylic acid as a dispersant. SD9139: Pigment using a sorbitan compound having ethylene oxide as a dispersant. SD9134: Conductive carbon (acetylene black) produced by using acetylene gas as a pigment for SD9139. SD9020 and SD9139 are mainly dispersants. The only difference is that no amphoteric surfactant is used in each carbon black.

[0061]

[Table 1]

Table 2 shows the surface resistance and the applicability at each humidity. The applicability was evaluated on the basis of the following criteria, after being applied by a slide bead applicator. G1: A uniform coating surface. G2: Slight repelling is observed. G3: Repelling is somewhat common. G4: Repelling and coating unevenness are observed. G5: The coating liquid aggregates and strong unevenness occurs.

[0063]

[Table 2]

The samples of Table 2 were prepared at 25 ° C. 50% and 30 ° C.
As a result of measuring the surface resistance under the condition of 70%, almost the same surface resistance as shown in Table 2 was shown. That is, it can be confirmed that there is no dependency on humidity, and the coating solution has good aging properties and stable antistatic properties can be obtained.

As is evident from Table 2, the present invention using an amphoteric surfactant regardless of the type of carbon black is excellent in coatability, in particular, its antistatic properties are not dependent on humidity, and its antistatic properties are quite excellent. It can be said that. Therefore, it has been clarified that the embodiments of the present invention provide a silver halide photographic light-sensitive material which is excellent in antistatic property without humidity dependency.

Example 2 The amount of carbon black and the amount of surfactant in the coating solution for the antistatic layer which also served as the backing layer in Example 1 were each 1 shown in Table 1
/ 5, and the amount of gelatin was 1/1.
5 was prepared. At the same time, a coating solution was prepared as an adjacent layer so that the amount of gelatin became 3 g / m ² . The antistatic layer and the adjacent layer were coated on the support used in Example 1 so that the adjacent layer was an upper layer. The evaluation was performed in the same manner as in Example 1. Table 3 shows the results.

[0067]

[Table 3]

As in Example 1, a layer adjacent to the carbon layer containing the carbon black of the present invention and the amphoteric surfactant can provide high conductivity with a small amount of carbon black without inferior in antistatic properties. Therefore, the embodiments of the present invention are excellent in antistatic properties independent of humidity, can provide high conductivity when the amount of carbon black is 0.05 g / m ² or less, and can be used for silver halide photographic photosensitive materials requiring light transmittance. It has been clarified that the antistatic layer of the material can be provided in a wide range.

The transmission densities of the layers obtained in Tables 2 and 3 were measured. As a result, the transmission density of carbon black of 0.5 g / m ^{2 in} Table 2 was 3.0 to 4.0, and the transmission density of carbon black in Table 3 was 3.0. The transmission density of carbon black 0.1 g / m ² is 0.2 to 0.4,
Even with a silver halide photographic light-sensitive material requiring light transmission, high conductivity can be obtained with a small amount of carbon black.

Example 3 A backing layer containing 3 g / m ² of silica particles having an average particle size of 3.5 μm (coulter counter method) on one side of a 175 micron subbed polyethylene terephthalate film. m ² ), the surface on the opposite side was subjected to corona discharge machining, and then 0.7 g / m ^{2 of} the carbon black shown in Example 1 and the surfactant (10
% Solution) 0.3 ml / m ^2, and a silica powder having an average particle diameter of 3.5 [mu] (Fuji Sylysia manufactured SY445) 0.9g / m ²
Undercoat layer (gelatin 3.5 g / m ² )
-Sensitized silver chloride emulsion with 0.1 g / m ² -phenyl-3-pyrazolidone (0.8 g gelatin / g
(including m ² ) as silver nitrate to give 1.0 g / m ² . The combination of the carbon black and the surfactant in the undercoat layer was the same as in Example 1.

As hardening agents, 2,4-dichloro-6-
Sodium hydroxy-s-triazine was added to the undercoat
The emulsion layer contained 0 mg / m ² and 80 mg / m ² of N-methylolethylene urea. After drying,
No. 21602 in Example 2 (a polymer containing a copolymer of acrylamide and imidazole of No. 3 and containing hydroquinone as a developing agent at a ratio of 0.5 g / m ² ) described in Example 2 A lithographic printing plate was prepared by adding and drying 4 mg / m ² of pullulan of 277747.

The surface resistance of these lithographic printing plates was measured before and after development in the same manner as in Example 1.
The developing treatment was carried out at 30 ° C. for 20 seconds with the following transfer developer, followed by the following neutralizing solution at 25 ° C. for 20 seconds, excess liquid was removed with a squeeze roller, and dried at room temperature.

<Transfer Developer> Water 700 ml Potassium hydroxide 20 g Anhydrous sodium sulfite 50 g 2-mercaptobenzoic acid 1.5 g 2-methylaminoethanol 15 g Water is added to make 1 liter.

<Neutralizing solution> Water 600 ml Citric acid 10 g Sodium citrate 35 g Colloidal silica (20% solution) 5 ml Ethylene glycol 5 ml Add water to make 1 liter.

As the surface resistance value, the same measurement value as in Example 1 was obtained. That is, the lithographic printing material of the present invention exhibited excellent conductivity before and after treatment at 10 ^-4 to 10 ^-5 , but the comparative lithographic printing material showed 10 ^-8 to 10 ^-12 .

Example 4 A planographic printing material was prepared according to Example 3. However, 0.75 g / m ² of the carbon black of Example 1 and 0.3 ml / m ² of a surfactant (10% solution) in the same combination as in Example 1 were contained in the backing layer. For these lithographic printing materials, the surface resistance was measured in the same manner as in Example 3. As a result, a result similar to that of Example 3 was obtained.

[0077]

By providing a layer containing carbon black and an amphoteric surfactant, the antistatic property of the photographic light-sensitive material is improved. In particular, high antistatic performance having no humidity dependency can be obtained. Further, it is possible to provide a silver halide photographic light-sensitive material having improved stability over time of a coating solution of a carbon black-containing layer, and having transparency even though carbon black is used, and having stable antistatic properties. . In particular, the present invention is suitable for a lithographic printing material to which a silver complex salt diffusion transfer method using carbon black as an antihalation pigment is applied.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI G03F 7/07 G03F 7/07 7/11 503 7/11 503

Claims (5)

[Claims] 1. A silver halide photographic material having at least one silver halide emulsion layer on a support,
A silver halide photographic material having a layer containing carbon black and an amphoteric surfactant. 2. A lithographic printing material having at least an undercoat layer, a silver halide emulsion layer and a physical development nucleus layer on a support, wherein at least one layer constituting the lithographic printing material comprises carbon black and an amphoteric surfactant. A lithographic printing material comprising: 3. The lithographic printing material according to claim 2, wherein the undercoat layer contains carbon black and an amphoteric surfactant. 4. The lithographic printing material according to claim 2, wherein the lithographic printing material has a backing layer, and the backing layer contains carbon black and an amphoteric surfactant. material. 5. The carbon black / binder weight ratio in the layer containing the carbon black and the amphoteric surfactant is at least 1/1, and the amount of the binder is at least 1 g / m ^{2 with} respect to the carbon black-containing layer. The silver halide photographic light-sensitive material according to any one of the preceding claims, wherein the material has an adjacent layer.