JPH0617992B2 - Antistatic silver halide photographic light-sensitive material - Google Patents

Description

The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an antistatic silver halide photographic light-sensitive material.

(B) Prior art and its problems The photographic light-sensitive material is processed through steps such as coating, drying, cutting and finishing with an emulsion containing silver halide grains on a support made of film or paper. Static electricity accumulates due to contact, friction, peeling, and the like with the inner transport roller or between the front and back surfaces of the photographic photosensitive material. When the amount of accumulated static electricity increases, the photosensitive material is exposed to light and after development, undesired spots called static marks or dendritic or feathered fog occur. Further, this static mark is not only generated during the manufacturing process, but may also be generated by exposure, winding, rewinding, contacting, rubbing, peeling, etc. during the use of a silver halide photographic material. However, this is a very serious drawback, and the commercial value of the light-sensitive material is significantly impaired.

Such a statistic mark is more likely to occur particularly in recent years due to the increased sensitivity of photographic light-sensitive materials and the increased opportunities for severe handling such as high-speed coating, high-speed photography, and high-speed automatic processing. Further, the accumulated static electricity is one of the causes of obstacles such as dust sticking to the surface of the photosensitive material and hindering the uniformity of coating.

It is preferable to add an antistatic agent to the photographic light-sensitive material in order to prevent these damages due to static electricity, but substances that adversely affect photographic performance cannot be used. That is, it is not possible to use a material which adversely affects the sensitivity, tone, fog, storability, scratch resistance and adhesion resistance of the photographic light-sensitive material, so that application of the antistatic agent to the photographic light-sensitive material is subject to numerous restrictions.

One method of eliminating the damage due to static electricity is to manufacture or handle the photographic light-sensitive material under conditions of high humidity where static electricity is unlikely to occur. In this case, adhesion between film surfaces occurs and there is a limit, and the environment Is very constrained and unacceptable.

Hitherto, hygroscopic substances, water-soluble inorganic salts, surfactants, fluorine-containing surfactants, polymers and the like have been proposed as antistatic agents for photographic light-sensitive materials.

These are disclosed, for example, in US Pat.
982, 561 and 3,754, 924. However, even if these substances do not have a fatal effect on the photographic performance, they adversely affect the decrease in sensitivity and the decrease in density during long-term storage, and the viscosity of the coating emulsion increases to form a coating film. However, depending on the type of support and the type of emulsion, the antistatic effect may be small.

On the other hand, inorganic or organic fine particles known as a matting agent are added to the photographic material to prevent the adhesion of the film surface, and to reduce the contact area at the time of contact, friction and peeling to reduce the charge amount. Although attempts have been made widely to reduce the amount, the matting agent itself imparts almost no conductivity to the photographic material.

(C) Object of the Invention It is an object of the present invention to provide an antistatic silver halide photographic light-sensitive material that generates less static electricity.

(D) Structure of the present invention The present inventors have conducted earnest research to obtain a silver halide photographic light-sensitive material in which static electricity is less generated, while considering the above-mentioned drawbacks of the prior art. In a silver halide photographic light-sensitive material having one light-sensitive silver halide emulsion layer, a betaine surfactant is contained on one side of the support and an anionic surfactant is contained on the other side. Have found that the above drawbacks can be ameliorated. Examples of the betaine-based surfactant used in the present invention include carboxybetaine type, sulfobetaine type, imidazolium betaine type and the like.

Some specific examples of the betaine-based surfactant used in the present invention are shown below, but the present invention is not limited thereto.

(1) (2) (3) (Four) (Five) The anionic surfactant used in the present invention includes, for example, sodium higher alkyl sulfate ester, sodium higher alkylbenzene sulfonate, sodium alkylphenyl polyethylene glycol sulfate, sulfosuccinate ester, sodium fatty acid, sodium alkylphosphonate and the like. It The addition amount of both betaine and anionic surfactants was 1 kg of coating liquid.
It is in the range of about 0.001 to 2 g, preferably 0.005 to 1 g, but amounts outside this range may be used.

In the present invention, both sides of the support may be used in combination with other types of surfactants in addition to the betaine-based surfactant or the anionic surfactant, but in order to obtain the necessary antistatic ability, Although the amount of the surfactants of the above-mentioned types to be used varies somewhat depending on the sensitivity and surface properties of the light-sensitive material, the support, etc., it is desirable to use less than 50% of all the surfactants in the same layer. The optimum amount varies depending on the case, but the balance between the front side and the back side is important.

Examples of the surfactant-containing layer according to the present invention include a protective layer, a backcoat layer, an emulsion layer, a filter layer, an overcoat layer, an undercoat layer, an antihalation layer, an intermediate layer, an ultraviolet protection layer, a timing layer and a developer layer. In order to achieve the object of the present invention, it is preferable that the uppermost layers on the front and back sides of so-called photographic light-sensitive materials, such as the protective layer and the back coating layer, are surfactant-containing layers.

When applying the surfactant according to the present invention, a binder is not particularly necessary, but one or more natural or synthetic polymers such as gelatin, gelatin derivatives, polyvinyl alcohol and polyvinylpyrrolidone may be used. In the surfactant-containing layer according to the present invention, a compound well known in the art, for example, a hardener, a matting agent, a fluorescent whitening agent, an antistatic agent, a thickener, silver halide, a physical development nucleus, an antifoggant, Optical sensitizers, ultraviolet absorbers, antihalation dyes, couplers, developing agents and precursors thereof may be added.

The above-described effects are remarkably exhibited when the silver halide emulsion used in the present invention is produced by any of the acidic method, the neutral method and the ammonia method.

The present invention relates to the properties of a silver halide photographic emulsion, for example, the composition of silver halide (eg, silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide), and the crystal form of silver halide. It can be implemented regardless of size.

The emulsion used in the present invention can contain various additives. For example, chemical sensitizers (for example, sulfur sensitizers such as thiourea and hypo, noble metal sensitizers such as gold, platinum and iridium compounds, reduction sensitizers) and the like can be used in combination. Further, spectral sensitizers, supersensitizers, stabilizers, antifoggants, developers, development accelerators, hardening agents, hardening accelerators, couplers, desilvering accelerators, dye removal improving agents, whitening agents. , Thickeners, precursors thereof, and the like.

Examples of the protective colloid of the silver halide emulsion used in the present invention include gelatin, modified gelatin, albumin, agar, gum arabic, natural products such as alginic acid, polyvinyl alcohol, polyvinylpyrrolidone, copolymers of acrylic amide, acrylic acid and vinyl imidazole. And water-soluble synthetic resins such as

Suitable supports for use in the present invention include, for example, glass, cellulose acetate film, polyethylene terephthalate film, paper, baryta-coated paper, and polyolefin (eg, polyethylene, polypropylene, etc.) coated paper. These supports may be subjected to corona treatment by a known method, or may be subjected to subbing processing by a known method, if necessary.

The exposure of the silver halide photographic light-sensitive material of the present invention is not limited to light, but may be X-ray, γ-ray, electron beam or the like.

The silver halide photographic emulsion used in the present invention is coated with a protective layer, an intermediate layer, an ultraviolet absorbing layer, an undercoat layer or other silver halide emulsions, if necessary.

The silver halide photographic light-sensitive material to which the present invention can be applied includes black and white photographic materials, color photographic materials, general use, printing,
There is no particular limitation on the type and use such as X-ray film and electron microscope film.

Examples will be described below to more specifically describe the present invention, but the present invention is not of course limited thereto.

Example 1 A chemically ripened silver chloroiodobromide emulsion was coated with an amount of silver of 5 g / m ² ,
Gelatin amount 4 g / m ² , gelatin amount 1.4 g / m as protective layer
^It was adjusted to ² and simultaneously coated and dried according to a conventional method. A surfactant was added to the protective layer as shown in Table 1.

As a support, a polyethylene terephthalate film having a thickness of 175 μ was undercoated, and a gelatin backing layer was provided on the back surface in advance. Surfactants were added to the backing layer as shown in Table 1. These samples at 25 ° C
After left in a dark room at 20% RH and 25 ° C. and 50% RH for 2 hours, development was performed after rubbing with a rubber roller to measure the degree of generation of static marks.

The development was carried out with a developing solution having the following composition at 20 ° C. for 2 minutes.

Water (approx. 80 ° C) 500 ml Metol 31 g Hydroquinone 12 g Anhydrous sodium sulfite 45 g Anhydrous sodium carbonate 67.5 g Potassium bromide 1.9 g Water added 3,000 ml Table 1 shows the measurement results of the degree of static mark generation in these samples. .

The degree of occurrence of static marks was visually judged and classified as follows.

A: Static marks are not observed at all.

B: Static mark is slightly recognized.

C: Static marks are considerably recognized.

D: Static marks are generated over the entire surface.

As is apparent from Table 1, Sample 1 in which the compound (1) which is a betaine-based surfactant is added to one side and the compound (6) which is an anionic surfactant is added to the other side, Sample 1 generates static marks. Was not recognized at all. On the other hand, the generation of static marks was observed in Samples 2 and 3 in which the front and back joint surfactants were used.

Example 2 A chemically ripened silver chlorobromide emulsion was prepared so as to have a coated silver amount of 4 g / m ^2, and coated and dried according to a conventional method. A polyethylene terephthalate film was used as a support. The back surface of this polyethylene terephthalate film was previously coated with a gelatin solution so that the amount of gelatin was 4 g / m ² . As shown in Table 2, a surfactant was added to the protective layer in the emulsion layer and to the back gelatin layer. The degree of generation of static marks was measured in the same manner as in Example 1, but instead of the rubber roller, a rubber roller attached so that the back surface of the sample was on the outside was used. The sample with the same No. as the test sample was used. Table 2 shows the measurement results of the degree of static mark generation of these samples.

As is clear from Table 2, samples 1, 2, 3, 4, 5, 6,
In Comparative Example 7, static marks were found in Comparative Samples 8, 9 and 10, but not at all.

Compound (7) Compound (8) C ₁₈ H ₃₇ -COONa

Claims (1)

[Claims] 1. A silver halide photographic material having at least one light-sensitive silver halide emulsion layer on a support,
Halogen characterized in that it contains a betaine-based surfactant as a main surfactant on the uppermost layer on one side of the support and an anionic surfactant as a main surfactant on the other side. Silver halide photographic light-sensitive material.