JPS61203445A - Silver halide photographic sensitive material - Google Patents

Abstract

PURPOSE:To reduce the generation of static electricity by forming layers including a photosensitive silver halide emulsion layer on a support and incorporating a surfactant contg. fluorine into the top layer on one side of the support and an anionic surfactant into the top layer on the other side. CONSTITUTION:Layers including at least one photosensitive silver halide emulsion layer are formed on a support, a surfactant contg. fluorine is incorporated into the top layer on one side of the support, and an anionic surfactant is incorporated into the top layer on the other side to obtain a silver halide photographic sensitive material. The surfactant contg. fluorine may be a compound represented by formula I or II, and the anionic surfactant may be sodium higher- alkylsulfate or sodium higher-alkylbenzenesulfonate. A protective layer, a back coat layer and an emulsion layer may be formed as the top layers.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a silver halide photographic light-sensitive material, and more particularly to an antistatic silver halide photographic light-sensitive material.

@) Prior art and its problems Photographic light-sensitive materials are processed through steps such as coating a support made of film or paper with an emulsion containing silver halide particles, drying, cutting, and finishing. Static electricity is accumulated due to contact, friction, peeling, etc. with the transport roller of the photosensitive material or between the front and back surfaces of the photosensitive material. When the amount of accumulated static electricity increases, it is discharged and the photosensitive material is exposed to light, and after development, spots, dendritic, or feather-like fog called static marks occur even though they are not intended. In addition, these static marks are not only generated during the manufacturing process, but also due to contact, friction, peeling, etc. during exposure, winding, unwinding, and development processing when using silver halide photographic materials. This is a very serious drawback and significantly reduces the commercial value of the photosensitive material.

Such static marks have become more likely to occur, particularly in recent years, as photographic materials have become more sensitive, and are subject to harsh handling such as high-speed coating and high-speed automatic processing.

In addition, this accumulated static electricity is one of the causes of problems such as adhesion of dust to the surface of photosensitive materials and interference with coating uniformity.
It is also one.

In order to prevent these problems caused by static electricity, it is preferable to add an antistatic agent to the photographic light-sensitive material, but substances that adversely affect photographic performance cannot be used. In other words, the use of antistatic agents in photographic materials is subject to a large number of restrictions, as it is prohibited to use substances that adversely affect the sensitivity, tone, fog, preservability, scratch resistance, and adhesion resistance of photographic materials. .

One way to eliminate problems caused by static electricity is to manufacture or handle photographic materials under high humidity conditions where static electricity is less likely to occur. This cannot be accepted because the environment in which it can be handled is extremely restricted.

Hitherto, hygroscopic substances, water-soluble inorganic salts, surfactants, fluorine-containing surfactants, polymers, and the like have been proposed as antistatic agents for photographic materials. These include, for example, US Patent 2
, No. 882, 157, No. 2.98Z651, No. 375
No. 4924, etc. However, although these substances do not have a fatal effect on photographic performance, they
This may adversely affect sensitivity and density loss during long-term storage, increase the viscosity of the coated emulsion and make it difficult to form a coating, and depending on the type of support and emulsion, electrostatic charge may occur. Prevention may be less effective.

On the other hand, inorganic or organic fine particles known as matting agents are added to photographic materials to prevent adhesion of film surfaces and to reduce the amount of charge by reducing the contact area during contact, friction, and peeling. Although attempts have been made to reduce the amount, the matting agent itself hardly imparts electrical conductivity to the photographic material.

(C1 Purpose of the Invention The purpose of the present invention is to provide a silver halide photographic material which generates less static electricity and is antistatic.

(D) Structure of the present invention The inventors of the present invention have conducted extensive research in order to obtain a silver halide photographic light-sensitive material that generates less static electricity while taking into consideration the drawbacks of the prior art described above. In a silver halide photographic material having one light-sensitive silver halide emulsion layer, the uppermost layer on one side of the support contains a fluorine-containing surfactant, and the uppermost layer on the other side contains an anionic interface. It has been found that the above drawbacks can be improved by incorporating an activator.

Examples of the fluorine-containing surfactant used in the present invention include Japanese Patent Publication No. 47-9303, Japanese Patent Publication No. 48-43130, German Publication No. L95Q121, German Publication No. 1.96L638,
Unexamined Japanese Patent Publication No. 46-7781, No. 48-44182, No. 1
33023, 1972-113221, U.S. Patent No. 35
No. 88906, Japanese Patent Application No. 53-18399, etc. can be referred to. Anionic or amphoteric organic fluorine-containing compounds are preferred. Some specific examples are shown below, but it goes without saying that the invention is not limited to these.

(1) CFs (CF2 )s C00NH4(
21CF3 (CF2)? 902 N Hz
COONaC,H.

(3) CF3(CF213-C)I,CI(,-5
O,N-CH2-COONa2HIl (4) CF, (CF,)7-5o, -N-CH,
-COOKC, H.

(5) CF, (CF2), -5o, -N-CH
,-3o,HC,H.

(61CF, (CF, l, -9o, K (force CF3 (CF,) u-CH2-050, N These include sodium sulfonate, sodium alkylphenyl polyethylene glycol sulfate, sulfosuccinate, sodium fatty acid, sodium alkylphosphonate, etc.The amounts of the fluorine-containing surfactant and anionic surfactant added to the top layer are both Approximately 0.01 to approximately 2 OL per coating liquid IKfP, preferably 0.
The range is from 0.05 to IOP, but amounts outside this range may also be used.

In the present invention, it is possible to use other types of surfactants in addition to fluorine-containing surfactants or anionic surfactants in the eh layers on both sides, but in order to obtain the necessary antistatic ability, The use of other types of surfactants may vary somewhat depending on the sensitivity, surface properties, support, etc. of the photosensitive material, but it is desirable that they account for 50% or less of the total surfactants in the same uppermost layer. The optimal amount varies depending on each case, but
The balance between the front and back sides is important.

Examples of the uppermost layer in the present invention include, but are not limited to, a protective layer, a backing layer, an emulsion layer, a single filter layer, and an overcoat layer. Although the binder used in the uppermost layer is not particularly necessary, one or more natural or synthetic polymers such as gelatin, gelatin derivatives, polyvinyl alcohol, and polyvinylpyrrolidone may be used.

The top layer of the present invention contains compounds well known in the art, such as hardeners, matting agents, optical brighteners, antistatic agents, thickeners, silver halides, physical development nuclei, antifoggants, and optical sensitizers. , couplers, developing agents, precursors thereof, and the like can be added.

The silver halide emulsion used in the present invention can significantly exhibit the above-mentioned effects regardless of whether it is produced by an acidic method, a neutral method, or an ammonia method.

The present invention relates to the properties of silver halide photographic emulsions, such as the composition of silver halide (for example, silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide), and the crystal form of silver halide. It can be carried out regardless of crystal habit or 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, and reduction sensitizers) can also be used in combination.

Father spectral sensitizer, supersensitizer, stabilizer, antifoggant, developer, development accelerator, hardener, hardening accelerator, coupler, desilvering accelerator, dye stripping improver, brightener , a thickener, a precursor thereof, and the like.

Protective colloids for 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, and copolymers of acrylamide, acrylic acid, and vinylimidazole. Water-soluble synthetic resins such as

Suitable supports for use in the present invention include, for example, glass, acetic acid/cellulose film, bolyene terephthalate film, paper, baryta-coated paper, and polyolefin (e.g., bolyene, polypropylene, etc.) coated paper. One example is kimono.

These supports may be corona treated by a known method, and may also be undercoated by a known method if necessary.

The exposure of the silver halide photographic light-sensitive material of the present invention is not limited to only light, but may also include exposure to X-rays, γ-rays, electron beams, and 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. Silver halide photographic materials to which the present invention can be applied include black and white photographic materials, color photographic materials, general purpose materials, printing materials, X-ray film materials,
The type and use are not particularly limited, such as for electron microscope film.

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

Example 1 Chemically ripened silver chloride iodobromide emulsion coated silver amount 5P/
rrl, gelatin 1t4P/m", gelatin amount for the protective layer was adjusted to 1.4P/m, and simultaneously coated and dried according to a conventional method.As shown in Table 1, the protective layer contained surfactant. Add the agent to your friend.

A polyethylene terephthalate film having a thickness of 175 μm was used as a support, and a gelatin backing layer was previously provided on the back side.

These samples with surfactants added to the backing layer as shown in Table 1 were heated at 25°C, 20% R)i and 25°C, 50% RH.
After being left in a dark room for 2 hours, development was performed after rubbing with a rubber roller, and the degree of static polymer formation was measured.

Development was carried out at 20° C. for 2 minutes using a developer having the following composition.

Water (approximately 80°C) 50 QWLl Metol 31fP Hydroquinone 12y-Anhydrous sodium sulfite 459-Anhydrous sodium carbonate
675f potassium bromide
1.9? Take a sip of water
3.0007d Table 1 shows the measurement results of the degree of static mark generation for these samples.

The degree of static mark occurrence was determined by visual inspection according to the following classifications.

A: No static marks were observed at all.

B: Static marks are slightly observed.

C: Static mark Kana 9 is recognized.

D: Static marks occur over the entire surface.

@1 As is clear from Table 1, Compound (10), which is a fluorine-containing surfactant, was added to one top layer, and Compound (14), which is an anionic surfactant, was added to the other top layer. Sample 1
No static marks were observed at all. On the other hand, in Samples 2 and 3 in which the same type of surfactant was used on the front and back surfaces, significant static marks were observed to occur, especially in the case of low humidity.

Example 2 A chemically ripened silver chlorobromide emulsion was coated with a silver amount of 4y/y,
Gelatin amount 3? /i, 1 amount of gelatin as a protective layer? /-
It was adjusted so that A polyethylene terephthalate film was used as a support. A gelatin solution was applied in advance to the back side of this polyethylene terephthalate film so that the amount of gelatin was 4 P/m'. Surfactants were added to the protective layer and the gelatin layer on the back side as shown in Table 2. The degree of generation of static marks was measured in the same manner as in Example 1, except that instead of the rubber roller, a rubber roller attached to the sample with the back side facing outward was used. The sample to be pasted was from the same grave as the test sample. Table 2 shows the measurement results of the degree of staccoma generation in these samples.

(The following is a blank space) Compound (15) As is clear from Table 2, Sample 1.2.3.4.5.6.
In Sample No. 7, the occurrence of staccoma was observed in Comparative Samples 8, 9, and 10, but no occurrence was observed at all.

Claims (1)

[Claims] (1) In a silver halide photographic material having at least one photosensitive silver halide emulsion layer on a support, the uppermost layer on one side of the support contains a fluorine-containing surfactant, and the other side contains a fluorine-containing surfactant. A silver halide photographic material comprising an anionic surfactant in the uppermost layer thereof.