JPS6120027A - Photosensitive material - Google Patents

Abstract

PURPOSE:To prevent electrostatic phenomena, especially, occurrence of static electricity in photosensitive materials under low humidity by incorporating particles contg. an F-contg. low-mol.wt. compd. at least in the surface of the photosensitive material so as to disclose them out of the outermost layer of the photosensitive material. CONSTITUTION:The particles disclosed out of the outermost layer of the photosensitive material are generally called as a matting agent, and each particle has a surface contg. an F-contg. low-mol.wt. compd. They are prepared by dipping, e.g., silica, into the soln. of the F-contg. low-mol.wt. compd. not dissolving the matting agent and drying it to locate the compd. on the surface. Among F-contg. low-mol.wt. compds, compd. having COOH, OH, CHO, COCl or epoxy group at the end of molecule are especially superior for covering the surface of the matting agent. The matting agent is mixed with a hydrophilic colloid, such as gelatin, which is the binder of the photographic constituent layers, applied, and dried to obtain the outermost layer of the photographic sensitive material in which the matting agent is located at the outermost layer.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a photographic light-sensitive material, and more particularly to a photographic light-sensitive material with improved electrostatic properties in a low-humidity atmosphere.

(Prior Art) Generally, a photographic light-sensitive material is constructed by coating a similarly insulating photographic constituent layer, such as a photosensitive layer, on an insulating glass film support.

Therefore, when handling photographic light-sensitive materials, +91j materials are easily charged due to friction and peeling, and dust absorption, electric shock,
It is known that various phenomena such as ignition occur, which impairs product value.

For example, a silver halide photographic light-sensitive material is manufactured by coating a highly sensitive photographic layer on an insulating glass film support as described above. During the winding and rewinding of the photosensitive material, the application of various constituent layers including the photosensitive layer, and the transportation process during drying, the surface of the coating layer of the photosensitive material may be subjected to friction or peeling from other substances. When charged and discharged, the photosensitive material is exposed to light, which may result in uneven exposure due to irregular static electricity called static marks.

Furthermore, static electricity is generated in photographic light-sensitive materials not only during manufacturing but also during processing to obtain image I, which can lead to static electricity, adhesion of dust, or the formation of static marks as described above. This may cause a malfunction.

The above-mentioned static marks are more likely to occur as the sensitivity of the photographic light-sensitive material increases, and in addition to the recent increase in the sensitivity of photographic light-sensitive materials, there are also opportunities for harsh mechanical handling due to high-speed whitening processing. Due to the increase in
Furthermore, it is thought that the above-mentioned failures tend to occur frequently.

Therefore, methods of preventing such charging of photographic light-sensitive materials have been studied, and various improvement measures have been proposed.

For example, U.S. Pat. No. 2,322,037 discloses that powders such as silica, starch, polymethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, cellulose acetate propionate, and ethyl cellulose, so-called matting agents, are used in the surface layer of photosensitive materials to produce photographic films. A rotor technique has been described that prevents static charging.

In addition to the above-mentioned matting agents used in photographic materials, inorganic matting agents such as titanium oxide, barium sulfate, magnesium oxide, zinc carbonate, calcium carbonate, glass spheres, and talc are also well known.

The effect of these matting agents can be achieved by minimizing the surface that contacts other surfaces of the adjacent photographic light-sensitive materials or the surface that contacts the surface of the conveyor roll during the manufacturing process.
It is thought that the purpose of this method is to reduce the generation of static electricity caused by contact separation between the facing tiles.

However, most of the conventionally known matting agents are
Although it tends to slightly reduce charging on its own, it cannot be said to be very effective in terms of the amount of static electricity generated.Moreover, the recent advances in the sensitivity of photographic materials and the dramatic increase in coating speed during manufacturing Under conditions such as increasing opportunities for severe mechanical handling due to increased processing speed and high-speed automatic processing, the effectiveness of the above-mentioned matting agent in preventing static electricity is extremely small.

On the other hand, in addition to the use of the above-mentioned matting agent, for example, the surface of the support may be treated with a hygroscopic substance or a conductive material, and/or the constituent layers of the silver rhodanide photographic light-sensitive material, especially the surface layer thereof, may be treated. It is also known to incorporate the above-mentioned substances into the photosensitive material to make it conductive and to make it difficult to accumulate static electricity.

However, most of these rapidly lose their effectiveness in low humidity regions, and it is difficult to obtain satisfactory antistatic performance, and the same problem remains.

(Problems to be Solved by the Invention) Therefore, the present invention relates to providing a method for preventing the electrostatic properties of a photographic light-sensitive material in a low-humidity atmosphere, particularly for preventing the generation of static electricity.

(Means for Solving the Problems) According to the present invention, particles having at least a fluorine-containing low-molecular-weight compound on the surface are exposed from the outermost layer of the photosensitive material, thereby forming a photographic material. It was found that the electrostatic properties were improved.

The present invention will be explained in more detail below.

The particles used in the present invention that are exposed from the outermost layer are generally called matting agents, and are particularly characterized by having a fluorine-containing low-molecular compound on the surface of the particles. . Existing here exposed from the outermost layer means that the outermost layer has a certain degree of surface roughness.
It is not necessary that the particles themselves are exposed from the layer.

First, the matting agents used in the present invention include inorganic matting agents such as silica, titanium oxide, barium sulfate, magnesium oxide, zinc carbonate, calcium carbonate, glass spheres, and talc, as well as polymethyl methacrylate. , polystyrene, polyvinyl acetate, polyvinyl alcohol, cellulose acetate glochionate, ethyl cellulose, starch, and pensoquanamine-formaldehyde condensate. Further, matting agents other than those mentioned above may also be freely used as long as they do not adversely affect the photographic properties.

According to the present invention, the matting agent according to the present invention is produced by immersing the matting agent in a solution of a fluorine-containing low-molecular compound that does not dissolve the above-mentioned matting agent and drying it, thereby forming a low-molecular compound containing fluorine on its surface. can be made to exist.

Next, the above-mentioned fluorine-containing low-molecular compound used in the present invention will be discussed.

Typical specific examples of the fluorine-containing low molecular weight compound used in the present invention are shown below.

(Exemplary compounds) (i) CF, C00H (2) C,F,,C'0OH (5) (7,CH,OH (6) (CFs)! CHOH (7) C, FI9C1H1OH (B) CHF, CF , CF, CH,OH. Such compounds are commercially available as shown below.

Trifluoroacetic acid and its derivatives as Exemplified Compound (1), hexafluoroisoglonoclonol as Exemplified Compound (5) and Exemplified Compound (6) are manufactured by Fuji Glass Co., Ltd.
Ortho-) +3 fluoromethylbenzyl alcohol of Exemplified Compound (9), Ortho-trifluoromethylbenzaldehyde of Exemplified Compound (10), Exemplified Compound (11)
ortho-1-nofluoro-methylbenzoyl chloride, ortho-1 of exemplified compound (3)
Trifluoromethylbenzoic acid is commercially available from Central Glass Co., Ltd., and exemplified compound (13) is available from Shin-Etsu Silicone Co., Ltd., respectively.

Among the above-mentioned fluorine-containing low-molecular-weight compounds, compounds having a carboxyl group, hydroxyl group, aldehyde group, carbonyl chloride group, or epoxy group at the terminal have particularly excellent covering power on the surface of the matting agent, and are preferably used in the present invention. be able to. The fluorine-containing low molecular weight compound of the present invention is not limited to the above-mentioned exemplified compounds.

Next, referring to the photographic light-sensitive material of the present invention, the photographic light-sensitive material referred to in the present invention refers to a support used in the photographic light-sensitive material, and this support (substrated if necessary, or a backing layer). A photographic light-sensitive material as an intermediate product in which one or more photographic constituent layers are coated on the support (including those coated with a non-rodanized silver emulsion layer, a subbing layer, an intermediate layer, etc.); Photographs of layers, filter layers, anti-reaction layers, protective layers, backing layers, etc.
-Includes all gold-coated photographic materials as formed products.

Therefore, in the present invention, the presence of the matting agent having the above-mentioned fluoride-containing low molecular weight compound on the surface (referred to as the matting agent according to the present invention) in the outermost layer of the photographic light-sensitive material means that the above-mentioned This means that the matting agent according to the present invention is present on the outermost surface of the photographic light-sensitive material as an intermediate product and a finished product. When a matting agent is present through layers, when it is present in the outermost layer of an intermediate product coated with one or more of the constituent layers of the photographic light-sensitive material, and when the matting agent is present in the outermost layer of an intermediate product coated with one or more of the constituent layers of the photographic light-sensitive material, and when the matting agent This includes the case where it is present in the outermost layer on the coated side, or in the outermost layer of a backing layer on the opposite side of the photosensitive layer across the support.

In order to make the matting agent according to the present invention exist in the outermost layer of a photographic light-sensitive material, it may be mixed with a hydrophilic colloid such as gelatin, which is a binder for a photographic constituent layer, applied by a conventional coating method, and dried. Other means include:
The matting agent according to the present invention may be mixed into the outermost layer of the constituent layers of the photographic light-sensitive material, or the constituent layer and the matting agent may be separately sprayed or supercoated and then dried.

The particle size of the matting agent according to the present invention is 1 μm to 10 μm, preferably 1 μm to 5 μm, but in order to exhibit the effects of the present invention, it is necessary that at least the grains of the matting agent be exposed from the constituent layers. When it is mixed with a binder, it is preferably larger than the dry film thickness.

The amount of the above-mentioned matting agent applied is more effective for the purpose of improving the matte effect, but it is preferable that the amount applied is such that it does not have an adverse effect on transparency or sharpness. The range is 10 to 500 m9/rrl s, more preferably 50 to 200 to 4'.

The matting agent according to the present invention can be used in combination with other matting agents, but from the viewpoint of effectiveness, it is preferable to use a smaller amount than the matting agent according to the present invention.

Examples of the support used in the photographic material of the present invention include cellulose triacetate film, polyester film such as polyethylene terephthalate film, polycarbonate film, polystyrene film,
Included are hydrophobic films or sheets such as polyolefin films, polyethylene laminated papers, and the like.

The photographic material of the present invention is preferably a silver halide photographic material, such as a general black-and-white photographic material, a special black-and-white photographic material, a color photographic material, a printing photographic material, an X-ray photographic material, etc. Includes intermediate products and finished products.

When the photographic material of the present invention is a silver halide photographic material, silver halide emulsions include silver bromide, silver chloride,
Various silver halide grains such as silver chlorobromide, silver iodobromide, and silver chloroiodobromide are used dispersed in a hydrophilic polymer binder, and examples of the binder include gelatin,
Gelatin derivatives, colloidal albumin, agar, gum arabic, alginic acid, e.g. acetyl containing 1119-2
Cellulose derivatives such as cellulose acetate hydrolyzed in a 6-cell cavity, acrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing 6rn urethane carboxylic acid groups or cyanoacetyl groups, such as vinyl alcohol, vinyl cyanacetate copolymers, polyvinyl Alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, a polymer obtained by polymerizing a protein-heavy saturated acylated protein with a monomer having a vinyl group, and the like can be used. The silver halide emulsion is then treated with chemical sensitizers, such as sulfur sensitizers such as allylthiocarbamide, thiourea, allyl isothiocyanate, sodium thiosulfate, cystine, active or inactive selenium sensitizers, such as potassium chloroaurate. , gold compounds such as auric trichloride, potassium auric thiocyanate, and 2-aurothiabenzothiazole methyl chloride; palladium compounds such as ammonium chloroparadate and sodium chloropalladite; platinum compounds such as potassium chloroplatinate; and a noble metal sensitizer such as a ruthenium compound, a rhodium compound, an iridium compound, or a combination of such sensitizers. In addition to chemical sensitization, this emulsion can also be reduced sensitized with a reducing agent and stabilized with triazoles, imidazoles, azaindenes, benzothiazolium compounds, zinc compounds, cadmium compounds, mercaptans, or mixtures thereof. It is possible to contain a sensitizing compound of the cleaved thioether, quaternary ammonium salt or polyalkylene oxide type. This emulsion may also contain, for example, glycerin, hydroxyalkanes such as 1,5-bentanediol, esters of ethylene bisglycolic acid, bisethoxydiethylene glycol succinate, water-dispersible fine particulate polymer compounds obtained by emulsion polymerization, etc. It can contain wetting agents, plasticizers, film property improvers, etc., and further contains ethyleneimine compounds, vinylsulfone compounds, dioxane derivatives, oxypolysaccharides, dicarboxylic acid chlorides, methanesulfonic acid vinylesters, etc. (Fllll, saponin, coating aids such as sulfosuccinates, fluorescent brighteners,
Various photographic additives such as surfactants and antistaining agents can be contained.

Furthermore, this halogenated emulsion contains cyanine dyes, merocyanine dyes, complex cyanine dyes,
Optical sensitization may be carried out using a photochromic film or the like. Furthermore, layers other than the silver halide emulsion layer may contain various couplers such as achromatic couplers, colored couplers, and I inhibitor-releasing couplers. The same binder as mentioned above can be used as the binder.

By exposing the matting agent according to the present invention to the outermost layer of the photographic constituent layers of a photographic light-sensitive material according to the present invention, a photographic material free from charging failures such as static mark failures can be obtained. Moreover, according to the present invention, the use of the above-mentioned matting agent does not have any adverse effect on photographic properties such as sensitivity, gradation, capri, etc. of the light-sensitive material.

Hereinafter, the present invention will be described in more detail with reference to Examples.
The present invention is not limited thereby.

Example 1 Silica matting agent (matting agent-1) 10F with an average particle size of 3μ
300g of fluorine-containing low molecular weight compound (Exemplary Compound-13)
After dispersing for 9 minutes with an ultrasonic dispersion machine, the resulting dispersion was sprayed into hot air at 100 to 120°C with a spray gun and dried, and the resulting matting agent was used as a matting agent. -2.

Next, 3.5.9 gelatin per kg of emulsion and 100
A silver iodobromide gelatin high-sensitivity X-ray emulsion containing g of silver iodobromide (containing 3 mol of silver iodide) was subjected to gold-sulfur sensitization during the second ripening process, and then stabilized. 4-Hydroxy-6-methyl-1,3,:',8,7-chitrazaindene compound as agent, glyoxal as hardening agent, and saponin as coating aid were added, and the thickness was 175 mm after subbing treatment.
Sample 1 was obtained by coating and drying a polyethylene terephthalate film support of 50 μm to a dry film thickness of 7 μm, and then coating and drying a protective layer having the following composition to a dry film thickness of about 0.5 μm. .

(Protective film composition) (1/m”) Gelatin 0.59 Di-2-ethylhexyl sulfo 0.01g Sodium succinate glyoxal 0.011! The above-mentioned matting agent-1 was protected as above at a ratio of 501v/rrl. In addition to the film composition, the obtained sample is designated as sample-2,
Furthermore, the above-mentioned matting agent according to the present invention-2 50 m97
A sample obtained by adding the above-mentioned protective film composition to the ratio of m is designated as Sample-3.

Next, for each sample, 4
The humidity was controlled for a period of time, and frictional charging and static mark generation tests using neoprene rubber were performed, and the results shown in Table 1 below were obtained.

The above charge amount was measured in a 20% RH atmosphere at 23°C with a frictional charge of 1 between the neoprene rubber and the sample, and the static mark was measured in a 20% RH atmosphere at 23°C. After adjusting the humidity of the time sample, rub it with a neoprene rubber rod.
After visualizing the image, the blackening was observed and judged according to the grade below.

Grade 1: No occurrence, I2: Slight occurrence, I3: Occurrence, I4: Slightly frequent occurrence, I5: Occurrence all over the surface. Table 1 As shown in the above table, the protective layer was coated with a ma-nod agent. Sample-1 to which no silica matting agent was added and sample-2 to which silica matting agent was added were both positively charged (1) and had strong static marks.

On the other hand, a loaf sample to which the matting agent-2 according to the present invention was added
In No. 3, the amount of charge was small, and there were almost no static marks.

Furthermore, the samples of the present invention showed no decrease in sensitivity or occurrence of capri fc.

C) Effect of the invention) A photographic material in which particles having at least a low molecular weight compound containing fluorine on the surface are exposed from the outermost layer has a small amount of charge and no static mark. The occurrence of is extremely low, and the photographic properties are not deteriorated.

Claims (1)

[Claims] A photographic light-sensitive material characterized in that particles having at least a fluorine-containing low-molecular compound on the surface are exposed from the outermost layer of the light-sensitive material.