JPS6120028A - 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. resin at least in the surface of the photosensitive materal 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. resin. They are prepared by dipping the matting agent into the soln. of the F-contg. resin not dissolving the matting agent and drying it, or polymerizing an F-contg. monomer by plasma to graft the F-contg. resin with the surface of the matting agent. A polymer or copolymer having monomer units, such as fluoroethylene, is prepared by the solution, bulk, and suspension polymn. methods.

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 plastic film support.

Therefore, when handling photographic materials, it is known that they are easily charged with electricity due to friction, peeling, etc., and that various phenomena such as dust attraction, electric shock, and ignition occur, which impair commercial value.

For example, a silver halide photographic light-sensitive material is manufactured by coating a constituent layer in which a highly sensitive photographic light-sensitive layer is coated on an insulating plastic film support as described above, and transporting it during drying. During the process, the coating layer surface of the photosensitive material is charged due to friction and peeling with other substances, and the photosensitive material is exposed to light during discharge, and after this phenomenon, irregular static electricity called so-called static marks occurs. Uneven exposure may occur.

In addition, static electricity is generated in photographic light-sensitive materials not only during manufacture, but also during processing to obtain an image, which can lead to static electricity, adhesion of dust, and 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 is also an opportunity for them to be subjected to harsh mechanical handling due to high-speed automatic processing. Due to the increase in
Furthermore, it is thought that the above-mentioned failures tend to occur frequently.

Therefore, methods for preventing the charging of photographic forest materials have been studied, and six improved means have been proposed.

For example, U.S. Pat. No. 2,322,037 describes silica, starch, polymethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, cellulose acetate.
A technique is described in which a so-called matting agent, a powder such as propionate or ethyl cellulose, is used in the surface layer of a photosensitive material to prevent charging of a photographic film.

In addition to the above-mentioned matting agents used in photosensitive materials, inorganic matting agents such as titanium oxide, barium sulfate, magnesium oxide, zinc carbonate, calcium carbonate, glass beads, and talc are also 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 objective is to reduce the generation of static electricity caused by the contact 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 that effective from the viewpoint of static electricity generation.Moreover, recent improvements in the sensitivity of photographic light-sensitive materials and drastic increases in coating speed during production In addition, under conditions such as increased opportunities for severe mechanical handling due to high-speed automatic processing, etc., the contribution of the following matting agents to antistatic properties 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 can be treated using conductive properties across hygroscopic substances, and the constituent layers of the silver halide photosensitive material, especially its A method is also known in which the above-mentioned substances are contained in the surface layer to impart conductivity to the photosensitive material, thereby accumulating static electricity.

However, most of these lose their effectiveness rapidly in the rising temperature range, and do not have satisfactory antistatic performance.
It is difficult to obtain Fi, 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 under a low-humidity atmosphere, particularly for preventing the generation of static electricity.

(Means for Solving the Problems) According to the present invention, particles having fluorine-containing resin on at least the surface are exposed from the outermost layer of the photosensitive material, thereby improving the electrostatic properties of the photographic photosensitive material. was found to be 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 resin on the surface of the particles. Here, the existence of the particles exposed from the outermost layer means that the outermost layer is given a certain degree of surface roughness, and the particles themselves do not necessarily need to be exposed.

First of all, regarding the matting agent used in the present invention, examples of the manting agent include inorganic matting agents such as silica, titanium oxide, barium sulfate, magnesium oxide, zinc carbonate, calcium carbonate, glass spheres, and talc, as well as polyester. Conventionally known materials such as methyl methacrylate, polystyrene, polyvinyl acetate, polyvinyl alcohol, cellulose acetate propionate, ethyl cellulose, starch, pensoquanamine-formaldehyde condensate (')
Mention may be made of matting agents.

ti Matting agents other than those mentioned above may also be freely used as long as they do not adversely affect the photographic properties.

The matting agent according to the present invention can be prepared by immersion treatment in a solution of a fluorine-containing resin that does not dissolve the above-mentioned matting agent and drying, or by a method of grafting a fluorine-containing layer onto the surface of the matting agent by plasma polymerization. A fluorine-containing resin can be present on the surface.

Next, referring to the fluorine-containing resin according to the present invention, the above-mentioned polymers or copolymers having a single cap unit as exemplified below can be mentioned.

(Exemplary monomer unit) (1) C) (2=CHF (2) CH, = cF'.

(3) CHF'=CP.

(4) CF! = ”Ft (5) CF, = CFC/ (6) cH, = C(CF,)F (7) CFt= C(CF,)F (10) CH, =C(CH,)-COOCH,CF
.

(11) CH,=C(CH,)-COOCH,C,
F.

(12) Cl-1,= CH C00CH! (CFt)nH (n=2~9)
C00CH2(CFrinH(n=2~9)(17)
CH, = CH C00CH2CH, (CF, )nF (n = 2
~8) (1,8) CH,= CH ■ ■ C, HIl (20) CH.

The polymer or copolymer fat having the above-mentioned exemplary monomer units according to the present invention can be easily produced by a conventionally known polymerization method such as a solution polymerization method, a bulk polymerization method, or a suspension polymerization method. .

The method for synthesizing the fluorine-containing resin used in the present invention will be described below.

Synthesis Example 1 (Polymerization method of exemplified compound 12) CI-1:
CH C00CH, (CF, ), H10011゜αα′-azobisisobutyronitrile (AIBN) 2.0.9
and 5 oocc of methyl ethyl Kent were placed in a third flask, and the mixture was refluxed for 10 hours.Then, the reaction solution was poured into a large amount of water with vigorous stirring to precipitate the reaction product. The precipitate was then filtered, washed with water, and dried in air at 60°C to obtain the exemplary monomer (1) according to the present invention.
A polymer of 2) was obtained. Our yield was 92.3 g (92.3% of the theoretical yield).

Small (R, elemental analysis, etc.) shows that this substance is a compound example (12
) was confirmed to have a polymer composition of

The intrinsic viscosity in acetone at 5°C was 0.15 m1/11.

Synthesize! 12 (t) Polymerization method of monohydrate compound boiled 13) COO
CH2 (CF2), H100g, AIBN 2.0
．． 9 was subjected to reaction treatment in the same manner as in Synthesis Example 1 to obtain a polymer of exemplified monomer (13) according to the present invention. The yield was 93g (yield 9
3%), and it was confirmed by NMR, elemental analysis, etc. that this substance had the polymer composition of Compound Example (13).

Intrinsic viscosity in acetone at 25°C is o, 12rnl/
l/de k.

Synthesis Example 3 (polymerization method of Exemplified Hardware Store 15) was reacted and treated in the same manner as Synthesis Example 1 to obtain a polymer of Exemplified Monomer (15) according to the present invention. Success/failure was 91.9 (yield 91chi),
According to NMR, elemental analysis, etc., this substance is a compound example (15)
It was confirmed that the polymer composition was as follows. Intrinsic viscosity in acetone at 25°C is 0.12 ml/11 tf
c.

Synthesis Example 4 (Exemplary Compound 190 Polymerization Method) C1-], =
C-CH.

C00CHCF', HCF.

C Yi H11100, 9, AIBN 2. Synthesis example 1 of OF
The example monomer (15
) was obtained. The concentration was 921/(yield 92%), and NMR, elemental analysis, etc. showed that this substance was a compound example (
It was confirmed that the polymer had a polymer composition of 19). The intrinsic viscosity in acetone at 25°C was 0.131 N//g.

Synthesis Example 5 (Polymerization method of exemplified compound 17) CH,=CH C00CH*CHtt (CF 4F 100 El
, AlBN2-0# was reacted and treated in the same manner as in Synthesis Example 1 to obtain an exemplary polymer (17) according to the present invention. The yield is 93.5.9 (yield 93.5), and N
It was confirmed by MR, elemental analysis, etc. that this substance had a polymer composition of compound (17). Intrinsic viscosity in acetone at 25°C: 0.13 vrl/l/'t'
h ivy.

The molecular weight of the fluorine-containing resin used in the present invention is:
5000-1.000.000, preferably #'i1
It is 0,000 to 20,000.

Next, the photographic light-sensitive material of the present invention will be described. The support used in the photographic light-sensitive material and the photographic light-sensitive material referred to in the present invention, as well as the support (subbed-treated if necessary, and the backing layer) A photographic light-sensitive material as an intermediate product in which one or more photographic constituent layers are coated on the support, and a silver rhodanide emulsion layer and a subbing layer are coated on the support. It includes all photographic materials as finished products coated with photographic constituent layers such as layers, intermediate layers, filter layers, antihalation layers, protective layers, and backing layers.

Therefore, in the present invention, the matting agent having the above-mentioned fluorine-containing resin according to the present invention on the surface (referred to as the matting agent according to the present invention) is present in the outermost layer of the photographic light-sensitive material. This means that the matting agent according to the present invention is present on the outermost surface of the photographic light-sensitive material as a finished product.
When a matting agent is present in the outermost layer of an intermediate product coated with one or more of the constituent layers of the photographic 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 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, for example, it can be mixed with a hydrophilic colloid such as gelatin as an inder of the photographic constituent layer, applied by a conventional coating method, and dried. Alternatively, 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 layers and the matting agent may be sprayed or supercoated separately and then dried. .

The particle size of the matting agent according to the present invention is 0.1μ to 10μ, preferably 1 to 5μ, but in order to express the effects of the present invention,
Since it is necessary that at least the matting agent particles be exposed from the constituent layer, when the matting agent particles are mixed with a binder, it is preferably larger than the dry film thickness thereof.

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 adversely affect transparency or sharpness. 10 to 500#/m, more preferably 5
0~200rn9/n? is within the range of

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.

Supports used in the photographic material of the present invention include, for example, cellulose triacetate films, polyester films such as polyethylene terephthalate films, polycarbonate films, polystyrene films,
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 silver rhodanide photographic material, and there are various types such as general black and white photographic material, special black and white photographic material, color photographic material, printing photographic material, X) gland photographic material, etc. This includes intermediate products and finished products.

When the photographic light-sensitive material of the present invention is a silver halide photographic light-sensitive material, there are various silver halide emulsions such as silver bromide, silver chloride, silver chlorobromide, silver iodobromide, silver chloroiodobromide, etc. silver halide particles dispersed in a hydrophilic polymer binder are used, and binders include, for example, gelatin, gelatin derivatives, colloidal albumin, agar, gum arabic, alginic acid, and acetyl-containing materials.
Cellulose derivatives such as cellulose acetate hydrolyzed to 6%, acrylamide, imidized polyacryleamide, casein, vinyl alcohol polymers containing urethane carboxylic acid groups or cyanoacetyl groups such as vinyl alcohol, vinyl cyanoacetate copolymers, Polyvinyl alcohol, polyvinylpyrrolidone, hydrolyzed polyvinyl acetate, a polymer obtained by polymerizing a protein or a saturated acylated protein with a heptamer having a vinyl group, and the like can be used. The silver halide emulsion is then treated with chemical sensitizers, such as allylthiocarbamide, thiourea, allyl isothiocyanate, sodium thiosulfate, cystine-specific sulfur sensitizers, active and inactive selenium sensitizers, etc. Gold compounds such as potassium chloroaurate, auric trichloride, potassium auric thiocyanate, 2-aurothiabenzothiazole methyl chloride, palladium compounds such as ammonium chloroparadate, sodium chloropalladite, and potassium chloroaurate. - This emulsion can be sensitized using a combination of platinum compounds and noble metal sensitizers such as ruthenium compounds, rhodium compounds, and iridium compounds. In addition to sensitization, reduction sensitization can be performed using reducing agents such as triazoles, imidazoles, and azain f.
It can be stabilized with pentyl thiazolium compounds, zinc compounds, cadmium compounds, mercaptans or mixtures thereof, and also contains sensitizing compounds such as thioethers, quaternary ammonium salts or polyalkylene oxides. You can force it. This emulsion may also contain, for example, glycerin, hydroxyalkanes such as l,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., as well as ethyleneimine compounds, vinyl sulfone compounds, dioxane derivatives, oxypolysaccharides, dicarboxylic acid chlorides,
Hardening agents such as methanesulfonic acid vinylester, saponin,
Various photographic additives such as coating aids such as sulfosuccinates, fluorescent brighteners, surfactants, and antistaining agents can be included.

Furthermore, this silver halide emulsion contains a cyanine dye, a merocyanine color complex, a composite cyanine dye, ≠4≠÷・, ゛ −
It may contain various couplers such as colorless couplers, colored force groups, and phenomenon suppressor-releasing couplers, which may be optically sensitized using . Layers other than the silver halide emulsion layer can also contain the various photographic additives mentioned above, and the same binders as mentioned above can also be used.

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 practical examples, but the present invention is not limited thereto.

Example 1 Titanium oxide matting agent (matting agent-1) 1 with an average particle size of 5μ
01 as the exemplary monomer unit (]2) Cn=4 according to the present invention
The polymer was immersed in 500 rnl of a 10x1 thiacetone solution and dispersed for 9 minutes using an ultrasonic disperser.
b) A titanium oxide matting agent whose surface was coated with a fluorine-containing material was obtained by spraying it into hot air at ℃. This matting agent is referred to as matting agent-2.

Next, 35.9 g of gelatin per kg of emulsion and 100 g of gelatin.
After performing gold-sulfur sensitization during the second ripening on a silver iodobromide gelatin high-sensitivity X-ray emulsion containing silver iodobromide (containing 3 molt of silver iodide) of No. 9, as a stabilizer 4-Hydroxy-6-methyl-1+ 3+ 3 a * 7-titrazaindene compound, glyoxal as a hardening agent, saponin as a coating aid, and subbing treatment, thickness 175
Sample- I got 1.

(Protective film composition) (Fl/rt?) Gelatin 1.0g Sodium di-2-ethylhexyl sulfosuccinate 0.01) Glyoxal 0.01.9 The above matting agent -1f3 (ratio of 1/d) Sample f-: Material-2 obtained by adding the above protective film composition to the above protective film composition, and further adding the above-mentioned matting agent-2 according to the present invention to the above protective film composition at a ratio of 30 μ/m'. The obtained sample is
Set it to 3.

Next, each sample was conditioned for 4 hours in an atmosphere of 20% RH at D°C, and the amount of frictional charge using neoprene rubber was measured and a static mark generation test was performed.The results are shown in Table 1 below.

The above charge amount is the amount of frictional charge between the neorene rubber and the sample, and was measured in a 23'C, 20% RH atmosphere.Static marks in 1 indicate 4 hours at 5°C and 20% RH atmosphere. After adjusting the humidity of the sample, rub it with a neoprene rubber ball.
After development, the degree of blackening was observed and judged according to the following grade.

Grade 1: No occurrence, I2: Slight occurrence, I3: Occurrence, I4: Slightly frequent occurrence, I5: Occurrence all over the surface.As shown in Table 1 above, no matting agent was added to the protective layer. Sample-1 without oxidation and silica matting agent added
Sample-2 was both highly positively charged and had strong static marks.

On the other hand, a sample to which 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.

16 In the sample of the present invention, no decrease in sensitivity or occurrence of fog was observed.

(Effect of the invention) A photosensitive material in which particles containing fluorine at least on the surface are exposed and present in the outermost layer of the photographic light-sensitive material has a small amount of charge, and static marks occur. is extremely low, and does not deteriorate photographic properties.

Agent Patent Attorney No 1) Parent-in-law −ρ　−

Claims (1)

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