JPS6114632A - Photosensitive material - Google Patents

Abstract

PURPOSE:To reduce electrostatic chargeability and to prevent the generation of static marks, especially, in a low humidity atmosphere by leaving specified F-contg. copolymer particles disclosed to the outermost layer of a photosensitive material. CONSTITUTION:The outermost layer on the photosensitive layer side of the photosensitive material or the backing layer of the support contains as a matting agent, fine particles in a size of 1-5mum dispersed into a binder, and made of a copolymer represented by formula I in which A is a monomer having >=2 ethylenically unsatd. double bond and B is a monomer having alpha,beta-ethylenically unsatd. double bonds and contg. F; x is 0.5-50mol%; y is 0-49.5mol%; and z is 50-99.5mol%: such as formula II. As a result, static marks due to charging in the manufacturing process of the photosensitive material and its handling, especially, even in a low humidity atmosphere, static electricity trouble can be prevented.

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a photographic material, and more particularly, the present invention relates to a photographic material having improved electrostatic properties particularly in a low-temperature atmosphere.
Regarding photosensitive materials. (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 due to friction or peeling, and can cause various phenomena such as dust attraction, electric shock, and ignition, which can damage the product value. There is. For example, a halogenated scissor photographic light-sensitive material is manufactured by coating a highly sensitive photographic layer on an insulating plastic film support as described above, and the manufacturing process, namely 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. The photosensitive material is exposed to light during discharge, and after development, uneven exposure due to irregular static electricity called so-called static marks may occur. Static electricity is generated in advanced photographic materials not only during manufacture, but also during processing to obtain images, which can lead to static electricity, buildup 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, the opportunity for them to be subjected to harsh mechanical handling due to high-speed automatic processing has increased. 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. Patent No. 2,322,037 describes silica, starch,
A technique is described in which a so-called matting agent, a powder of polymethyl methacrylate, polyvinyl acetate, polyvinyl alcohol, cellulose acetate propionate, ethyl cellulose, etc., is used in the surface layer of a photosensitive material to prevent charging of a photographic film. In addition to the above, inorganic matting agents such as titanium oxide, barium sulfate, magnesium oxide, zinc carbonate, calcium carbonate, glass bulbs, and talc are also well known as capping agents used in Saita Yoshinkan Genkansho. ing. The effects of these matting agents can be achieved by minimizing the surface that contacts other surfaces of the adjacent photographic material or the surface of the conveyor roll during the manufacturing process.
This is thought to be aimed at reducing the generation of static electricity caused by contact separation between parts. However, although most of the conventionally known matting agents tend to reduce static electricity by themselves, they cannot be said to be very effective when viewed from the lid that generates static electricity. Increasing the sensitivity of photosensitive materials or! ! ! Under conditions such as a significant increase in coating speed during manufacturing and increased opportunities for severe mechanical handling due to high-speed automatic processing, the contribution of the above-mentioned matting agent to antistatic properties is very small. Furthermore, although polymethyl methacrylate and polystyrene pearl polymers are widely used as mausoleum mantle agents, these organic mantle agents swell or dissolve in organic solvents, making them unusable. have. In addition to using a matting agent, for example, the surface of the support may be treated with a hygroscopic material or a conductive material, or the constituent layers of a halogenated photographic light-sensitive material may be treated. In particular, a method is known in which the above-mentioned substances are contained in the surface layer of the photosensitive material to impart electrical conductivity to the photosensitive material and thereby make it difficult for the photosensitive material to accumulate moisture. However, most of these lose their effectiveness in low humidity areas, making it difficult to obtain satisfactory antistatic performance, and problems still remain. (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. A second object of the present invention is to provide a photographic material containing a matting agent that can be used even in an organic solvent and having excellent electrostatic properties. (Means for Solving the Problems) According to the present invention, the above-mentioned problems are solved by a photographic light-sensitive material in which fluorine-containing copolymer particles represented by the following general formula are exposed from the outermost layer of the light-sensitive material. be able to. General formula % Formula %) In the formula, A is a monomer having at least two ethylenically unsaturated double bonds, B is a monomer having α, β-ethylenically unsaturated double bonds, and C is α, β- Represents a fluorine-containing septamer having an ethylenically unsaturated double bond, where X is 05
˜50 mol%, Y i ; It O ˜49.5 mol%, 2
represents 50 to 995 mol%. The present invention will be explained in more detail below. First, to explain in detail the fluorine-containing copolymer represented by the general formula according to the present invention, examples of the monomer represented by the monomer unit A in the copolymer represented by the general formula include divinylbenzene, allyl, Acrylate, allyl methacrylate, 1,3-butylene diacrylate, 1,3-butylene dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, vinyl acrylate, vinyl methacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, ethylene dimethacrylate Acrylate, ethylene dimethacrylate, 1,6-hexane diacrylate,
Mention may be made of 1,6-hexane dimethacrylate. Examples of the monomer represented by the monomer unit B include ethylene, propylene, 1-butene, isobutyne, 2-
Methylbenzene, 2-methylbutene, 1.1,4.4-
Tetramethylbutadiene, styrene, α-methylstyrene, vinyl acetate, allyl acetate, methyl methacrylate,
Examples include ethyl acrylate. These B
Among the monomers represented by , methyl methacrylate and styrene are outstanding in terms of hardness. Examples of the monomer represented by 1ζC include the above-mentioned compounds. fl) CO3-CIIF f2)
CO3-CF'2f31 CHF = CP2f
4) CF″2= CF2Qo) CO3-C(
CH3) -C00CH2CF3(Ill C1-1
2=C(CH3)-C00CH2C2F. (12) CO3-CH C00CH2 (CF2) rIH (n = 2-9) Q
3) Cl42=C-CHs C00CH2 (CF2). II (n =
2-9) (141C112=C-e113 C00CII2CH20(CF2).F (.Eng.2
~8) 0η CO3-C1 C00C112C112(CF2)nF (n
= 2~8) 111elf. =C1( ■ C00CI(2CI(CH2(C1!'2)nF
(n = 2~8)〇II (19) C112=C-('II3C00('
ll-CF211CF3 C211゜C00C-CF2CFHCF3 "Furthermore, regarding the molar ratio represented by x, y, and t in the above general formula, since the matting agent itself is insoluble in the solvent, X must be 05 or more. Therefore, in order to improve the excellent electrostatic properties, it is necessary to set 2 to 50 or more.Representative examples of the fluorine-containing copolymer according to the present invention 1 represented by the general formula are described below. Iton (1) C1-13+
CHCH2+ (x:y:z=lO:30:6(1)
(2)
CH3t31
C113(x:z~40:6(1)
I C0O('112 +C112-C11+ (x:y:z=10:10:80)
(-C1l-CI!2+(x:y:z=5:25near 0) The present invention is not limited to the fluorine-containing 1-copolymer ita-isomer as mentioned above. According to the present invention, the copolymer particles containing silane can be prepared as follows: Preparation Example 1 Calcium carbonate in 200 m7 of a 2% gelatin aqueous solution 12
Add y and disperse with a homogenizer for 20 minutes. Next, add 13 g of divinylbencef to this → 70
Leisoprohil acrylate 13.3. SJ, methyl methacrylate-1-3,09 and Hensoylperoquind 0.5.9 were added and polymerized at 80-85°C in a nitrogen stream for 15 minutes with stirring at a speed of 1000 revolutions/minute. As a result of observing the obtained emulsion with an optical microscope, 2
~5μ polymer oil droplets were observed. This -1 full gene was centrifuged to obtain a matting agent of particles +1 size 2 to 57+. The yield was 96%, and Motoki analysis confirmed that it was the desired Example 7-layer copolymer compound (1). A photosensitive material refers to a support used in a photographic photosensitive material, and this support (including those that have been subjected to undercoating processing or coated with a backing layer, etc., if necessary).
A photographic light-sensitive material as a coated intermediate product having one or more photographic constituent layers thereon, and a halogenated emulsion layer, a subbing layer, an intermediate layer, a filter layer, an antihalation layer, It includes all photographic light-sensitive materials as finished products coated with photographic constituent layers such as protective layers and backing layers. Therefore, in the present invention, the fact that the fluorine-containing 1-copolymer particles according to the present invention (referred to as the matting agent according to the present invention) are present in the outermost layer of the photographic light-sensitive material is based on the above-mentioned intermediate layer d.
) 1 means that the matting agent according to the present invention is applied to the outermost surface of the photographic light-sensitive material as a finished product. An intermediate product coated with one or more of the constituent layers of the photographic light-sensitive material, in which a mantle agent is present on the surface or back of the light-sensitive material support directly or via a subbing layer. The outermost layer of the photographic material as the final product is the outermost layer on the side on which the photosensitive layer is coated, or the outermost layer of the backing layer on the opposite side of the support from the photosensitive layer. This includes the case where it is interposed in the outer layer. In order to make the mantle agent according to the present invention RF present in the outermost layer of a photographic light-sensitive material, for example, it is mixed with a hydrophilic colloid such as seratin, which is a binder of the photographic JLC constituent layer, coated by a conventional coating method, and dried. good. Other means include mixing the matting agent according to the present invention into the outermost layer of the photographic photosensitive layer and the capping agent, or spraying the component layer and the capping agent separately or drying after drying. 1 is enough. The particle size of the matting agent according to the present invention is 01μ to 10μ, preferably 1μ to 5μ, but in order to achieve the effect of the present invention, it is necessary that at least the matting agent ladle is exposed from the constituent layer. Therefore, if the binder is mixed with the binder, it must be larger than the dry film thickness.In addition, when particles are exposed from the layer, Table 1 of the culm 1η in the layer is used.
It is not necessary that h−f(0σ) be b\out. In addition, when applying the above-mentioned matting agent, the more the matting agent is applied, the more effective it is for the purpose of improving the matting effect, but it is preferable to apply the matting agent to a degree that does not adversely affect transparency or sharpness, and generally 10 ~50owy/m', and furthermore, the matting agent according to the present invention can be used in combination with other matting agents, but the effectiveness Therefore, it is preferable to use the matting agent according to the present invention. The following 1c are used in the photographic material of the present invention. With a support (-te1f1 example: triacetic acid (ζrul)-sunoyl, poly, [thiL/nra-L phthalate fi II)
, etc. 1; Polycarbonate film 11, polystyrene film, polyolefin Filno 8, polyethylene' nominated paper, etc. (includes water-based films or sheets, etc.). (As a material, halogenated photosensitive material is 6F IF l, general photosensitive material for black and white, photosensitive material for special black and white (photosensitive material for ladle, dip, electric shock material for printing, electric shock for X-ray) 4 (including intermediate products and finished products of various materials). Silver halide emulsion used in 1 when the material is a halogenated photographic light-sensitive material. In J. Examples of the binder include seratin, seratin conductor, -loid albumin, agar, acetate, alkinoic acid, and acetyl-containing binder hydrated to a concentration of 19 to 26%.
Cellulose derivatives such as cause acetate, acrylamide, imidized polyacrylamide, casein, vinyl alcohol polymers containing urethane carboxylic acid caps or cyanoacetyl caps such as vinylal-7-al, vinylcyanoacetate copolymers, polyvinyl alcohol, polyvinylpyrrolidone Polyvinyl acetate, hydrolyzed polyvinyl acetate, a polymer obtained by polymerizing a proteinaceous compound or a saturated unsaturated proteinaceous compound with a vinyl capped hexamer, etc. can be used. And)・Silver halide emulsion is a chemical sensitizer,
For example, sulfur sensitizers such as A11-YA carbamide, thiourea, allyl inthiocyate, sodium thiosulfate, cystine, active or inactive selenium sensitizers, such as potassium chloroosete, auric trichloride, etc.

[-]
gold compounds, such as ammonium chloride, potassium auryl thiol, 2-aurothiabenzothiazole methyl chloride, etc.

[Balanium compounds such as copafate, sodium chlorovaladite, plananium compounds such as potassium chlorobragoate, and yellow metal sensitizers such as ruthenium compounds, rhodium compounds, iridium compounds, etc. The emulsion can be sensitized by using a combination of sensitizers.In addition to chemical sensitization, this emulsion can also be reduced sensitized with a reducing agent. It can be stabilized with zolium compounds, zinc compounds, cadmium compounds, mercaptans or mixtures thereof, and can contain sensitizing compounds such as thioethers, quaternary ammonium salts or polyalkylene oxides. This emulsion may also contain, for example, glycerin, human oxyalkanes such as 1,5-bentanediol, esters of ethylene bisglycolic acid, diethylene glycol succinate, water-dispersible fine particulate polymer compounds obtained by emulsion polymerization, etc. It can contain wetting agents, plasticizers, membrane property improvers, etc. In addition, ethyleneimine compounds, vinyl sulfone thread compounds, dioxane derivatives, oxypolysaccharides, dicarboxylic acid chlorides, vinistyl methanesulfonic acid, etc. hardening agent, → Toboane, sulfony]
Coating aids for monophosphate, fluorescent brighteners, surfactants,
[gamma]nf-:1 b') It is possible to contain various photographic additives such as staining agents. Furthermore, this silver halide emulsion contains /anine dye, merocyanine dye, cyanine dye, ←γ, , ・
- You may also feel the mineralogy j11g using -1, - etc. Coupler(s) such as colorless couplers, colored couplers, development inhibitor releasing couplers, etc. may not be included. of·
Various photographic additives such as those mentioned above can be incorporated in layers other than the silver halide milk edge layer, and the same binders as those mentioned above can be used. . By exposing and intervening the matting agent according to the present invention in the outermost layer of the true constituent layer of a photographic light-sensitive material according to the present invention, it is possible to obtain a zero-sensitive material free from charging failures such as static mark failures. Moreover, according to the present invention, the sensitivity of the photosensitive material can be improved by using the above-mentioned capping agent.
The present invention will be described in more detail with reference to Examples below.
The present invention is not limited thereby. Example 1 A second silver iodobromide gelatin high-sensitivity After performing gold sensitization and sulfur sensitization during ripening, 4-hydroxy-6-methyl-1,3,3a was used as a stabilizer. A 7-chitrazaindene compound, glyoxal as a hardening agent, and saponin as a coating aid were added, and the mixture was coated onto a polyethylene terephthalate film support with a thickness of 175 μm that had been subbed treated so that the dry film thickness was 7 μm, and then dried. A protective layer having the following composition was coated and dried to a dry film thickness of about 1 μm to obtain Sample-1. (Protective layer composition) (9/ln'') Gelatin 10g Sea 2
- Sodium ethylhexyl sulfosuccinate
0.01. jZ Glyoxal 0.01. ! i+ 50 Q
/y('), and the resulting sample was designated as sample-2. On the other hand, for comparison, PMMA with an average particle size of 3μ was added in the same manner as described above so that the amount was 50ml/m". The sample obtained by adding it to the protective layer composition is referred to as Sample-3.Next, each sample was conditioned for 4 hours at 23°C in a 20% rtn W atmosphere, and the amount of triboelectric charge was measured using neoprene rubber. A tick mark generation test was carried out, and the results were obtained as shown in Table 1 below.The above band [originated] due to the frictional electrification between the neorene rubber and the sample. The static mark is 23°Cl2O%
After conditioning the humidity of the sample in an RI-T atmosphere for 4 hours, rubbing it with a neorene rubber rod and developing it, the degree of blackening was observed and judged according to the following grade. Grade 1: No occurrence Grade 2: Slight occurrence 3゛ Occurrence 4: Slightly frequent occurrence 5: Occurrence all over the surface - As shown in the table above, Sample 1 in which no matting agent was added to the protective layer and Comparative All samples 3 containing a matting agent were positively charged to a large extent, and static marks were also strongly generated. However, in sample 2 to which the capping agent according to the present invention was added, the amount of charge was small and almost no static marks were observed. Example 2 The following composition solution was applied to the side of a cellulose triacetate film support at a rate of about 20xl/m' using a roll/j-ting method, dried for 3 minutes with a 9 (1') J, and then After surface 1 of the support was undercoated by a conventional method, the same high-sensitivity X-ray emulsion and protective layer as Sample-1 prepared in Example 1 were coated in order and dried to obtain Sample-4. Composition liquid) Cellulose diacetate 20g Methanol 700ml Acetone
300m/Meanwhile, a matting agent according to the present invention (exemplary copolymer (1+ particles)) is added to the above composition liquid.
Sample-5 is a sample prepared in the same manner as Sample-4 above, except that 6011i'/yj of 6011i'/yj was added. Each sample obtained above was treated in the same manner as in Example],
The results obtained are shown in Table 2 below. As shown in Table 2 above, Sample-5, in which the matting agent of the present invention was added to the surface coating layer of the support, had a small amount of charge and almost no static marks were observed. Ta. Although a matting agent such as polymethyl methacrylate and polystyrene was added to Comparative Sample 4, it swelled and dissolved in the liquid, making it unusable. (Effects of the Invention) The photographic light-sensitive material of the present invention, in which the fluorine-containing Kyodo polymer particles according to the present invention are exposed from the outermost layer of the light-sensitive material, has the following features:
Particularly in a low humidity atmosphere, the amount of charge is small, and static marks are hardly observed.

Claims (1)

[Scope of Claims] A photographic light-sensitive material characterized in that fluorine-containing copolymer particles represented by the following general formula are exposed from the outermost layer of the light-sensitive material. General formula -(A)_x-(B)_y-(C)_z- [wherein A is a monomer having at least two ethylenically unsaturated double bonds, B is α,β-ethylenically unsaturated A monomer having a double bond, C represents a fluorine-containing monomer having an α,β-ethylenically unsaturated double bond, and x is 0
．． 5 to 50 mol%, y is 0 to 49.5 mol%, z is 50
It represents ~99.5 mol%. ]