JPH0148934B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an antistatic synthetic polymer resin molded article. Conventionally, synthetic polymer resin molded articles have been used in large quantities as general-purpose materials and products because they are generally easy to manufacture, can be supplied in large quantities at low cost, and have excellent properties such as electrical insulation.
However, synthetic polymer resin molded products are generally easily charged with electricity, so their appearance is easily soiled due to the adhesion of dust and dirt, and accumulated static electricity can affect the human body (electric shock), spark discharge, and electronic circuit materials. There are problems such as noise generation. Various methods have been tried in the past to prevent this charging (accumulation of static electricity).
This includes methods of adding conductive materials such as metal powder and carbon black, methods of blending and applying static neutralizing agents such as surfactants, chemical treatments such as acid etching, etc.
Flame treatment, active radiation (electron beam, ultraviolet light, radiation, etc.)
There are methods of introducing hydrophilic functional groups onto the surface through a surface graft reaction, etc., and methods of treating the surface with low-temperature plasma of an inorganic gas. However, none of these methods can provide a sufficient antistatic effect, or even if they can, they have the drawback of significantly altering the bulk properties of the original synthetic polymer resin molded product. Yes, and no method has been proposed to satisfy them. From this point of view, the present inventors conducted extensive research on a method of low-temperature plasma treatment of the surface of synthetic resin molded products, and found that C-Cl or C
- Synthetic polymer resin molded products that do not have F bonds can be treated with low-temperature plasma of organosilicon compounds that have Si-Cl bonds in their molecules, without changing the bulk properties of the resin molded products. It was confirmed that a sufficient antistatic effect with excellent durability and durability could be imparted to the material, and the present invention was completed. The present invention will be explained in detail below. First, the synthetic polymer resin molded article targeted by the present invention is one in which the synthetic polymer resin does not have C-Cl or C-F bonds in the molecule (therefore, it is different from vinyl chloride resin and foam). These include low-pressure, medium-pressure, and high-pressure polyethylene, polypropylene, polystyrene, saturated or unsaturated polyester, vinylon, polyacetate, polysulfone, polycarbonate, polyurethane, and polyimide. , polyamide (nylon 6, nylon 12, etc.), polyamideimide, polyvinyl alcohol, polyacrylic,
Polymethacrylic, acrylonitrile styrene copolymer, acrylonitrile butadiene styrene copolymer, ethylene vinyl acetate copolymer, urea resin, melamine resin, silicone resin, polyphenylene oxide, polyarylate, polyparaxylene, polyphenol, epoxy resin, Examples include polydiallyl phthalate, block copolymers, graft copolymers, and mixtures of different polymer resins. When manufacturing molded products using the synthetic polymer resin described above, there is no problem in adding various compounding agents, additives, processing aids, etc., such as plasticizers, stabilizers, lubricants, etc. , filler,
Extending agents, face weights, dyes, heat-resistant agents, flame retardants, antioxidants, light absorbers, surfactants, cross-linking agents, anti-fogging agents, moisture-proofing agents, elasticity improvers and the like can be mentioned. The molding method may be a casting method, melt extrusion method, calender method, stretching method, compression method, or any other molding method conventionally adopted for molding each polymer resin, and there are no particular restrictions on the type and shape of the molded product. There isn't. In addition, this molded product may be subjected to heat treatment, stretching treatment, shrinkage treatment,
crosslinking, sandblasting, corona discharge, solvent treatment,
Secondary processing such as actinic radiation treatment may be performed, and the effects of the present invention will not be adversely affected by this. The present invention improves the surface characteristics of the molded product by treating the surface of the synthetic polymer resin molded product with low-temperature plasma of an organosilicon compound, improving durability and
It imparts long-lasting antistatic properties, but in order to obtain this effect, the organosilicon compound needs to have a Si--Cl bond in its molecule. Examples of such organosilicon compounds include dihydrodienemethylchlorosilane, monohydrodienedimethylchlorosilane,
Trimethylchlorosilane, dimethylethylchlorosilane, phenyldimethylchlorosilane, triethylchlorosilane, vinyldiethylchlorosilane, tri(2-propenyl)chlorosilane, 2,
4,4-trimethyl-2-chloro-2,4-disilapentane, chloromethyldimethylchlorosilane, di(chloromethyl)methylchlorosilane, trichloromethyldimethylmethylchlorosilane, trichloromethyldimethylchlorosilane, monohydrodienemethyldichlorosilane, ethyldichlorosilane , phenyldichlorosilane, 4-chlorophenyldichlorosilane, dimethyldichlorosilane, methylethyldichlorosilane, vinylmethyldichlorosilane, divinyldichlorosilane, 2,
2-dimethyl-4,4-dichloro-2,4-disilapentane, methyltrichlorosilane, ethyltrichlorosilane, vinyltrichlorosilane, phenyltrichlorosilane, 1-methylvinyltrichlorosilane, 2-chlorovinyltrichlorosilane, 2,2 -Dichloroethyltrichlorosilane and the like are exemplified. The method of low-temperature plasma treatment involves placing a synthetic polymer resin molded product in a low-temperature plasma generator, and increasing the pressure inside the device to preferably 10 torr or less while flowing the organosilicon compound gas through the device. This is carried out by a method of adjusting and holding the gas, generating low-temperature plasma under this gas pressure, and exposing the molded product to the low-temperature plasma. In addition to this organosilicon compound, inert gases such as helium and argon, nitrogen,
Inorganic gases such as oxygen, air, hydrogen, water vapor, carbon dioxide, and carbon monoxide, and organic compound gases other than organosilicon compounds may be allowed to coexist. In the above treatment method, if the pressure inside the organosilicon compound device is 10 Torr or more, it will be difficult to obtain a treated molded product with excellent antistatic properties, so the gas pressure of this low-temperature plasma should be 10 Torr or less. The range is preferably from 1 to 0.005 Torr. Low-temperature plasma treatment at this gas pressure imparts excellent antistatic properties, but when the gas pressure increases above 10 Torr, the antistatic properties rapidly decrease (accompanied by an increase in surface resistance). This is completely unexpected from the knowledge obtained in conventional plasma polymerization and plasma treatment. The conditions for generating low-temperature plasma include, for example, applying a power of several KHz to several hundred MHz and several W to several hundred KW to the electrodes, and using either internal electrode or external electrode (electrodeless) method. Good too. Further, a sufficient reforming effect can be obtained regardless of the type of discharge (glow discharge, corona discharge, etc.). The plasma processing time varies depending on the applied power and the like, but generally several seconds to several tens of minutes is sufficient. In the low-temperature plasma treatment, two or more types of organosilicon compounds may be mixed or used in combination, and a synergistic effect may be expected in some cases. In addition, in order to impart not only antistatic properties but also other properties to synthetic polymer resin molded products, other organic compounds and/or
Alternatively, it is effective to mix or use the above-mentioned inorganic gases in combination, and this provides excellent antistatic properties (reduction in surface resistance) with excellent durability and sustainability.
It has the advantage that it not only provides properties such as wettability, adhesiveness, printability, abrasion resistance, mold releasability, heat resistance, water resistance, migration resistance, etc. Next, a specific example will be given. Example 1 Each synthetic polymer resin sheet shown in Table 1 was set in a plasma generator, the pressure inside the device was reduced to 10 ^-3 Torr, and then the atmosphere was introduced to reduce the pressure inside the device to 0.07 Torr under atmospheric circulation. After that, trimethylchlorosilane vapor was introduced, and while mixing with the flowing atmosphere, the atmospheric partial pressure was adjusted to 0.07 Torr and the trimethylchlorosilane partial pressure was adjusted to 0.1 Torr, and then high-frequency power of 13.56MHz and 1KW was applied to create a low-temperature plasma. was generated and the sheet was processed for 1 minute. Surface specific resistance value (*1) and frictional charging voltage (*2) for sheets treated in this way and sheets that were not subjected to plasma treatment
was measured to evaluate antistatic properties. The results are in Table-1
It was as shown in. (*1) Measured with SM-15E manufactured by Toa Denpa Kogyo Co., Ltd. (ohm) (*2) Measured with a rotary static tester manufactured by Koa Shokai (volt) Conditions: Cotton cloth, 200g load, 750rpm, 60 seconds

[Table] Example 2 Each synthetic polymer resin plate shown in Table 2 was set in a plasma generator, and after reducing the pressure inside the device to 10 ^-4 , argon gas was introduced and the inside of the device was heated under gas flow.
After that, chloromethyldimethylchlorosilane vapor was introduced and mixed with flowing argon gas to keep the argon partial pressure constant at 0.1 torr, and the chloromethyldimethylchlorosilane partial pressure was adjusted to 0.1 torr.
110K after changing to Torr, 0.5 Torr, and 1.5 Torr and holding the adjustment.
A high frequency power of Hz5KW was applied to generate low temperature plasma and the plate was treated for 30 seconds. The physical properties of each plate treated in this manner were measured in the same manner as in Experiment No. 1, and the results were as shown in Table 2.

[Table] Example 3 Each synthetic polymer resin film shown in Table 3 was set in a plasma generator, and after reducing the pressure inside the device to 10 ^-4 Torr, methyltrichlorosilane gas was introduced to reduce the pressure in the system to 0.05 Torr. Adjusted to 13.56MHz after holding
A high-frequency power of 200 W was applied to generate low-temperature plasma, and the film was processed for 3 minutes. The physical properties of the thus treated film were measured in the same manner as in Experiment No. 1, and the results were as shown in Table 3.

【table】

[Table] Example 4 Each synthetic polymer resin film shown in Table 4 was set in a plasma generator, and after reducing the pressure inside the device to 10 ^-2 Torr, nitrogen gas was introduced and the inside of the device was heated under gas flow. was adjusted to 0.05 torr, then vinyldimethylchlorosilane gas was introduced, and while mixing with flowing nitrogen gas, the nitrogen partial pressure was adjusted to 0.05 torr and the vinyldimethylchlorosilane partial pressure was adjusted to 0.05 torr and held at 13.56M.
High-frequency power of 100 W of Hz was applied to generate low-temperature plasma, and the film was processed for 5 minutes. The physical properties of the film thus treated were measured in the same manner as in Experiment No. 1, and the results were as shown in Table 4.

[Table] Reference example As a comparative example, each synthetic polymer resin film shown in Table 5 was set in a plasma generator, and after reducing the pressure inside the device to 10 ^-2 Torr, argon gas was introduced and the device was placed under gas flow. Adjust the inside to 0.05 Torr,
A high-frequency power of 100 W at 13.56 MHz was applied to generate low-temperature plasma, and the film was processed for 5 minutes. The physical properties of the thus treated film were measured in the same manner as in Experiment No. 1, and the properties were as shown in Table 5.

【table】

【table】

Claims (1)

[Claims] 1 The surface of a synthetic polymer resin molded product that does not have C-Cl or C-F bonds in its molecules is
1. A method for producing an antistatic synthetic polymer resin molded article, which comprises treating with a low-temperature plasma of an organic silicon compound having a bond.