JPH0262579B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Field of Application] The present invention relates to a method for producing a molded article of a polyvinyl chloride resin composition having antistatic properties. More specifically, the present invention relates to a method for producing a polyvinyl chloride resin composition molded article that maintains antistatic ability and has excellent durability. [Prior Art] Polyvinyl chloride resins are used in a wide range of applications because of their characteristics such as good processability, high strength, and low cost. However, since polyvinyl chloride resin molded products have low electrical conductivity and are easily charged, they have serious problems such as noise generation in precision equipment due to accumulated static electricity. As a solution to this problem, methods have been adopted such as applying an antistatic agent to the surface of the molded product, and mixing the antistatic agent into the molded product during manufacture. However, the former method has the problem that the surface of the molded product obtained by the antistatic agent is sticky, and the latter method has essentially poor compatibility between the antistatic agent and the polyvinyl chloride resin. There are also problems in that the durability of maintaining the antistatic ability of the resulting molded product is poor, and the antistatic agent bleeds out during manufacturing, making it difficult to maintain quality. As a method to solve these problems, (1)
A method in which a cationic surfactant is kneaded into polyvinyl chloride resin and the surface of the resulting molded product is treated with low-temperature plasma (Japanese Patent Application Laid-Open No. 16005-1985), (2) anion,
A method in which an antistatic agent selected from nonionic and amphoteric surfactants is kneaded into polyvinyl chloride resin, and the surface of the resulting molded product is treated with low-temperature plasma (Japanese Patent Application Laid-Open No. 1983-60533); and (3) polyvinyl chloride resin. A method in which the surface of a vinyl chloride resin molded product is treated with low-temperature plasma, and then an aqueous surfactant-containing solution or a solvent inert to the molded product is applied to the surface (Japanese Patent Application Laid-Open No. 75429/1983).
etc. are known. However, even with these methods, there are problems with external factors (friction, wear, etc.) affecting the product.
The maintenance durability of antistatic ability is still incomplete, and the plate-out phenomenon during processing also remains as a problem that has not been fully solved. or,
The surface resistance of molded products obtained by coating or kneading these surfactants on the surface is limited to 10 ¹⁰ Ω, and the volume resistivity is almost the same as that without additives, so further improvements are needed. It was wanted. [Problems to be solved by the invention] (i) The antistatic ability imparted to the polyvinyl chloride resin molded product is permanently maintained. (ii) The processability and characteristics of the molded product are not impaired. (iii) ) A wide range of
Surface resistance of 10 ⁷ to 10 ¹¹ Ω and/or 10 ⁶ to 10 ¹⁰ Ω
To obtain an antistatic polyvinyl chloride resin molded product having characteristics such as having a volume resistivity of cm. [Means and effects for solving the problems] The method for producing an antistatic polyvinyl chloride resin composition molded article of the present invention includes 100 parts by weight of a polyvinyl chloride resin and 1 to 150 parts by weight of a monomer. -and,
The present invention is characterized in that the surface of a molded article made from a composition comprising at least one dicarboxylic acid ester compound of poly-alkylene glycol monoalkyl ether is treated with low-temperature plasma. As mentioned above, the method of the present invention allows molded products to have a wide range of surface resistance from 10 ⁷ to 10 ¹¹ Ω and/or volume resistivity from 10 ⁶ to ^{10 10} Ω cm without impairing the processability and various properties of the molded product, and to permanently A molded article that can maintain antistatic properties can be obtained. The polyvinyl chloride resins used in the method of the present invention include soft polyvinyl chloride resins, hard polyvinyl chloride resins, copolymer resins of vinyl chloride and olefins such as ethylene, propylene, or isobutylene, and vinyl chloride resins. and styrene, copolymer resins of vinyl chloride and dienes such as butadiene or isoprene, copolymer resins of vinyl chloride and acrylic acid, halogenated olefins, or vinyl acetate. , and the above resin, and a modifying resin such as ABS,
There are resins mixed with rubber such as SBR or NBR. Polyvinyl chloride resins contain plasticizers, stabilizers, fillers, flame retardants, surfactants, antioxidants, ultraviolet absorbers, anti-mold agents, lubricants, pigments, etc. as appropriate depending on the purpose. You can leave it there. In the method of the present invention, 1 to 150 parts by weight of at least one dicarboxylic acid ester compound of mono- and poly-alkylene glycol monoalkyl ether is mixed with 100 parts by weight of the polyvinyl chloride resin. When the amount of the above-mentioned compound to be mixed is less than 1 part by weight, the antistatic effect of the resulting molded product will be insufficient;
If the amount exceeds 1 part by weight, the chemical or physical properties of the resulting molded article will be unsatisfactory. The dicarboxylic acid ester compound of mono- and poly-alkylene glycol monoalkyl ether used in the present invention is, for example, the following general formula (): K0109 (However, in the above formula, represents a member selected from the formula and aromatic dibasic acid residues, and A ₁ and A ₂ each have 2 to 2 carbon atoms.
represents a member selected from the alkylene group of 4,
R ₁ and R ₂ each represent a member selected from a straight chain or branched alkyl group having 3 to 15 carbon atoms, and m ₁ and m ₂ are each independently 1 to 15.
Represents the integer 7. ) can be selected from a group of compounds represented by The mono- and poly-alkylene glycol monoalkyl ethers used in the production of the above-mentioned ester compounds useful in the present invention include propanol and 1 to 7 moles of ethylene oxide, 1 to 4 moles of propylene oxide, or 1 to 3 moles of butylene oxide. Addition compound: Addition compound of butanol and 1 to 6 mol of ethylene oxide, 1 to 4 mol of propylene oxide, or 1 to 3 mol of butylene oxide:
Addition compound of hexanol with 1 to 5 moles of ethylene oxide, 1 to 3 moles of propylene oxide, or 1 to 2 moles of butylene oxide: Addition of heptanol with 1 to 5 moles of ethylene oxide, 1 to 3 moles of propylene oxide, or 1 to 2 moles of butylene oxide Compound: octanol and ethylene oxide 1
-4 mol, addition compound with 1-3 mol of propylene oxide or 1-2 mol of butylene oxide: nonanol and 1-4 mol of ethylene oxide, 1-2 mol of propylene oxide or 1-2 mol of butylene oxide
Addition compound with 2 moles of decanol: Addition compound of decanol with 1 to 3 moles of ethylene oxide, 1 to 2 moles of propylene oxide or 1 mole of butylene oxide:
Dodecanol and 1 to 2 moles of ethylene oxide, 1 mole of propylene oxide or 1 mole of butylene oxide
Addition compound between tridecanol and 1 to 2 moles of ethylene oxide, 1 mole of propylene oxide or 1 mole of butylene oxide: Addition compound between tetradecanol and 1 mole of ethylene oxide, 1 mole of propylene oxide: and
An example is an addition compound of pentadecanol and 1 mole of ethylene oxide. In addition, dicarboxylic acids used in the production of ester compounds useful in the present invention include adipic acid,
Examples include azelaic acid, sebacic acid, succinic acid, brassylic acid, tetrahydrophthalic acid, and phthalic acid. In the present invention, at least one type of ester compound of the mono- and polyalkylene glycol monoalkyl ether and the dicarboxylic acid is mixed with the polyvinyl chloride resin. At this time, since the ester compound has the same chemical and physical properties as the plasticizer, the amount of the plasticizer added can be appropriately reduced depending on the amount of the ester compound added. The polyvinyl chloride resin and the above-mentioned ester compound are kneaded by a conventional method, and the resulting composition is used to form a desired molded article. This molding method is not particularly limited, and ordinary extrusion molding, injection molding, calendar molding, inflation molding, compression molding, etc. can be used. The obtained molded article is subjected to surface treatment using low temperature plasma. Generally, low-temperature plasma treatment is performed using low-temperature plasma of a gas that does not have plasma polymerizability under a pressure of 0.001 to 10 torr. Such gases include helium, neon, argon, nitrogen,
One or more mixed gases selected from nitrous oxide, nitrogen dioxide, oxygen, air, carbon monoxide, carbon dioxide, hydrogen, chlorine, hydrogen chloride, sulfur dioxide gas, hydrogen sulfide, etc. are used. Generation of low temperature plasma can also be accomplished by conventional methods. Generally, the gas pressure is adjusted in the generator to between 0.001 and 10 Torr, and between the electrodes e.g.
Apply a power of 10 to 500 watts at 13.56 MHz. The discharge at this time may be either a polar discharge or a non-polar discharge, and the plasma treatment time is generally several seconds to several tens of minutes depending on the applied voltage. In addition to the above-mentioned methods, the plasma treatment may use low frequency waves, microwaves, or direct current as the discharge frequency band, and plasma generation methods include glow discharge, corona discharge, spark discharge, Any method such as silent discharge may be used. There is also no particular limitation on the structure of the electrode. [Example] The present invention will be explained in more detail with reference to Examples below. Example 1 A polyvinyl chloride resin composition having the composition shown in Table 1 was kneaded with a heating roll at a heating temperature of 160° C. and a kneading time of 10 minutes, and formed into a film with a thickness of 0.5 mm. Each test piece taken from these polyvinyl chloride resin composition film samples was placed in a predetermined position in a low-temperature plasma processing device, and the pressure inside the device was increased.
Evacuate to 10 ^-5 Torr and introduce a mixed gas of CO and Ar (CO/Ar = 70/30) to reduce the pressure inside the device.
Adjusted to 0.2Torr. The low-temperature plasma treatment was performed for 5 minutes on both sides of the film sample using a high-frequency power source (manufactured by Nippon Koshuha Co., Ltd.) with a frequency of 13.56 MHz and a power consumption of 100 watts.

[Table] The surface resistance and tensile strength of the obtained samples are
shown in the table. Here, the tensile test was performed on each sample before plasma treatment using Strograph T (manufactured by Toyo Seiki Co., Ltd.) at an ambient temperature of 20°C according to JISK-6301.
The tensile speed was 200 mm/min. Further, each of these samples was subjected to a water resistance test by immersing them in hot water at 70°C for 60 hours, and then a tensile test was conducted. The results of these tensile tests are shown in Table 2. Surface resistance is 20℃, 60℃ according to ASTM-D-257.
%RH atmosphere using an electrometer (manufactured by Takeda Riken). From Table 2, when the amount of the phthalate compound of ethylene glycol mono(2-ethylhexyl) ether added is less than 1 part by weight (formulation 1,
and 2), it is found that there is no effect of improving antistatic properties, and when the amount is more than 150 parts by weight (Blend 7), an extreme decrease in strength is caused. In addition, in the sample subjected to plasma treatment, no deterioration in antistatic effect over time was observed, and good durability was exhibited.

【table】

[Table] Example 2 Polyvinyl chloride resin composition with the following composition: Formulation A Formulation B Polyvinyl chloride (Kanevinyl S-1003) 100
100 Phthalate ester compound of ethylene glycol mono(2-ethylhexyl) ether
70 − DOP − 70 Epoxidized soybean oil 3 3 Ba-Zn stabilizer 2 2 New Elegan B (cationic surfactant)
-2 was molded under the same conditions as Example 1. The molded product made from Formulation B exhibited a plate-out phenomenon on the surface of the heating roll. This sample was subjected to low temperature plasma treatment under the same conditions as in Example 1. Table 3 shows the performance of the molded product obtained. In the soap water resistance test, industrial soap (Nitsusan Yurex Paste H manufactured by Nippon Oil & Fats) was used.
The sample was immersed in a 1% aqueous solution of 70°C at a temperature of 70°C, then washed with water for 3 hours, dried with hot air at 40°C for 1 hour, and then subjected to measurement. Table 3 shows that according to the method of the present invention, it is possible to obtain a molded article with surface resistance and volume resistivity so low that they cannot be obtained with the surfactant (formulation B), and the antistatic ability of this molded article. It can be seen that the durability is also excellent.

〔Effect of the invention〕

The antistatic polyvinyl chloride resin composition molded article obtained by the method of the present invention has a low surface area that cannot be obtained with surfactant-added compositions without deteriorating the physical and chemical properties of the polyvinyl chloride resin. A resistance value (10 ⁷ to 10 ¹¹ Ω) and/or a low volume specific resistance value (10 ⁶ to 10 ¹⁰ Ωcm) can be obtained, and the resulting molded product has excellent antistatic ability maintenance durability. The antistatic polyvinyl chloride resin composition molded products produced by the method of the present invention and having the above-mentioned effects can be used for containers, wind pipes, semiconductors, cases for electronic parts, various mats, computers, clean room related supplies, etc. It is useful for

Claims (1)

[Scope of Claims] 1 100 parts by weight of polyvinyl chloride resin;
The surface of a molded article made from a composition containing 150 parts by weight of at least one dicarboxylic acid ester compound of mono- and poly-alkylene glycol monoalkyl ethers is treated with low-temperature plasma. A method for producing an antistatic polyvinyl chloride resin composition molded article. 2. The dicarboxylic acid ester compound of mono- and poly-alkylene glycol monoalkyl ether has the following general formula () K0108 (However, in the above formula, Represents a member selected from acid residues, and A ₁ and A ₂ each have 2 to 4 carbon atoms.
represents an alkylene group, R ₁ and R ₂ each represent a member selected from linear and branched alkyl groups having 3 to 15 carbon atoms, and m ₁ and m ₂ each independently represent an integer of 1 to 7. represent ) The method according to claim 1, wherein the method is selected from organic compounds represented by: 3. The method according to claim 1, wherein the low-temperature plasma treatment is performed using low-temperature plasma of a gas that does not have plasma polymerizability under a pressure of 0.001 to 10 Torr.