JPH06200171A - Resin composition having excellent antistaticity - Google Patents

Abstract

PURPOSE:To provide a resin composition keeping the excellent properties of base resin and causing little deterioration of antistaticity even after the use over a long period. CONSTITUTION:The objective resin composition is composed of (A) a thermoplastic resin, (B) an alkylene oxide copolymer containing ethylene oxide as a component and (C) an organic sulfonic acid metal salt expressed by the general formula (R-SO3)nM [(n) is 1-2; R is alkyl or alkylphenyl; M is alkali metal or alkaline earth metal) or an a metal salt dissociative into ions and expressed by the formula MXn [(n) is 1-2; M is alkali metal or alkaline earth metal; X is halogen, SCN, Clo4, BF4, PF6, B[phi]4 (phi is phenyl), CF3SO3 or CF3CO2].

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a thermoplastic resin composition having excellent antistatic properties. Here, the antistatic property means that the surface electric resistance is small and static electricity is hardly generated on the surface of the resin product.

[0002]

2. Description of the Related Art Thermoplastic resins have the advantages of easy molding, excellent properties of molded articles and economical advantages.
Widely used for various purposes. Thermoplastic resins generally have good electrical insulation properties and are often used as electrical insulators in electrical parts as well, but on the other hand, there is a problem that molded products are easily charged and dust is easily attached and contaminated. Therefore, a grade having antistatic property has been developed. For example, it may be a thermoplastic resin in which polyethylene oxide or an organic sulfonic acid metal salt is blended alone. In addition to this, an antistatic polystyrene resin composition obtained by adding a sulfonic acid metal salt of polyethylene oxide and an alkylphenyl compound is disclosed in Japanese Patent Application Laid-Open No. 2-233743, and in Japanese Patent Application Laid-Open No. 3-227357, a A rubber-reinforced styrenic resin to which ethylene oxide and a metal salt which forms a solid solution with ethylene oxide are added is described.

[0003]

Recently, however, electronic products have become more sophisticated and higher in density, and malfunctions due to electrification have increased, and stains on OA equipment have become disliked. The requirements for the above have become more and more strict, and conventional antistatic thermoplastic resins have not been able to sufficiently meet the requirements. Another problem is that the initial antistatic property is greatly deteriorated when cleaning is performed during processing or during use. The present invention researches and completes a resin composition capable of maintaining excellent antistatic properties for a long period of time without impairing the excellent mechanical properties and processability of the thermoplastic resin as a base. It was done.

[0004]

According to the present invention, 100 parts by weight of a thermoplastic resin and a weight average molecular weight of 20,000 to 1 are used.
2 to 40 parts by weight of an alkylene oxide copolymer having 1,000,000 ethylene oxide as a component,
General formula _{(R-SO 3) n M} (1) However, n = 1 to 2, R represents an alkyl group or an alkylphenyl group M is an organic sulfonic acid metal salt represented by an alkali metal or alkaline earth metal, Or MX _n (2) where n = 1 to 2, M is an alkali metal or an alkaline earth metal X is a halogen atom, SCN, ClO ₄ , BF ₄ , PF
₆ , B [φ] ₄ (where φ is a phenyl group), CF ₃ S
Disclosed is a resin composition having excellent antistatic properties, which comprises 0.3 to 10 parts by weight of an ion dissociative metal salt represented by O ₃ or CF ₃ CO ₂ . Among them, as the thermoplastic resin, a polyolefin resin, polyvinyl chloride resin,
A mixture of one or more selected from the group consisting of polymethacrylic acid ester-based resins and polystyrene-based resins is preferably used, and the alkylene oxide copolymer has a molar composition ratio of ethylene oxide of 40 or less. It is preferably about 99%. Furthermore, among the organic sulfonic acid metal salts used for the resin composition having excellent antistatic property, the general formula is (R—SO ₃ ) _nM (3) where n = 1 to 2 and R are The alkyl group having 1 to 30 carbon atoms or the alkylphenyl group M is preferably an organic sulfonic acid metal salt represented by an alkali metal or an alkaline earth metal.

[0005]

Embodiments As a result of repeated studies for achieving the above-mentioned object, the present inventor has found that a thermoplastic resin has a weight average molecular weight of 2 or less.
The alkylene oxide copolymer having ethylene oxide as one component was blended at a concentration of 10,000 to 10,000,000, and a specific metal salt was added as a third component, whereby the antistatic property of the present invention was excellent. A resin composition was found. This will be described in detail below. First, the components to be blended will be described. As the thermoplastic resin to be added to the resin composition of the present invention having excellent antistatic property, a thermoplastic resin which is generally used at present can be used.
For example, polyolefin resins such as polyethylene and polypropylene; styrene resins such as polystyrene, acrylonitrile-styrene copolymer (AS resin) and acrylonitrile-butadiene-styrene copolymer (ABS resin); polymethyl methacrylate, polymethacrylic acid. Polymethacrylic acid ester resins such as ethyl; vinyl acetate resins; polyvinyl alcohol; vinyl chloride resins; fluorine-containing resins, polyester resins, polyamide resins, polycarbonate resins and the like.

Next, an alkylene oxide copolymer containing ethylene oxide as one component used in the present invention (hereinafter, referred to as
It is abbreviated as an alkylene oxide copolymer. Examples of the component other than ethylene oxide) include propylene oxide, butylene oxide, cyclohexene oxide, styrene oxide and epichlorohydrin. Of these, propylene oxide is preferred. The alkylene oxide copolymer component can be produced by copolymerizing ethylene oxide with other copolymerized alkylene oxide in the presence of a suitable alkali, metal catalyst and the like. The manufacturing method is not particularly limited, and a known method can be used. Further, the method described in Japanese Patent Application No. 196973 of 1991 can be used. There is no particular limitation on the composition ratio of ethylene oxide and other alkylene oxide in the copolymer, but a resin composition in which the molar composition ratio of ethylene oxide in the alkylene oxide copolymer is 40 to 99% is preferable. By doing so, the crystallinity of the copolymer can be lowered, the compatibility with the resin is improved, and a resin composition excellent in antistatic property can be obtained.
The weight average molecular weight of the alkylene oxide copolymer is usually 20,000 to 10,000,000, preferably 10
It is in the range of 10,000 to 6,000,000. 20,
If less than 000, sufficient antistatic effect cannot be obtained and 1
When it exceeds 0,000,000, it becomes difficult to knead with other components, and the surface condition of the molded product is also not preferable.

The general formula added as the third component
(1): (R-SO₃)_nOrganic sulfonic acid represented by M
Metal salt and general formula (2): MX_nIon solution represented by
The releasable metal salt will be described. The general formula is shown in (1)
The organic sulfonic acid metal salt having 1 to 30 carbon atoms
Linear or branched alkyl group or alkylphenyi
Sulfonic acid metal salt having a vinyl group (shown by the general formula (3)
Preferred), for example, methyl, octyl, dodecyl
Gold alkyl sulfonates such as le, stearyl and behenyl
Alkylphenyls such as genus salts and dodecylbenzene
Examples thereof include sulfonic acid metal salts. Metals that make up salt
As for lithium, potassium, sodium, etc.
Potassium metal and magnesium and calcium
It can be arbitrarily selected from the potassium earth metals. one
As the ion dissociable metal salt represented by the general formula (2),
Alkali metals such as lithium, potassium and sodium,
And alkaline earth gold such as magnesium and calcium
Genus and Fluorine (F^-), Chlorine (Cl^-), Bromine (B
r^-), Iodine (I ^-), Thiocyanic acid (SCN^-),
Perchloric acid (ClO_Four ^-) Metal salts that release ions such as
It can be arbitrarily selected from among. Besides this, Tetra
Fluoroboric acid (BF_Four ^-), Hexafluorophosphoric acid
(PF₆ ^-), Tetraphenyl boric acid (B [φ]_Four ^-)
(However, φ indicates a phenyl group), trifluoromethane
Sulfonic acid (CF₃SO₃ ^-) Or trifluoroacetic acid
(CF₃CO₂ ^-) In metal salts that release ions such as
You may choose from. The above general formula is (1) or
The metal salt represented by (2) may be used alone or as a mixture of two or more kinds.
You may add it. In addition to the above, the antistatic resin of the present invention
The composition should contain plasticizers and antioxidants that do not impair antistatic properties.
Anti-static agent, heat stabilizer, UV absorber, lubricant, compatibilizer, face
Materials, reinforcing agents and the like can be added.

Further, the blending ratio of these components will be described. The mixing ratio of the thermoplastic resin and the alkylene oxide copolymer is such that 2 to 40 parts by weight of the alkylene oxide copolymer is added to 100 parts by weight of the thermoplastic resin. If the blending amount of the alkylene oxide copolymer is less than 2 parts by weight, it is difficult to obtain sufficient antistatic property or stable antistatic effect. On the other hand, if the amount exceeds 40 parts by weight, the surface quality of the molded product deteriorates, and the excellent mechanical properties of the thermoplastic resin as the base cannot be maintained, which is not preferable. The metal salt represented by the general formula (1) or (2) is mixed in an amount of 0.3 to 10 parts by weight with respect to 100 parts by weight of the thermoplastic resin. When the amount is less than 0.3 parts by weight, sufficient antistatic effect cannot be obtained, and when the amount is more than 10 parts by weight, the surface quality of the molded product is deteriorated and sometimes the molded product is colored, which is preferable. Absent. If there are other components to be added, an appropriate amount can be added depending on the purpose of addition.

Further, a method for producing the resin composition of the present invention having excellent antistatic property will be described. A thermoplastic resin, an alkylene oxide copolymer, and a metal salt represented by the general formula (1) or (2) in a predetermined mixing ratio are added to, for example, a single-screw extruder, a twin-screw extruder, a kneader, a twin-screw kneader, etc. And kneading may be performed in a temperature range of 70 to 250 ° C. There are no particular restrictions on the kneading machine used, the kneading method, the timing of addition of the blending components, and the like.

[0010]

EXAMPLES Further, the resin composition of the present invention having excellent antistatic properties will be specifically described with reference to Examples and Comparative Examples.
The compounding components used in the examples and comparative examples, the methods for obtaining the same, and the methods for measuring the physical properties of the obtained resin compositions were the ones described below. In addition, the inside of [] is the abbreviation used in Table 1 which shows an Example and a comparative example collectively. A. Compounding component of resin composition having excellent antistatic property (1) Thermoplastic resin a) ABS resin: [ABS]: ABS resin (Toyolac (registered trademark) 100 (manufactured by Toray Industries, Inc.) b) Polyvinyl chloride resin: [PVC]: Polyvinyl chloride resin (Aron Powder (registered trademark) V-
500W-16 (manufactured by Toagosei Co., Ltd.) c) Polypropylene resin: [PP]: Polypropylene resin (UP Polypro FS4012 (manufactured by Union Polymer Co., Ltd.) (2) Alkylene oxide copolymer: [PAO]: Acquisition method: Using the organozinc compound-alcohol catalyst, the charged amounts of ethylene oxide and propylene oxide were changed to obtain the following three types of alkylene oxide copolymers having different molar composition ratios of ethylene oxide and propylene oxide. According to nuclear magnetic resonance spectrum analysis: a) ethylene oxide (95%)-propylene oxide (5%) copolymer: [A] b) ethylene oxide (75%)-propylene oxide (25%) copolymer: [B ] C) Ethylene oxide (60%)-Propylene oxide (40%) Copolymer: [C] (3) Polyalkylene oxide (homopolymer) a) Polyethylene oxide (PEO-1 (Sumitomo Seika Co., Ltd.): [D] (4) The general formula is (1) or (2). A) Metal salt represented by the formula: a) Organic sulfonate metal salt represented by the general formula (1): Sodium methanesulfonate: [V] Sodium stearylsulfonate: “W” Sodium octylsulfonate: [X] Dodecylbenzene Sodium sulfonate: [Y] b) Ion-dissociative metal salt represented by the general formula (2) NaSCN: [Z] The unit of the compounding amount shown in Table 1 is the thermoplastic resin 10.
It is the weight part of each component with respect to 0 weight part.

B. Method of measuring physical properties of resin composition (1) Antistatic property (unit of numerical value shown in table: Ω) The resin composition was molded into a thickness of 1 mm by hot press and 10 cm.
Two x10 cm test pieces were produced. One of these
The test piece was kept for 24 hours in an atmosphere of 23 ° C. and 50% RH to obtain a test piece before cleaning. After immersing the remaining test piece in pure water for 5 minutes, the surface is washed with pure water from a washing bottle,
A test piece after washing was held in an atmosphere of 23 ° C. and 50% RH for 24 hours. The surface resistivity of each of these test pieces was measured and evaluated as the antistatic property and the stability of the antistatic property over time. The surface resistivity was measured by using a hyper insulation meter (SM-8210 manufactured by Toa Denpa Kogyo Co., Ltd.) and measuring voltage 100.
V was measured at an application time of 1 minute. (2) Hardness (Unit of numbers shown in the table: Shore D) According to JIS K7215, the hardness was measured using a durometer (Ueshima Seisakusho: Shore hardness meter D type). (3) Tensile strength (Unit of numbers shown in the table: kg / c
m ² ) According to JIS K7113, a tensile tester (manufactured by Shimadzu Corporation: Autograph AG-500A) was used, and the tensile speed was measured at 50 mm / min.

Examples 1 to 10 and Comparative Examples 1 to 3 Based on 100 parts by weight of ABS resin, the alkylene oxide copolymer or ethylene oxide homopolymer in the compounding amounts shown in Table 1 and the general formula (1) are shown. An organic sulfonic acid metal salt or an ion dissociative metal salt represented by (2) described above, and 0.3 part by weight of an antioxidant (Ciba Geigy Corporation: Irganox 1010), a Henschel mixer (Mitsui Miike Kako Co., Ltd. ): FM20B), and blended in powder form. Using an electrically heated two-roll kneader (TM type manufactured by Yasuda Seiki Co., Ltd.), this blend was
The mixture was kneaded for 0 minutes at a temperature of 140 to 160 ° C. to produce a resin composition having excellent antistatic property of the present invention and a resin composition for comparison. Various physical properties were measured by molding these resin compositions into the above predetermined shapes by hot pressing. The results are shown in Table 1. It was found that the resin composition of the present invention having excellent antistatic property is superior in antistatic property and is not inferior in mechanical properties as compared with Comparative Example.

Example 11 and Comparative Example 4 A polyvinyl chloride resin was used as the thermoplastic resin, and the alkylene oxide copolymer or ethylene oxide homopolymer and the organic sulfonic acid metal salt were blended in the amounts shown in Table 1, except that A resin composition was obtained in the same manner as in Example 1. Various physical properties were measured by molding these resin compositions into the above predetermined shapes by hot pressing. The results are shown in Table 1.
It was shown to. It was found that the resin composition of the present invention having excellent antistatic property is superior in antistatic property and is not inferior in mechanical properties as compared with Comparative Example.

Example 12 and Comparative Example 5 A polypropylene resin was used as the thermoplastic resin, and 160 to 1
A resin composition was obtained in the same manner as in Example 1 except that the alkylene oxide copolymer or ethylene oxide homopolymer and the organic sulfonic acid metal salt were mixed at 80 ° C. in the amounts shown in Table 1. Various physical properties were measured by molding these resin compositions into the above predetermined shapes by hot pressing. The results are shown in Table 1. Compared to the comparative example,
It was found that the resin composition of the present invention having excellent antistatic property has excellent antistatic property and is not inferior in mechanical properties.

Table 1-a Example 1 2 3 4 5 Thermoplastic resin ABS ABS ABS ABS ABS PAO A B C B B compounding amount 10 10 10 2 30 metal salt X X X X X compounding amount 2 2 2 2 2 2 surface Resistance Before washing 3.2 × 10 ¹⁰ 2.3 × 10 ¹⁰ 3.5 × 10 ¹⁰ 5.8 × 10 ¹⁰ 2.4 × 10 ¹⁰ After washing 3.6 × 10 ¹⁰ 1.2 × 10 ¹⁰ 1.9 × 10 ¹⁰ 4.2 × 10 ¹¹ 1.5 × 10 ¹⁰ Hardness 76 75 74 75 68 Tensile strength 400 375 385 455 280 Molded product surface Good Good Good Good Good Good

Table 1-b Example 6 7 8 9 10 Base resin ABS ABS ABS ABS ABS PAO BBBBBB Compounding amount 1010101010 Metal salt WWYZV Compounding amount 0.582222 Surface resistance Before washing 3.1 × 10 ¹⁰ 3.4 × 10 ⁹ 1.4 × 10 ¹⁰ 2.5 × 10 ¹⁰ 6.5 × 10 ¹⁰ After washing 7.0 × 10 ¹¹ 4.5 × 10 ¹⁰ 2.8 × 10 ¹⁰ 5.9 × 10 ¹⁰ 8.5 × 10 ¹¹ Hardness 74 73 72 76 74 Tensile strength 370 350 380 425 365 Molded product surface Good Good Good Good Good Good

Table 1-c Example 11 12 Comparative Example 1 Comparative Example 2 Comparative Example 3 Base resin PVC PP ABS ABS ABS PAO BBBBBD Mixing amount 10 10 10 50 10 Metal salt Y X W X X X blending amount 2 2 0.2 2 2 Surface resistance Before washing 3.0 × 10 ⁹ 7.6 × 10 ¹¹ 2.8 × 10 ¹¹ 1.4 × 10 ¹⁰ 8.7 × 10 ¹¹ After washing 5.2 × 10 ¹⁰ 5.2 × 10 ¹² 1.1 × 10 ¹⁴ 3.5 × 10 ¹⁰ 1.2 × 10 ¹² Hardness 39 69 69 74 62 73 Tensile strength 150 285 380 195 395 Molded product surface Good Good Good Stickiness Good

[0018]

[0019]

EFFECT OF THE INVENTION The resin composition of the present invention having excellent antistatic properties is free from the drawback of conventional antistatic resin compositions, that is, the antistatic property is not significantly deteriorated by washing, and the resin composition can be used for a long period of time. Holds stable. This is based on a thermoplastic resin, and in order to impart antistatic property, since the alkylene oxide copolymer and the above-mentioned organic sulfonic acid metal salt or ion-dissociative metal salt are blended, both blending components are An antistatic resin composition having an excellent antistatic synergistic effect can be obtained. Furthermore, in the resin composition excellent in antistatic property of the present invention,
It has the effect of maintaining the same excellent mechanical properties and molding processability as the base resin. Therefore, it can be easily and safely used for electronic parts and office automation equipment, and is expected to have a wide range of uses.

Claims (4)

[Claims] 1. A thermoplastic resin having 100 parts by weight and a weight average molecular weight of 20,000 to 10,000,000.
And 2 to 40 parts by weight of an alkylene oxide copolymer containing ethylene oxide as a component and having a general formula of (R—SO ₃ ) _nM (1) where n = 1 to 2 and R is an alkyl group or an alkylphenyl group. Group M is an organic sulfonic acid metal salt represented by an alkali metal or alkaline earth metal, or MX _n (2) where n = 1 to 2, M is an alkali metal or alkaline earth metal X is a halogen atom, SCN, ClO ₄ , BF ₄ , PF
₆ , B [φ] ₄ (where φ is a phenyl group), CF ₃ S
A resin composition having excellent antistatic properties, which comprises 0.3 to 10 parts by weight of an ion dissociative metal salt represented by O ₃ or CF ₃ CO ₂ . 2. The thermoplastic resin is one or more selected from the group consisting of a polyolefin resin, a polyvinyl chloride resin, a polymethacrylate ester resin and a polystyrene resin. 1. A resin composition having excellent antistatic property according to 1. 3. The resin composition having excellent antistatic property according to claim 1, wherein the molar composition ratio of ethylene oxide in the alkylene oxide copolymer is 40 to 99%. . 4. The organic sulfonic acid metal salt according to claim 1 has the general formula (R—SO ₃ ) _nM (3) where n = 1 to 2 and R is an alkyl group having 1 to 30 carbon atoms. The group or the alkylphenyl group M is a compound represented by an alkali metal or an alkaline earth metal.
The resin composition having excellent antistatic property according to 2 or 3.