JP2995504B2 - Antistatic polyolefin resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an antistatic polyolefin resin, and more particularly to an antistatic polyolefin resin which does not cause yellowing even when a phenolic antioxidant is added to the polyolefin resin.

[0002]

2. Description of the Related Art Polyolefin resins generally have excellent mechanical properties and are useful for molded articles, films, fibers and the like.
However, polyolefin resins have problems such as high chargeability and dust adhesion, and in order to prevent these, various antistatic agents are usually added to polyolefins. As antistatic agents added to polyolefin resins, amine compounds such as N, N-dihydroxyethyllaurylamine and N, N-dihydroxyethylstearylamine are frequently used. In addition, at the same time, in order to impart thermal stability and anti-oxidation deterioration during polyolefin resin molding processing, generally, an antioxidant or a heat stabilizer such as a phenol-based, phosphorus-based, or sulfur-based compound is added to the polyolefin. I have.

[0003]

When these amine-based antistatic agents and phenolic antioxidants are used in combination, there is a problem that the polyolefin resin molded article turns yellow during long-term storage. In particular, N, N-
Except for dihydroxyethyllaurylamine, no effective antistatic agent has been found with a small amount of addition, which is a serious problem.

[0004] Yellowing is often promoted by heat, ultraviolet rays and nitrogen oxides, but also occurs when stored in the dark at room temperature in the air. Therefore, the conventional antistatic agent and the combination of various antioxidants including a phenolic antioxidant cannot simultaneously satisfy the antistatic property and the antioxidant property without causing yellowing. was there.

[0005]

Means for Solving the Problems In view of such circumstances, the present inventors have conducted intensive studies to obtain a polyolefin resin composition having good antistatic properties and antioxidant properties without yellowing. If a specific antistatic agent is blended with the polyolefin resin, even when any phenolic antioxidant is used in combination, it does not cause yellowing over time, and has good antistatic properties and antioxidant properties. It has been found that a polyolefin resin composition having the same can be obtained, and the present invention has been completed.

That is, the present invention relates to a polyolefin resin to which a phenolic antioxidant has been added, wherein (a) an alkane sulfonate or an alkylaryl sulfonate having an alkyl moiety having 8 to 18 carbon atoms and (b) an acyl moiety. Of a fatty acid diethanolamide having 8 to 22 carbon atoms in a weight ratio of 95/5 to 5/95 in an amount of 0.00.0 parts by weight based on 100 parts by weight of the polyolefin resin.
Another object of the present invention is to provide an antistatic polyolefin resin composition in which 5 to 2 parts by weight are blended.

The polyolefin resin used in the present invention includes high-pressure low-density polyethylene, low-pressure linear low-density polyethylene, medium-low pressure high-density polyethylene, polypropylene, ethylene-propylene block and random copolymer, polybutene-1, Examples thereof include poly-4-methylpentene-1 and the like and mixtures thereof. Further, a mixture obtained by adding a synthetic rubber, an inorganic filler, and the like to these polyolefin resins may be used.

As the (a) alkane sulfonate or alkylaryl sulfonate having 8 to 18 carbon atoms in the alkyl portion, which is blended in the antistatic agent used in the present invention, for example, the following general formula (1): What is represented is mentioned.

R ¹ SO ₃ M (1) wherein R ¹ represents an alkyl group having 8 to 18 carbon atoms or an alkylaryl group having 8 to 18 carbon atoms in the alkyl group;
M represents an alkali metal. )

Specific examples of these sulfonates (a) include sodium octanesulfonate, sodium decanesulfonate, sodium dodecanesulfonate, sodium tetradecanesulfonate, sodium hexadecanesulfonate, sodium octadecanesulfonate, average carbon number Sodium alkanesulfonate of 14.5, potassium alkanesulfonate having an average carbon number of 11.5, sodium decylbenzenesulfonate, sodium dodecylbenzenesulfonate, sodium tetradecylbenzenesulfonate and the like can be mentioned. When the number of carbon atoms in the alkyl portion of the sulfonate (a) is out of the range of 8 to 18,
The antistatic effect becomes insufficient. Also, when M is a metal other than an alkali metal, for example, calcium, a sufficient antistatic effect cannot be obtained.

The fatty acid diethanolamide (b) in which the acyl moiety has 8 to 22 carbon atoms is represented by the following general formula (2).

R ² CON (CH ₂ CH ₂ OH) ₂ (2) (wherein, R ² CO represents an acyl group having 8 to 22 carbon atoms)

Specific examples of the fatty acid diethanolamide (b) include lauryl diethanolamide, stearyl diethanolamide and the like. If the number of carbon atoms in the acyl group of the fatty acid diethanolamide is out of the range of 8 to 22, a sufficient antistatic effect cannot be obtained.

The compounding ratio of the alkanesulfonic acid salt or the alkylarylsulfonic acid salt (a) to the fatty acid diethanolamide (b) is from 95/5 to 5/95 by weight, preferably from 70/30 to 30/70. And 60 /
40-40 / 60 is more preferred. If the compounding ratio is out of this range, a sufficient antistatic effect cannot be obtained. The amount of the antistatic agent obtained by mixing the alkane sulfonate or the alkylaryl sulfonate (a) and the fatty acid diethanolamide (b) at a specific ratio to the polyolefin resin is 0 per 100 parts by weight of the polyolefin resin. 0.05 to 2 parts by weight, preferably 0.1 to 1 part by weight. If the addition amount is less than 0.05 part by weight, a sufficient antistatic effect cannot be obtained, while if it exceeds 2 parts by weight, the resin surface becomes sticky or adversely affects the resin properties.

The polyolefin resin composition of the present invention contains a phenolic antioxidant in order to prevent oxidative deterioration and thermal aging of the resin. Examples of phenolic antioxidants include 2,6-di-t-butylhydroxytoluene (trade name: BHT, manufactured by Wako Pure Chemical Industries), pentaerythrityl-tetrakis [3- (3,5-di-t-butyl) -4
-Hydroxyphenyl) propionate] (trade name: I
RGANOX1010, manufactured by Ciba Geigy Japan), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (trade name: IRGANOX)
1076, manufactured by Nippon Ciba Geigy). Further, various antioxidants other than phenolic compounds can be used in combination. For example, tris (mono, dinonylphenyl) phosphite (trade name: ADK STAB 329K, manufactured by Asahi Denka Kogyo), tris (2,4-di-t) -Butylphenyl) phosphite (trade name: ADK STAB 2112, manufactured by Asahi Denka Kogyo) and the like, distearyl 3,3'-thiodipropionate (trade name: Sumilizer TPS, manufactured by Sumitomo Chemical Industries), etc. Can be used.

The method for producing the polyolefin resin composition of the present invention is not particularly limited, and any known method can be used. For example, polyolefin resin, alkane sulfonate or alkylaryl sulfonate (a) and fatty acid diethanolamide (b) which are antistatic agents of the present invention, phenolic antioxidant, phosphorus antioxidant,
A method in which a sulfur-based antioxidant and other resin additives are heated and kneaded together if necessary, or an alkane sulfonate or an alkylaryl sulfonate (a) which is an antistatic component and a fatty acid diethanolamide (b) And a method of producing an antistatic agent masterbatch, mixing this master pellet with resin pellets containing various antioxidants, and molding.

As the heating kneading apparatus, kneading machines which are usually used, for example, various extruders, Banbury mixers, kneaders, mixing rolls and the like can be used. Alternatively, in an extruder for a molding machine, heating and kneading can be performed simultaneously with molding. It is also recommended to pre-mix before heat kneading. As the premixing device, a commonly used mixer, for example, a drum blender, a V-type blender, a ribbon blender, a Henschel mixer and the like can be used.

The polyolefin resin composition of the present invention may contain, in addition to the above components, inorganic pigments and organic pigments suitable for polyolefins, metal soaps such as calcium stearate, and the like.

[0019]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Examples 1 to 10 and Comparative Examples 1 to 3 An antistatic agent and an antioxidant were added to the high-density polyethylene resin powder as shown in Tables 1 and 2, respectively. Table 1
The amount of each compound described in (2) and (2) indicates the amount added (parts by weight) based on 100 parts by weight of the polyethylene resin powder.

After preliminary kneading with a super mixer, resin pellets were produced with a twin screw extruder. This was subjected to injection molding (Examples 1 to 5, Comparative Examples 1 and 2) and blown film molding (Examples 6 to 10 and Comparative Example 3). Measure the antistatic effect of the molded article, and at room temperature
C. Stored in a gear oven and observed the degree of yellowing.
The antistatic effect was determined by leaving the sample in a room at 25 ° C. and 50% humidity, measuring the surface resistivity 3 days after molding, measuring the half-life of the charged voltage using a static honestometer (manufactured by Shisido Electrostatics), and a dirt chamber test.
The results of the dirt chamber test and the yellowing test are shown in Tables 1 and 2 as ○ for good and × for bad.

Examples 11 to 20, Comparative Examples 4 to 6 The compounds of the present invention, various antioxidants, etc. were blended in polypropylene resin powder as shown in Tables 3 and 4. The amount of each compound shown in Tables 3 and 4 is the amount added (parts by weight) based on 100 parts by weight of the polypropylene resin powder.
Is shown. After preliminary kneading with a super mixer, resin pellets were produced with a twin screw extruder. This was subjected to injection molding (Examples 11 to 15, Comparative Examples 4 to 5) and film formation (Examples 16 to 20, Comparative Example 6) using a T-die / extruder, and the antistatic property of the molded product was measured. Dark place at room temperature or 8
It was stored in a 0 ° C. gear oven and the degree of yellowing was observed. The antistatic effect was determined by leaving the sample in a room at 25 ° C. and 50% humidity, measuring the surface resistivity 3 days after molding, measuring the half-life of the charged voltage using a static honestometer (manufactured by Shisido Electrostatics), and a dirt chamber test. The dirt chamber test and yellowing test results are
Tables 3 and 4 show good as ○ and bad as ×.

[0023]

[Table 1]

[0024]

[Table 2]

[0025]

[Table 3]

[0026]

[Table 4]

As is clear from the results of the above Examples and Comparative Examples, the polyolefin composition of the present invention had good antistatic properties and was prevented from yellowing over time.

[0028]

As described above, the polyolefin resin composition of the present invention comprises:
It has good antistatic properties and does not cause yellowing over time despite the addition of a phenolic antioxidant.

──────────────────────────────────────────────────の Continuation of the front page (51) Int.Cl. ⁶ identification code FI C08K 5:42) (58) Investigated field (Int.Cl. ⁶ , DB name) C08L 23/00-23/36 C08K 5 / 00-5/42

Claims (1)

(57) [Claims] 1. A polyolefin resin to which a phenolic antioxidant has been added, wherein (a) an alkanesulfonic acid salt or an alkylarylsulfonic acid salt in which the alkyl moiety has 8 to 18 carbon atoms and (b) the carbon number of the acyl moiety. Is 8 ~
Fatty acid diethanolamide which is 22/95 /
An antistatic polyolefin resin composition, characterized in that an antistatic agent mixed in an amount of 5 to 5/95 is added in an amount of 0.05 to 2 parts by weight based on 100 parts by weight of the polyolefin resin.