JPS5863736A - Prevention of static electrification of polyolefin resin - Google Patents

Abstract

PURPOSE:To disperse an antistatic agent in good compatibility, and to improve the antistatic properties of resin without causing blooming phenomena on molded articles, by using a specific amine compound as the antistatic agent. CONSTITUTION:An amine compound shown by the formula (R is 8-22C straight- chain or branched-chain alkyl or alkenyl; m+n is 1-6) is added to polyolefin resin. The addition of an alkanesulfonate to it shows synergistic actions. The amount of the amine compound is 0.05-5pts.wt., preferably 0.1-2pts.wt. based on 100pts.wt. polyolefin resin. When the alkanesulfonate is used together with the amine compound, the total amounts of the amine compound and the alkanesulfonate are 0.05-5pts.wt., preferably 0.1-2pts.wt.

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to a method for preventing static electricity on polyolefin resins.

In general, polyolefin resin sheets, films, and other molded products have superior mechanical properties compared to those made of other synthetic resins, as well as low specific gravity and excellent chemical resistance. However, on the other hand, it has the disadvantage of being highly chargeable. Electrification causes ignition during the resin processing process, electric shock accidents, deterioration of continuous packaging workability and printability, adhesion of dust, etc., and is an extremely serious problem from both the resin processing and commercial value standpoints.

Conventionally, various antistatic agents have been proposed to prevent such charging properties. One known example is N,N-bis(2-hydroxyethyl)alkylamine, and attempts have been made to avoid the above-mentioned problems by kneading this into a resin and subjecting it to molding.

However, the above-mentioned amine compounds are somewhat inferior in their antistatic function, and also have the disadvantage that they do not exhibit their effectiveness until a certain period of time has elapsed during the molding process. I couldn't say that. Moreover, although this type of amine compound differs depending on the type of alkyl group and the type of polyolefin resin to which it is applied, it generally has poor compatibility with the resin, and blooming occurs on the resin surface as the molding process progresses. This phenomenon is likely to occur, especially when the amount added is increased in order to increase the antistatic effect. As a result, there was a problem that the surface of the molded resin became sticky and the surface condition was significantly impaired.

This invention was discovered as a result of intensive studies from the above viewpoint, and its gist is that polyolefin resin is treated as an antistatic agent with the following general formula; a linear or branched alkyl group or artenyl group, m+n is 1 to 6). A method for preventing static electricity of a polyolefin resin, characterized in that an acid salt is used in combination and both components are added to the polyolefin resin.

The amine compound represented by the above general formula used in this invention can be obtained by subjecting an aliphatic primary amine to an addition reaction with glycidol. Here, the number of moles of glycidol added, that is, m + n in the general formula
is 1 to 6, and mI! : Either one of n can be 0.

In addition, the aliphatic primary amine may be one having a straight chain or branched alkyl group or artenyl group having 8 to 22 carbon atoms, and specifically, caprylic amine, 2-
Ethylhexylamine, caprylamine, laurylamine, myristylamine, heptylamine, stearylamine, instearylamine, behenylamine, oleylamine, erucylamine, as well as mixtures of these, such as coconut oil alkylamine, tallow amine, and hardened tallow amine. Can be mentioned.

The inventors have discovered that the above-mentioned amine compound is more effective against polyolefin resins than conventional amine compounds, that is, N,N-bis(2-hydroxyethyl)alkylamines prepared by addition-reacting ethylene oxide with aliphatic primary amines. It has an excellent antistatic function, and when kneaded into the above resin and subjected to molding, it can exhibit its antistatic effect relatively quickly.Furthermore, it has good compatibility with various polyolefin resins, making it easy to mold and process. It has been found that the blooming phenomenon is less likely to occur.

As described above, the amine compound represented by the above general formula has an excellent antistatic function that causes problems with polyolefin resins such as ignition and electric shock accidents during the resin processing process, continuous packaging workability, and printing problems. It is an outstanding product that can effectively solve various problems such as a decrease in surface properties, as well as provide polyolefin resin molded products with good surface properties that do not cause the resin surface to become sticky due to blooming during the molding process. Effects can be obtained.

In addition, in the amine compound represented by the above general formula,
If the number of carbon atoms in the alkyl group (R) is 7 or less or 23 or more, or if m + n is 7 or more, the antistatic function will be poor, and the effects of this invention as described above will be impaired. cannot be obtained.

The amount of the amine compound represented by the above general formula added to the polyolefin resin is usually 0.05 to 5 parts by weight, preferably 0.1 parts by weight per 100 parts by weight of the polyolefin resin.
The amount is preferably 2 parts by weight. If the amount added is too small, a sufficient antistatic effect will not be obtained, and if it is too large, the surface condition of the resin molded article will deteriorate due to blooming phenomenon, which is not preferable.

Next, in this invention, when a tilkanesulfonate is used together with the amine compound represented by the above-mentioned general formula as an antistatic agent, and both components are added to the polyolefin resin, the synergistic effect results in a higher charge than the amine compound alone. It has been found that the prevention effect is even greater, and in this case, there is no particular adverse effect on the prevention of blooming during molding. .

The above alkanesulfonate generally has 10 to 2 carbon atoms.
It is derived from a compound obtained by a lead reaction or a sulfoxidation reaction of a paraffinic hydrocarbon of 0. As a salt, a water-soluble salt such as a sodium salt or a potassium salt→m is preferable.

Commercially available products include Valorado Knee manufactured by Bayer AG, West Germany, and Hostaplu 5A (5Q manufactured by Hoechst AG, West Germany).

When such alkanesulfonates are used together,
The amount is preferably 10 to 90% by weight, preferably 30 to 70% by weight based on the total amount with the amine compound. If this proportion is too small, the above-mentioned effect cannot be obtained by the combination, and if it is too large, the antistatic function peculiar to amine compounds will be impaired, which is not preferable. The amount added to the polyolefin resin is such that the total amount of the amine compound and the alkanesulfonate is usually 0.05 to 5 parts by weight, preferably 0.1 to 2 parts by weight, based on 100 parts by weight of the polyolefin resin.
It may be determined by weight parts.

Polyolefin resins applicable to this invention include a wide range of high-density polyethylene resins, low-density polyethylene resins, polypropylene resins, ethylene-propylene copolymer resins, and ground-modified polyolefin resins. In this invention, the above-mentioned antistatic agent is added to these resins, and if necessary, known additives are blended, and the resulting resins are subjected to various molding processes such as extrusion molding, injection molding, inflation, and stretching. This makes it possible to exhibit the excellent antistatic effect as described above and to obtain a resin molded product with good surface properties.

EXAMPLES Below, examples of the present invention will be described in more detail. In addition, the amine compounds A, B, and C used in each example
is an amine compound represented by the above general formula, which was produced by the following method.

Amine compound A> Laurylamine (total amine value 301) 746S+ (4,
Place 0 mole of glycidol (purity 95
%) 623 g (8.0 mol) was added dropwise over 1 hour.

Then, it is aged at 120 to 130°C for 2 hours, and N in the general formula where k is lauryl and both m and n are 1,
N-bis(2,3-dihydroxypropyl)laurylamine was obtained.

The total amine value of this amine compound was 165, and the tertiary amine value was 153. Hereinafter, this will be referred to as amine compound A.

Amine compound B〉 Stearylamine (total amine value 213) 1,3201
Amine compound A
Glycidol 779Li (10,
0 mol) was added dropwise. Then, it was aged at 130 to 135° C. for 2 hours to obtain N,N-bis(2,3-dihydroxypropyl)stearylamine in which k is stearyl and both m and n are 1. The total amine value of this amine compound was 134, and the tertiary amine value was 124. Hereinafter, this will be referred to as amine compound B.

Amine Compound C> Amine Compound B (837P (2.0 mol)) and 1.1 g of triethanolamine as a catalyst were placed in four flasks, and glycidol (31214.0 mol) was added under the same conditions as for Amine Compound A. It took 2 hours to drip. Then, it is aged at 130-135℃ for 3 hours, and k in the general formula is
An amine compound in which m and n are both stearyl and 2 was obtained. The total amine value of this amine compound is 98,
The tertiary amine value was 94. Hereinafter, this will be referred to as amine compound C.

Example 1 Low density polyethylene resin (Japan Petrochemical Co., Ltd. J50)
In addition, amine compounds A and B are used as antistatic agents.

c4 or these and the sodium salt of alkanesulfonic acid (
Add a mixture with Bayerl Valorato Ni);
This was rolled at 120°C for 5 minutes, then pressed at 150°C.
A sheet with a thickness of 1 m was produced by molding at 30° C. for 3 minutes. Surface specific resistance of this sheet (applied voltage 500
V) and the surface condition, the results are as shown in Table 1 below.

Note that the smaller the value of the surface resistivity, the better the antistatic effect. Further, the amount added in Table 1 means the number of parts (parts by weight) of the antistatic agent added to 100 parts by weight of the resin. Furthermore, the comparative examples listed in Table 1 are the results when no antistatic agent was added, when a conventional amine compound was added, and when a sodium salt of alkanesulfonic acid was added alone.

Example 2 High density polyethylene resin (Mitsui Petrochemical Co., Ltd. 2200)
J), amine compounds A, B,
C or a mixture of these and alkanesulfone sodium salt (Bayer Valorat) was added, and this was rolled at 150°C for 5 minutes and then pressed at 170°C.
A sheet having a thickness of 11KIn was produced by molding the product under conditions of 3 minutes. The surface specific resistance of this sheet (applied voltage s
The results of examining the surface conditions (oon) and surface conditions were as shown in Table 2 below. In addition, the amounts added in Table 2,
The comparative examples are the same as those in Table 1 above.

Example 3 Polypropylene resin (Mitsui Noblen JHH-G, Mitsui Toatsu Chemical Co., Ltd.) G, amine compound A as an antistatic agent
, B, C or a mixture of these and a sodium salt of an alkanesulfonic acid (Valorato Knee, manufactured by Bayer AG) was added, and the mixture was rolled at 170°C for 5 minutes and pressed at 180°C for 3 minutes. It was shaped into a sheet with a thickness of 1 m. The surface resistivity (applied voltage: 500 V) and surface condition of this sheet were investigated, and the results were as shown in Table 3 below. Note that the amounts added and the comparative examples in Table 3 are the same as those in Table 1 above.

As is clear from the results in Tables 1 to 3 above,
Use of the amine compound according to this invention as an antistatic agent
It can be seen that when this is done, a good antistatic effect is exhibited in a short time during the molding process, and the surface condition of the molded product is also improved. It is also clear that the antistatic effect can be further improved by using the above amine compound and alkanesulfonate together.

Patent applicant: NOF Corporation

Claims (1)

[Claims] +1J polyolefin resin has the following general formula: (wherein,
k is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and m+n is 1 to 6. How to prevent it. (2) The polyolefin resin has the following general formula: (wherein,
R is a linear or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and mn is 1 to 6. A method for preventing static electricity on polyolefin resin.