JPS5863737A - Prevention of static electrification of polyolefin resin - Google Patents

Abstract

PURPOSE:To improve the antistatic properties of a resin without causing smoking during molding processing and blooming phenomena on molded articles, by using a specific amine compound as an antistatic agent. CONSTITUTION:Polyolefin resin is blended with an amine compound shown by the formula (R is 8-22C straight-chain or branched-chain alkyl or alkenyl; X is H, 8-22C straight-chain or branched-chain saturated or unsaturated acyl and 1-3 X amoung 4 X are the acyls). The use of an alkanesulfonate (preferably, sodium salt or potassium salt) with the amine compound has synergistic actions. 100pts.wt. polyolefin is blended with 0.05-5pts.wt., preferably 0.1-2pts.wt. amine compound or amine compound and alkanesulfonate.

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, 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.

-Various antistatic agents have been proposed to prevent such charging properties. One of them is known as N@N-bis(2-hydroxyethyl)alkylamine,
Attempts have been made to avoid the above-mentioned problems by kneading this into 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 it. Moreover, although this type of amine compound differs depending on the type of its alkyl group and the type of polyolefin resin to which it is applied, it generally has poor compatibility with the resin, and a blooming phenomenon occurs in which it is eluted onto the resin surface during the molding process. This type of amine compound easily caused the phenomenon of peeling when the load was too high.As a result, the surface of the molded resin became sticky and the surface condition was significantly damaged. During the molding process, smoke was generated due to the volatilization of the amine compound, and this was likely to cause problems in the workability of the molding process.

This invention was discovered as a result of intensive studies from the above-mentioned viewpoint, and the gist thereof is to apply the antistatic agent to a polyolefin resin using the general formula; 22 linear or branched alkyl or alkenyl groups, X is a hydrogen atom or a linear or branched saturated or unsaturated acyl group having 8 to 22 carbon atoms, and 1 of the 4 -3 are the above-mentioned acyl groups] A method for preventing static electricity of a polyolefin resin characterized by adding an amine compound represented by A method for preventing static electricity by adding it to a resin.

The amine compound represented by the above general formula used in the present invention can be obtained by subjecting an aliphatic primary amine to an addition reaction with glycidol, and then further reacting with a fatty acid or a derivative thereof to esterify it.

Here, the degree of esterification is 1 out of 4 X in the general formula
The ratio is such that ~3 is an acyl group.

In addition, the aliphatic primary amine may be one having a straight or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and specifically, caprylic amine, 2-
Ethylhexylamine caprylamine, laurylamine, myristylamine, heptylamine, sterylamine, isostearylamine, behenylamine, oleylamine, erucylamine, etc., coconut oil alkylamine, beef tallow amine, hardened beef tallow which is a mixture of these. Examples include amines.

The fatty acids or derivatives thereof that are subjected to the esterification reaction after the addition reaction of glycidol to the above-mentioned aliphatic primary amines include those having a linear or branched saturated or unsaturated acyl group having 8 to 22 carbon atoms. That's fine. Specific examples of such fatty acids include caprylic acid, 2-ethyl hexanic acid, capric acid, lauric acid, myristic acid,
Examples include palmitic acid, stearic acid, isostearic acid, hehenic acid, oleic acid, erucic acid, and mixtures thereof such as coconut oil fatty acid, beef tallow fatty acid, palm oil fatty acid, and hydrogenated beef tallow fatty acid.

In addition, fatty acid derivatives include lower alkyl esters such as methyl esters and ethyl esters derived from each of the above-mentioned fatty acids, and fatty acid chlorides.

The inventors have discovered that the above-mentioned amine compound is superior to polyolefin resins compared to conventional amine compounds, that is, N,N-bis(2-hydroxyethyl)alkylamines prepared by addition-reacting ethylene oxide to aliphatic primary amines. Furthermore, when kneaded into the above-mentioned resin and subjected to molding, the antistatic effect can be exhibited 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, and furthermore, smoke generation during molding can be significantly suppressed.

In this way, the amine compound represented by the above general formula has an excellent antistatic function that prevents ignition and electric shock accidents during the resin processing process, which tend to cause problems with polyolefin resins, as well as problems in continuous packaging work and printing. In addition to effectively solving various problems such as deterioration in properties, there is no reduction in workability due to smoke generation during the molding process.
In addition, the outstanding effect of providing a polyolefin resin molded product with good surface properties that does not cause the resin surface to become sticky due to blooming during the molding process can be obtained.

In addition, in the amine compound represented by the above general formula,
Those in which the number of carbon atoms in the alkyl group (8) and acyl group (to) are 7 or less or 23 or more,
If all of the four X's are acyl groups, the antistatic function is poor and the effects of the invention described above 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.
It may be 2 parts by weight. If the amount added is too small, a sufficient antistatic effect cannot be obtained, while if it is too large, the surface condition of the resin or resin molded product will deteriorate due to blooming phenomenon, which is not preferable.

Next, in this invention, when an alkanesulfonate 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, their synergistic effect results in more antistatic properties than the amine compound alone. It has been found that the effect is even greater, and in this case, there is no particular adverse effect on the prevention of smoke generation during molding and the prevention of blooming phenomenon 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 paraffinic hydrocarbons, and the salt is preferably a water-soluble salt such as a sodium salt or a potassium salt. Commercially available products include Halorard Knee manufactured by Bayer AG, West Germany, and Hostaplu 5A60 manufactured by Hoechst AG, West Germany.

When such alkanesulfonates are used together,
The amount is preferably 10-90% by weight, preferably 30-70% 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 the amine compound will be impaired, which is undesirable.In addition, the amount added to the polyolefin resin should be determined by combining the above-mentioned amine compound with the above-mentioned one. The total amount of the alkanesulfonate is usually 0.05 to 5 parts by weight, preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the polyolefin resin.
The amount may be 2 parts by weight.

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, prevent smoking during molding, and 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〉 Stearylamine (total amine value 213) 130P (5,
0 mol) in a flask and heated to 100-1100C.
Glycidol (purity 9
5%) 779 g (10.0 mol) was added dropwise over a period of 1 hour.Then, it was aged at 130-1350C for 2 hours, and N.
N-bis(2,3-dihydroxypropyl)stearylamine was obtained.

The total amine value of this amine is 134, and the tertiary amine value is 12.
It was 4.

Next, amine 210 obtained by the above method! i + (0.5 mol) and stearic acid 250 p (0.9 mol) were placed in a four-loaf flask and subjected to an esterification reaction at 235°C for 1 hour under a nitrogen gas stream, whereby k in the above general formula was stearyl, 4 An amine compound was obtained in which an average of 1.8 of the X atoms were represented by stearoyl atoms and an average of 2.2 atoms were represented by hydrogen atoms.The acid value of this amine compound was 2.0, the total amine value was 60, and the tertiary amine The value was 59 and the melting point was 52°C.

Hereinafter, this will be referred to as amine compound A.

N...N-bis(2,3-dihydroxypropyl)stearylamine 1 obtained in the same manner as in the case of amine compound A
68F (0.4 mol) and stearic acid 278F (1.0
mol] in a flask and heated under a stream of nitrogen gas
By carrying out an esterification reaction at 5°C for 1 hour, k in the above general formula is stearyl, and the average of 4 X is 2.5.
An amine compound having stearoyl atoms and an average of 1.5 hydrogen atoms was obtained. The acid value of this amine compound is 6,
4. Total amine value is 49, tertiary amine value is 49, melting point is 5.
It was 3°C. Hereinafter, this will be referred to as amine compound B.

<Amine compound C> N,N-bis(
2,3-dihydroxypropyl)stearyl, amine 2
3x9 (o, ss mol) and lauric acid 198M0.99
mol) in a fourth flask and heated under a stream of nitrogen gas for 22 hours.
By performing an esterification reaction at 0°C for 1.5 hours,
K in the above general formula is stearyl, and an average of 1 out of 4 X
．． An amine compound having 8 lauroyl atoms and an average of 2.2 hydrogen atoms was obtained. The acid value of this amine compound is 2
．． 1. Total amine value is 72, tertiary amine value is 70, melting point -
It was 800. Hereinafter, this will be referred to as amine compound C.

Example 1 Low-density polyethylene resin (Nippon Petrochemical Co., Ltd., May 50),
Amine compounds A, B, C or a mixture of these and a sodium salt of alkanesulfonic acid (Valorat Knee, manufactured by Bayer) were added as antistatic agents, and this was rolled at 120°C for 5 minutes and pressed at 1506C. A sheet with a thickness of 1 m was produced by molding for 3 minutes. The surface resistivity (applied voltage: 500 V) and surface condition of this sheet, as well as the smoke generation properties during sheet processing, were investigated, and the results were as shown in Table 1 below.

Note that the smaller the value of the surface resistivity, the better the antistatic effect. Furthermore, the smoke generation during sheet processing is divided into the following five levels based on the state of smoke generation.If smoke is observed up to about 125 CII+ or more of the processing roll, it is classified as very high, and if smoke is observed up to about 15 cm above the processing roll. Thick, if smoke is observed up to about 10cm above the processed roll, medium, if smoke is only observed at about 15G of the processed roll, small, and if almost no smoke is observed, very small. ,Ta.

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, and the comparative example in the table means the number of parts added (parts by weight) of the antistatic agent to 100 parts by weight of the resin. These are the results when the sodium salt of alkanesulfonic acid was added alone.

/'' Example 2 High-density polyethylene resin (Mitsui Petroleum Chemical 2200J)
In addition, amine compounds A and B are used as antistatic agents.

C or sodium salts of these and alkanesulfonic acids (
Add a mixture with Bayer Valorato Knee],
This was rolled for 5 minutes at 150°C, then pressed for 17 minutes.
Molding was performed at 06C for 3 minutes to give a thickness of 1rIrI.
n sheets were produced. The surface resistivity (applied voltage of 500 V) and surface condition of this sheet were examined for smoke generation during sheet processing, and the results were as shown in Table 2 below. The addition amounts and comparative examples in Table 2 are the same as those in Table 1 above.

Example 3 A polypropylene resin (Mikata Noblen Jl-IH-G, manufactured by Mikata Toatsu Kagaku Co., Ltd.) was added with amino' compounds A, B, and C as an antistatic agent, or a sodium salt of these and an alkanesulfonic acid (Valorat, manufactured by Bayer).・Knee] was added, and this was formed by rolling at 1700°C for 5 minutes and press forming at 180°C for 3 minutes to produce a sheet with a thickness of 1 mm.

The surface resistivity (applied voltage of 500 V) and surface condition of this sheet were examined for smoke generation during sheet processing, and the results are shown in Table 3 below. In addition, the third
The amounts added and the comparative examples in the table are the same as in Table 1 above.

As is clear from the results in Tables 1 to 3 on the embankment,
When the amine compound according to the present invention is used as an antistatic agent, it exhibits an excellent antistatic effect in a short time during molding, produces less smoke during molding, and has a good surface condition of the molded product. I understand. 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 (2)

[Claims] (1) The polyolefin resin has the following general formula; (wherein, k is a straight or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and X is a hydrogen atom or a straight chain having 8 to 22 carbon atoms. or a branched saturated or unsaturated acyl group, and 1 to 3 of the 4 X are the above-mentioned acyl groups. How to prevent it. (2) The polyolefin resin has the following general formula; (wherein, k is a straight or branched alkyl group or alkenyl group having 8 to 22 carbon atoms, and X is a hydrogen atom or a straight chain having 8 to 22 carbon atoms. or a branched saturated or unsaturated acyl group, in which 1 to 3 of the 4 X are the above-mentioned acyl groups] and an alkanesulfonate. Features of polyolefin resin prevention method.