JPH02302453A - Antistatic agent for polyolefin resin - Google Patents

Abstract

PURPOSE:To obtain an antistatic agent, composed of an ester interchange reaction product of an ethylene oxide adduct of a specific aliphatic primary amine with a specified fatty acid monoglyceride, excellent in rapid acting properties and stability of antistatic effects and useful for polyolefin resins. CONSTITUTION:An antistatic agent obtained by reacting (A) an adduct of an aliphatic primary amine expressed by the formula (R is 16 to 22C aliphatic hydrocarbon group) with ethylene oxide, preferably 2mol ethylene oxide adduct of stearylamine and/or 2mol ethylene oxide adduct of cethylamine with (B) a monoglyceride of a 16 to 22C fatty acid, preferably stearic acid monoglyceride and/or palmitic acid monoglyceride at a molar ratio of the components (A):(B) within the range of (1:9) to (4:6), preferably (1:9) to (3:7), preferably in the absence of a catalyst and a solvent at 90 to 140 deg.C for 4 to 12hr. The abovementioned antistatic agent in an amount of 0.1 to 3wt.% based on polyolefin resins is added thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION The above invention relates to antistatic agents for polyolefin resins.

Conventionally, polyolefin resins such as polyethylene and polypropylene have been widely used as various molding materials for films, sheets, injection molded products, and the like.

In general, polyolefin resins have high electrical insulation properties and tend to generate and accumulate static electricity due to friction.

For example, such electrostatic charges can make it difficult to remove plastic films and reduce the efficiency of packaging processes, cause electric shocks to the human body during processing processes, impair the appearance of plastic products, and cause problems with printing and painting. It also becomes.

As a method for preventing charging of polyolefin resins, the use of antistatic surfactants has been carried out. There are two ways to prevent static electricity using a surfactant: 1. Applying a surfactant to the resin surface, and 2. Kneading the surfactant into the interior. It is excellent in that it can be mixed into a master pellet and has a long-lasting effect.

Internally kneaded antistatic agents are effective by migrating into the resin after molding and bleeding to the surface to form a uniform layer, so the antistatic effect is not expressed. Something fast is required.

Various types of internally kneaded antistatic agents for polyolefins have been proposed.

For example, Japanese Patent Publication No. 44-925 discloses a mixture of an ethylene oxide adduct of an aliphatic amine and a fatty acid ester of a polyhydric alcohol as an antistatic agent. In addition, Japanese Patent Publication No. 52-33654 and Special Publication No. 62-
No. 33256 discloses an esterification reaction product of an ethylene oxide adduct of an aliphatic amine and a fatty acid.

moreover.

Japanese Patent Publication No. 52-30015 discloses the combined use of an esterification reaction product of an ethylene oxide adduct of an aliphatic amine and a fatty acid and a fatty acid ester of a polyhydric alcohol.

However, all of these conventional antistatic agents were insufficient in terms of immediate effect.

The objective of the present invention is to provide an antistatic agent for polyolefin resins that exhibits antistatic effect quickly and can provide stable antistatic performance.

The antistatic agent for polyolefin resin of the present invention is as follows (
The molar ratio of a) and (b) is (a): (b) = 1
:9 to 4:6.

(a) General formula (I) CH, CH, OH RN...(1) CH,
An ethylene oxide adduct of an aliphatic-class amine represented by CH, OH (R: aliphatic hydrocarbon group having 16 to 22 carbon atoms); and (b) a fatty acid whose fatty acid residue has 16 to 22 carbon atoms. Monoglyceride The present invention will be explained in more detail below.

As component (a), which is one of the starting components of the transesterification reaction product of the present invention, a 2 mole ethylene oxide adduct of an aliphatic amine having 16 to 22 carbon atoms is used, particularly an oxidized ethylene oxide of stearylamine. Preferred are a 2 mole ethylene adduct, a 2 mole ethylene oxide adduct of cetylamine, or a mixture thereof.

If the carbon number of the aliphatic-class amine in component (a) is greater than 22, the antistatic ability will be poor, while if it is less than 16, the surface of the molded product will become sticky, which is not practical.

As the fatty acid monoglyceride of component (b), those having a fatty acid residue having 16 to 22 carbon atoms are used, and particularly preferred are stearic acid monoglyceride, valmitic acid monoglyceride, or a mixture thereof.

(b) When the number of carbon atoms in the fatty acid residue of component is greater than 22,
On the other hand, if it is smaller than 16, it will adhere to the mold during injection molding or bleed out excessively, making the surface of the molded article sticky, which is not practical.

A reaction product obtained by subjecting the above components (,) and (b) to a transesterification reaction is used as the antistatic agent of the present invention. These two components have a molar ratio of component (a) to component (b) of (a):(b)=1:9 to 4:6.
, preferably in the range of 1:9 to 3 Nia. If the amount of component (a) is too small beyond this molar ratio, the immediate effect of the antistatic ability will deteriorate. Furthermore, if the amount of component (a) is too large beyond the above ratio, the antistatic agent bleeds out onto the surface of the molded product, causing the surface to become sticky or white, impairing its aesthetic appearance, which is not practical.

In the transesterification reaction of both components (a) and (b) above, an alkali catalyst such as sodium hydroxide, potassium hydroxide, or sodium methylate may be added as appropriate; however, since component (a) itself is alkaline, , the reaction proceeds satisfactorily in the absence of a catalyst. The reaction temperature is suitably 40 to 140°C, and the reaction time is suitably 3 to 50 hours, and these are appropriately selected depending on the presence or absence of a catalyst, the molar ratio, and the like. Preferably (a),
(b) both components without a catalyst and without a solvent at 90 to 140°C,
Allow to react for 4-12 hours. The reaction products thus obtained include 40 to 80 vt% (preferably 45 to 75 wt%) of fatty acid monoglycerides and 2 to 30 vt% (preferably 2 to 30 vt%) of 2-mol ethylene oxide adducts of aliphatic-class amines.
15 wt%), 5 to 30 wt% (preferably 5 to 20 vt%) of a fatty acid monoester of a 2 mole ethylene oxide adduct of an aliphatic-grade amine, 1 to 1 to 30 wt% of a fatty acid diester of a 2 mole ethylene oxide adduct of an aliphatic-grade amine. 15 wt% (preferably 1 to 10 vt%), glycerin 1 to 10 wt% (
Preferably 1-5% + 1%), fatty acid diglyceride 2
~20wt% mixture.

In the present invention, it is believed that these components act synergistically to exhibit excellent antistatic ability. That is, it exhibits antistatic ability that is much more immediately effective than when an antistatic agent is prepared by simply mixing both components (a) and (b), which are the starting materials for the transesterification reaction.

The polyolefin resin to which the antistatic agent of the present invention is applied includes homopolymers such as ethylene, propylene, butylene, and pentene, copolymers of ethylene and propylene, copolymers of ethylene and vinyl acetate, and copolymers of ethylene and vinyl chloride. Examples include copolymers, copolymers of ethylene and acrylic esters, and the like.

The transesterification product of the present invention is 0.1 to 3.0% relative to the polyolefin resin. It is preferable to add Ovt%. If the amount added is too small, the antistatic effect will not be sufficiently expressed, while if it is too large, the mechanical properties of the molded product will be greatly affected.

When blending the antistatic agent of the present invention into the polyolefin resin, if necessary, lubricants such as higher alcohol, higher fatty acid amide, higher fatty acid jetanolamide, fatty acid metal soap, known antioxidants, ultraviolet absorbers, blocking agents, etc. It is possible to use inhibitors, colorants, fillers and other additives in combination.

When adding the antistatic agent of the present invention to a polyolefin resin, a conventional method such as kneading it with the polyolefin resin using a tri-blend booster is adopted. It is also possible to process the mixture into a masterbatch and dilute it for use.

The polyolefin resin using the antistatic agent of the present invention is
It can be applied to molded products of various shapes including sheets and films by press molding, injection molding, extrusion molding, blow molding, calendar molding, etc.

According to the antistatic agent for polyolefin resin of the present invention, by using the transesterification product of the ethylene oxide adduct of a specific aliphatic-class amine and an aliphatic monoglyceride, The molded product obtained by kneading it is excellent in terms of immediate antistatic effect, stability, and surface condition.

Large-1-Nuclide Synthesis Example 1 1 mol of stearylamine EO (hereinafter referred to as EO) 2 mol adduct and 9 mol of stearic acid monoglyceride were reacted at 120°C for 6 hours in an N2 atmosphere, resulting in a pale yellow color. powder was obtained. As a result of gas chromatography analysis, the obtained reaction product had a composition shown in Table 1 below.

Synthesis Example 2 2 moles of a mixture consisting of 80 vt% of a 2 molar adduct of stearylamine EO and 20 wt% of a 2 molar adduct of palmitylamine EO, 65 vt% of stearic acid monoglyceride,
A reaction product was obtained by reacting 8 mol of a mixture consisting of 35%+1% of valmitic acid monoglyceride at 140° C. for 8 hours in an N2 atmosphere.

As a result of gas chromatography analysis, the obtained reaction product had the composition shown in Table 1.

Comparative Synthesis Example 1 0.5 mol of stearylamine EO 2 mol adduct and 9.5 mol of valmitic acid monoglyceride were reacted under the same conditions as in Synthesis Example 1 to obtain a comparative reaction product that does not correspond to the scope of the present invention. . The composition ratio of the comparison product was as shown in Table-1.

Table 1: Composition of reaction products (vt%) Synthesis Examples 3 to 6 In the same manner as in Synthesis Example 2, reaction products according to the present invention were obtained using the compounds shown in Table 2 below as starting materials.

Note that Table 2 also lists the starting materials in Synthesis Examples 1 and 2 above.

Comparative Synthesis Examples 2 to 5 In the same manner as in Comparative Synthesis Example 1, reaction products shown in Table 3 below that do not fall within the scope of the present invention were obtained.

Note that in Table 1-3, the above-mentioned Comparative Synthesis Example 1 is also listed.

Table 3 = Starting materials and molar ratios of Comparative Synthesis Examples 1-5 Examples 1-6. Comparative Examples 1 to 11 Polypropylene resin with melt index 8 (g/10 min) (manufactured by Idemitsu Petrochemical Co., Ltd., Idemitsu Polypro J-740G)
) To 100 parts by weight, 0.4 parts by weight of the antistatic agents of the present invention and comparative examples shown in Table 4 were added and kneaded using an extrusion machine to prepare strand pellets.6 Then, the pellets were injected. Using a molding machine, the temperature of the cylinder is 230℃.
The sample was molded into a 5 mm plate and used as a sample for evaluation of antistatic effect and surface condition.

The antistatic effect was measured at a constant temperature of 20℃ and humidity of 65%.
The test was carried out in a constant humidity atmosphere, and the tests were carried out immediately after molding and after being left in the same atmosphere for 3 months.

The antistatic effect is achieved by measuring the surface resistivity using an ultra-super insulation meter (Toa Denpa).
The surface condition was determined by touch, with a value of 1012Ω or less being considered acceptable.

0: Not sticky (passed) Δ: Slightly sticky (fail) X: Sticky (fail) The above evaluation results are shown in Table 4.

Claims (1)

[Claims] 1.(a) General formula (I) ▲There are numerical formulas, chemical formulas, tables, etc.▼...(I) (However, R: an aliphatic hydrocarbon group having 16 to 22 carbon atoms) An ethylene oxide adduct of an aliphatic primary amine and (b) a fatty acid monoglyceride whose fatty acid residue has 16 to 22 carbon atoms are mixed in a molar ratio of (a):(b) in the range of 1:9 to 4:6. An antistatic agent for polyolefin resins, characterized in that it consists of a reaction product obtained by a transesterification reaction.