JPS60240782A - Antistatic agent composition - Google Patents

Abstract

PURPOSE:To provide the titled compsn. having an excellent persistent antistatic effect, consisting of a reaction product between a 1,2-epoxyalkane and monoethanolamine and a reaction product between a specified fatty acid and aminoethylethanolamine. CONSTITUTION:One mol of a 1,2-epoxyalkane of the formula (wherein R1 is a 10-28C alkyl) is reacted with 1-6mol of monoethanolamine in an inert gas atmosphere at 110-150 deg.C to obtain a reaction product (A). A fatty acid contg. a 7-21C alkyl or alkenyl group, such as lauric acid, is reacted with aminoethylethanolamine to obtain a reaction product (B). 70-97wt% component A is melt- mied with 30-3wt% component B.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an antistatic agent for synthetic resins. More specifically, the present invention relates to an antistatic agent composition that is highly effective (and has a permanent effect) on polyolefin resins, styrene resins, ABS resins, polyacrylic acid resins, and polymethacrylate resins.

Synthetic resins have excellent insulating properties, and this property is utilized, but once charged, they have low conductivity and are difficult to leak, causing various static electricity problems, which has become a problem. In other words, dust adhesion due to electrostatic charge occurs during molding or after processing, which poses a troublesome problem in distribution and use, and causes accidents such as fires and injuries due to electric shock caused by charged static electricity. It also becomes the source of errors in instruments. There is a strong desire to solve these problems. Furthermore, recently, when resins are used as substrates for electronic devices, the problem of dust adhesion due to charging has become severe, and there has been a growing demand for prevention of charging.

In addition, surface processing such as painting or plating on the surface of plastics has been increasing recently, and the static electricity generated in such cases has an impact on the surface processing, and as the processing process speeds up, There is a growing demand for antistatic properties even during the short time between molding and subsequent processing.

In other words, when using resins, there is a growing demand for permanent antistatic properties as well as antistatic properties during processing. I have a request.

In response to the above situation, there are many proposals regarding permanent antistatic agents, but there are very few kneaded-in types that are effective immediately after molding, and even if they are effective, the degree of effectiveness is extremely low. Conventional permanent antistatic agents show some effect after molding, but this varies depending on the type of resin.
The level of effectiveness of the antistatic agent is reached after 2 to 3 days at the earliest, and the effectiveness is maintained for 1 to 2 years or several years thereafter. Various compounds have been reported as antistatic agents that exhibit such effects. As an antistatic agent for polyolefins, a mixture of β-hydroxyalkyl-N-hydroxylamine obtained by the reaction of an olefin oxide and an alkanolamine is known (Tokuko Sho 3L).
-57561), although it has a permanent antistatic ability, it is not effective immediately after molding (it takes several days for the effect to appear, and it cannot be processed immediately after molding as mentioned above). Furthermore, it is not suitable when β-hydroxyalkyl-N
- A mixture of ethanolamine and N,N-di(β-hydroxyalkyl)-N-ethanolamine is used as an antistatic agent for ABS resin (Japanese Patent Publication No. 50-14'261) and polystyrene resin (Japanese Patent Publication No. 51-7499). Patents have been applied for, but these also have a permanent effect, but
The effect immediately after molding is low, and it is difficult to apply it to the above-mentioned uses. The latter two are β-hydroxyalkyl-
It is said that a mixture of N-ethanolamine and N1N-di(β-hydroxyalkyl)-N-ethanolamine is more effective than β-hydroxyalkyl-N-ethanolamine alone, but β-hydroxyalkyl-N-ethanolamine The higher the effect is, the greater the amount of the compound alone or the higher the content thereof, so the level of effect is low and the permanent effect is not sufficient.

In addition, these antistatic agents have the disadvantage that, when washed repeatedly with water to check durability and recovery of the effect, the recovery of the effect is slow, and the effect decreases with the number of washings.

As mentioned above, most of the reports that have been reported so far are intended to have a permanent antistatic effect, and are not intended to be effective immediately after molding and have a permanent effect. These durability effects are also of a low level and do not have a high antistatic effect over a long period of time. In addition, many compounds and compositions are considered to have immediate effects, but these have only temporary effects but are not long-lasting (and some are not permanent antistatic agents). It is impossible to mix them, or they have drawbacks such as warping and reducing the effectiveness.

The present invention was devised focusing on these points, and the effect begins to appear within a few hours after molding and kneading, and a high level of effect is achieved within a day, and the effect is permanent. It can last anywhere from one to two years to several years. In other words, the present stage is a 1,2-epoxyalkane represented by the general formula (1) (wherein R1 represents an alkyl group having 10 to 28 carbon atoms).
and monoethanolamine and 70 to 97% by weight of the reaction product (A) obtained by reacting a fatty acid having an alkyl group or alkenyl group having 7 to 21 carbon atoms with aminoethylethanolamine. Reaction product (B
) 3 to 30% by weight of an antistatic agent composition for synthetic resins.

The 1,2-epoxyalkane used in the present invention has an alkyl group having 10 to 28 carbon atoms in the epoxy ring, and 12-epoxyalkanes having these carbon atoms are used alone or in combination with two or more carbon atoms.
Use by mixing more than one species.

The reaction product of 12-epoxyalkane and monoethanolamine is obtained by reacting 21 moles of 12-epoxyalkane with 1 to 6 moles of monoethanolamine. This reaction is carried out using the above raw materials in a reactor under an inert gas at 110 to 15
This is done by heating at 0°C. The reaction product obtained here is a compound obtained by the addition reaction of one molecule of 1,2-epoxyalkane to one active hydrogen in a monoethanolamine molecule (hereinafter referred to as "1-1 addition"). (hereinafter referred to as "2-1 adduct") and a compound obtained by reacting two active hydrogen molecules in a monoethanolamine molecule with two molecules of 1,2-epoxyalkane (hereinafter referred to as "2-1 adduct"). It is a mixture, and the mixing ratio is 11-1 adduct J: r by weight ratio.
The 2-1 adduct and J-10:0 to 7:3 are good, and it is preferable to use as much of the "1-1 adduct" as possible because it is more effective.

If the amount of "2-1 adduct" exceeds 30% in the mixture, the effect is low and is out of the practical range.

The mixing ratio of "1-1 adduct" and "12-1 adduct" is determined by measuring the total amine value, partial amine value, and tertiary amine value, and the theoretical molecular weight of the tertiary amine compound (r2-1 adduct). I wonder. The reaction product (B) is obtained by reacting a fatty acid having an alkyl group or an alkenyl group having 7 to 21 carbon atoms with aminoethylethanolamine. Dacillin and ■ CH2CH20H Compound R2-C0NHCH2CH2NHCH2CH20H represented by general formula (3)...
・・・・・・・・・・・・・・・・・・・・・(3) The ratio of the mixture is based on the measured values of total amine value, secondary amine value, and tertiary amine value. However, the antistatic effect is not affected by the mixing ratio. Examples of fatty acids having an alkyl group or alkenyl group having 7 to 21 carbon atoms include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, behenic acid, etc., and these can be used alone or in combination. It will be done.

Industrially obtained mixed fatty acids include coconut oil fatty acids,
Examples include beef tallow fatty acid and other animal and vegetable oil fatty acids.

Reaction product (A) 70-97 obtained as above
% by weight and 3 to 30% by weight of a reaction product (B) obtained by reacting a fatty acid having an alkyl group or an alkenyl group having 7 to 21 carbon atoms with aminoethylethanolamine, but both reaction products are mixed. It is preferable to dissolve the substances and mix them uniformly before preparing the product, as this provides a consistent effect.

The present invention will be explained below using comparative examples and examples.

The reaction product hole used for this and the composition of the reaction product (Bl) are shown in Tables 1 and 2.

Table 1 Composition of reaction product (5) Table 2 Composition of reaction product (B) Next, the reaction product (5) in Table 1 and the reaction product (
B) was mixed at different ratios (weights), kneaded into a synthetic resin, and the antistatic properties were measured. The results are shown in Table 3. The test method is as follows.

(1) Preparation of measurement plate I) Polystyrene plate (hereinafter referred to as "H■-PS"): Add 1.5% by weight of the sample (Nos. 1 to 18 in Table 3) to impact-resistant polystyrene. After mixing uniformly, use an extrusion molding machine to create antistatic agent-containing pellets.
Next, it is molded using an injection molding machine at 220-230℃ to a thickness of 3.
It was molded into a mm plate.

The resin was treated in the same manner as the polystyrene plate to obtain an ABS plate.

111) High-density polyethylene plate (rHD-P)
(denoted as EJ): 0.5% by weight in high-density polyethylene resin
After adding the samples (1 to 18 in Table 3) and mixing uniformly,
Obtain pellets through an extruder and convert them into 200-21
A 3 mm thick plate was obtained by injection molding at 0°C.

+V) Polypropylene plate (hereinafter referred to as rPPJ): Polypropylene resin was treated in the same manner as the polyethylene plate to obtain a polypropylene plate.

(2) Measurement of antistatic properties Immediately after molding, 2 days after molding, molding 7
The half-life (seconds) after electrostatic charging after 1 day and 2 months after molding.
The antistatic property was measured using a stack honest meter (manufactured by Shishido Shokai).

(3) Measurements Nα1 to 2.8 to 11.17 to 18 in Measurement Results Table 3 are outside the scope of the present invention, and measurements Nα3 to 7.12 to 16 are within the scope of the present invention.

From those measurement results, i) the mixing ratio of reaction product: reaction product (B) was 97:
3 to 70: Those in the range of 30 are 2.
It showed excellent antistatic properties up to 100% of the time.

11) A mixture of reaction product (5) and reaction product FB) showed better antistatic properties immediately after molding than each of them alone.

Table 4 below shows the measurement results according to the examples. Table on the sample
Using the reaction product (5) of Table 1 and the reaction product (B) of Table 2, the mixing ratio (weight) is: (B1=90:
The measurement plate was prepared and the antistatic property was measured using the method described above.

Claims (1)

[Claims] 1. 12-epoxyalkane represented by general formula (1) (
However, R1 represents an alkyl group having 10 to 28 carbon atoms)
A reaction product obtained by reacting 70 to 97% by weight Makinto with monoethanolamine, a fatty acid having an alkyl group or an alkenyl group having 7 to 21 carbon atoms, and aminoethylethanolamine. (B)3
-30% by weight of an antistatic agent composition.