JPS60240781A - 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 specified alkylolamide. CONSTITUTION:One mol of a 1,2-epoxyalkane of formula I (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). An 8-22C satd. fatty acid such as lauric acid is reacted with an amine compd. such as monoethanolamine or diethanolamine in the presence of caustic alkali or sodium methylate at 140-210 deg.C to obtain an alkylolamide (B) of formula II [R2 is a 8-22C alkyl; R3 is H, methyl, (CH2CH2O)nH; n is 1-20] and an amine value of 20 or below. 70-97wt% component A is melt-mixed with 30-3wt% component B.

Description

[Detailed description of the invention] Wood is used as a lightning protection agent for intercalated resins. In particular, the present invention relates to an antistatic agent composition that has an immediate antistatic effect, is highly effective, and has a permanent effect.

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 and causing problems. 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. Low () Conventional permanent antistatic agents produce an 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, β-hydroxyalkyl-N- obtained by the reaction of olefin oxide and alkanolamine
Mixtures of hydroxylamine are known (Special Publication No. 3)
9-57561), although it has a permanent antistatic ability, it is not effective immediately after molding, and it takes several days for the effect to appear, and it cannot be processed immediately after molding as described above. It is not suitable if Furthermore, a mixture of β-hydroxyalkyl-N-ethanolamine and N,N-di(β-hydroxyalkyl)-N-ethanolamine was used as an antistatic agent, and ABS resin (Japanese Patent Publication No. 50-14'261) and polystyrene resin were used. (Japanese Patent Publication No. 51-7499) has been applied for, but these also have a permanent effect, but the effect immediately after molding is low, and it is difficult to apply them to the above-mentioned uses. In the latter two, a mixture of β-hydroxyalkyl-N-ethanolamine and N,N-di(β-hydroxyalkyl)-N-ethanolamine is
Although it is said to be more effective than hydroxyalkyl-N-ethanolamine alone, β-hydroxyalkyl-N-
Since the effect is higher when ethanolamine is used alone or in a larger amount, 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. There are also many compounds and compositions that are considered to have immediate effects, but these have only temporary effects but are not long-lasting, and they can be mixed with permanent antistatic agents. It is either impossible to do so, or it has drawbacks such as warping and reducing 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. That is, the present invention relates to a 1,2-epoxyalkane represented by the general formula (1) (wherein R1 represents an alkyl group having 10 to 28 carbon atoms)
70 to 97% by weight of the reaction product obtained by reacting monoethanolamine with an alkylolamide represented by the general formula (2) (wherein R2 is an alkyl group or aralkyl group having 8 to 22 carbon atoms, R3 is Hydrogen, methyl group, (CH2CH20)
This is an antistatic agent composition for synthetic resins, characterized in that it consists of 3 to 30% by weight (n H, n represents 1 to 20).

The 1,2-epoxyalkanes used in the present invention have an alkyl group having 10 to 28 carbon atoms in the epoxy ring, and 1,2-epoxyalkanes having these carbon atoms may be used alone or in a mixture of two or more. It will be done.

The reaction product of 12-epoxyalkane and monoethanolamine is obtained by reacting 1 mole of 1,2-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 1
This is done by heating at 50°C. The reaction product obtained here is generally a compound obtained by the addition reaction of one molecule of 12-epoxyalkane to one active hydrogen in a monoethanolamine molecule (hereinafter referred to as a "1-1 adduct"). ) and a compound obtained by reacting two active hydrogen atoms in a monoethanolamine molecule with two molecules of 1,2-epoxyalkane (hereinafter referred to as "2-1 adduct")
The mixing ratio is preferably [1-1 adduct J: r2'-1 adduct J = 10:0 to 7:3 in terms of weight ratio;
The more ``1-1 adducts'' there are, the more effective it is.
preferable. If the amount of "2-1 adduct" in the mixture exceeds 30%, the effect will be low and will be outside the practical range.

70 to 97% by weight of the reaction product thus obtained and 3 to 30% of the alkylolamide represented by general formula (2).
% by weight. The mixing method for both is to melt and mix the reaction product and the alkylolamide and then turn it into a product.
It is also preferred in order to obtain a uniform effect. The alkylolamide of general formula (2) can be obtained by reacting a saturated fatty acid having 8 to 22 carbon atoms with at least one of monoethanolamine, jetanolamine, N-methyl-N-hydroxylethylamine, and the like. The reaction is carried out by a known reaction method for producing an amide. That is, at 140 to 210°C in the presence of caustic alkali or sodium methylate, etc.
The reaction proceeds by heating at a temperature of .

The progress of the reaction is checked by measuring the amine value. When used in the present invention, it is preferable that the amine value in the alkylolamide is low; if it is high, it will cause discoloration after kneading the synthetic resin. The amine value is preferably 20 or less, preferably 10 or less. Examples of saturated fatty acids having 8 to 22 carbon atoms include simple fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid, and mixed fatty acids include coconut oil fatty acids, beef tallow fatty acids, and hydrogenated oil fatty acids of animal and vegetable oils. I get kicked.

The antistatic property was measured based on the mixing ratio of "1-1 adduct" and "2-1 adduct" in the reaction product of general formula (1) and monoethanolamine, and the results are shown in Table 1. show. "1
The ratio between the "-1 adduct" and the "2-1 adduct" was determined by measuring the total amine value, partial amine value, and tertiary amine value, and comparing them with the theoretical molecular weight of the tertiary amine compound. Further, the kneading conditions for polystyrene and polypropylene, the preparation of measurement plates, and the measurement of antistatic effect were performed as follows.

Table 1 (1) Preparation of measurement plate 1) Polystyrene plate: Add 1.5% by weight of the sample (Nα1 to 13 in Table 1) to impact-resistant polystyrene (hereinafter referred to as rHI-PSJ). After uniformly mixing, an antistatic agent-containing pellet is created using an extrusion molding machine, and then it is molded into a 3 mm thick pellet using an injection molding machine at 220 to 230°C.
It was molded into a plate.

11) Polypropylene plate: Polypropylene (hereinafter referred to as r
0.5% by weight sample (denoted as PPJ) (Nα1~ in Table 1)
13) was added to obtain pellets using an extrusion molding machine in the same manner as polystyrene, and the pellets were injection molded at 200 to 210°C to obtain a plate with a thickness of 3 mm.

(2) Measurement of antistatic effect For the measurement plate, 7 days after molding, at 20℃RH.
The antistatic effect was determined by measuring the half-life (seconds) using a static honest meter (manufactured by Shishido Shokai) under 40% conditions.

(3) From the measurement results shown in Table 1, the shorter the carbon chain length (R1), the better the effect, and the sample mixing ratio of 100:0 and 11-1 adducts was the most effective. As the amount of the "2-1 adduct" increases, the effect decreases. The mixing ratio of both from the viewpoint of practical antistatic effect is that Rt is Cl0-1
In the case of 2 + C14-16, 100:0-82:
18, and the ratio of 75:25 indicates a decrease in effectiveness.

When R1 is CI8-28, it is 100:O-95:5
It is effective at best, with decreasing effectiveness at 89:11. Therefore, when looking at R1 with CI2-28, it is “1-1
The mixing ratio of "adduct J: r2-1 adduct" is 100: O
Mixtures in the range of 70:30 are practical.

Next, the reaction product of general formula (1) and monoethanolamine and the alkylolamide of general formula (2) were mixed at different ratios (weight), kneaded into a synthetic resin, and the antistatic properties were measured. As a measurement example, the results are shown in Table 2. The alkylolamide used here was lauroyl jetanolamide, and the resin was kneaded using the method described above.
I-LPS, ABS, high density polyethylene (rHD)
-PEJ) and PP were measured at three points immediately after molding, 2 days later, and 7 days later.

From this result, the antistatic effect improves when the mixing ratio of alkanolamide is increased, but the effect decreases when it increases to 30% or more. No alkanolamide added (No. 1) and 296 (Nci2) had poor effects immediately after molding, and 35% (Nα8) also had poor effects immediately after molding. A mixing ratio of alkanolamide in a range of 3 to 30% is a range that is practically effective.

Examples are shown below. The content and mixing ratio (weight) of the reaction product of general formula (1) and monoethanolamine used in the examples (indicated by reaction product Nα in Table 1) and the compound of general formula (2) are shown below. -3, and put them in HI-PS, A
Table 4 shows the results of measurements using plates kneaded into BS, HD-PE, and PP resins. The kneading conditions etc. are as described above.

Table-3

Claims (1)

[Claims] 1 1,2-epoxyalkane represented by general formula (1) (
However, R1 represents an alkyl group having 10 to 28+ carbon atoms)
and monoethanolamine in an amount of 70 to 97% by weight, and an alkylolamide represented by the general formula (3) (wherein, R2 is an alkyl group having 8 to 22 carbon atoms. R3 is hydrogen, methyl group, (CH2CH20) n H'
% n indicates 1 to 20) 3 to 30% by weight.