JPH0464355B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an antistatic agent for synthetic resins. More specifically, it is an antistatic agent that can be kneaded into polyolefin resins, styrene resins, ABS resins, polyacrylic acid resins, and polymethacrylic acid resins to immediately provide an antistatic effect, which is highly effective and has a permanent effect. Regarding the composition. Synthetic resin has excellent insulating properties, and this property is utilized, but once charged,
Since it has low conductivity and is difficult to leak, it causes various static electricity problems and 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 electrostatic charge. 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 base materials for electronic devices, the problem of dust adhesion due to charging has become severe, and there has been a growing demand for prevention of static 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, , even during the short time between molding and next processing.
There is a growing demand for antistatic properties. In other words, in the use of 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-mentioned 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,
With conventional permanent antistatic agents, the effect appears after molding, although this varies depending on the type of resin, but it takes about 2 to 30 minutes at the earliest.
After 3 days, the antistatic agent reaches its level of effectiveness and continues to be effective for 1 to 2 years or even several years. Various compounds have been reported as antistatic agents that exhibit such effects. β obtained by the reaction of olefin oxide and alkanolamine as an antistatic agent for polyolefins.
-Hydroxyalkyl-N-hydroxylamine mixtures are known (Japanese Patent Publication No. 39-57561),
Although it has a permanent antistatic ability, it is not effective immediately after molding and takes several days to become effective, making it unsuitable for processing immediately after molding as mentioned above. do not have. Furthermore, a mixture of β-hydroxyalkyl-N-ethanolamine and N,N-di(β-hydroxyalkyl)-N-ethanolamine was used as an antistatic agent in ABS resin
-14261) and polystyrene resin (Special Publication No. 51-7499)
Patent applications have been filed for this method, 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. The latter two are β-hydroxyalkyl-N-ethanolamine and N,N-di(β-hydroxyalkyl)
It is said that a mixture of -N-ethanolamine is more effective than β-hydroxyalkyl-N-ethanolamine alone; however, the more effective β-hydroxyalkyl-N-ethanolamine is alone or the higher its content. The level of effectiveness is low and the permanent effect is not sufficient. In addition, these antistatic agents have the disadvantage that, when repeatedly washed 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 so far are
The purpose is to have a permanent antistatic effect, and it is not intended to be effective immediately after molding and has a permanent effect, and these durable effects are also of a low level and will not last for a long time. It does not have a high antistatic effect. 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 the effectiveness. The present invention was devised with attention to these points, and the effect begins to appear within a few hours after molding and kneading, and shows a high level of effect within a day.
The effect lasts from one to two years to several years, which can be considered permanent. That is, the present invention relates to a 1,2-epoxyalkane represented by the general formula (1). (However, R ₁ represents an alkyl group having 10 to 28 carbon atoms) and monoethanolamine, and 70 to 97% by weight of the reaction product obtained by reacting with the alkylolamide represented by general formula (2). (However, R ₂ is an alkyl group or aralkyl group having 8 to 22 carbon atoms, R ₃ is hydrogen, a methyl group,
(CH ₂ CH ₂ O)nH, n represents 1 to 20) 3 to 30% by weight, an antistatic agent composition for synthetic resins. The 1,2-epoxy alkanes used in the present invention have an alkyl group having 10 to 28 carbon atoms in the epoxy ring, and 1,2-epoxy alkanes having these carbon atoms may be used alone or in a mixture of two or more. 1.2
-The reaction product of 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 by heating the above raw materials in a reactor under an inert gas at 110-150°C. The reaction product obtained here generally consists of one active hydrogen in the monoethanolamine molecule,
A compound obtained by the addition reaction of one molecule of 1.2-epoxyalkane (hereinafter referred to as "1-1 adduct") and two molecules of 1.2-epoxyalkane reacting with two active hydrogens in the onoethanolamine molecule. It is a mixture of compounds obtained by reaction (hereinafter referred to as "2-1 adduct"), and the mixing ratio is "1-1 adduct": "2-1 adduct" = 10 by weight. :
0 to 7:3 is good, and as much as possible, "1-1 adduct"
The larger the amount, the higher the effect and is preferable. ``2'' in the mixture
-1 adduct exceeding 30% is less effective and falls outside the practical range. 70 to 97% by weight of the reaction product thus obtained and the alkylolamide 3 represented by the general formula (2). ~30% by weight. In order to obtain a uniform effect, it is preferable to mix the two by melt-mixing the reaction product and the alkylolamide and then producing the product. Alkylolamide of general formula (2) has 8 carbon atoms
-22 saturated fatty acids and at least one of monoethanolamine, diethanolamine, N-methyl-N-hydroxylethylamine, etc. The reaction is carried out by a known reaction method for producing an amide. i.e. 140-210 in the presence of caustic alkali, or sodium methylate, etc.
The reaction proceeds by heating at a temperature of .degree. The progress of the reaction is checked by measuring the amino value. When used in the present invention, it is desirable that the amine value in the alkylolamide be low; if it is high, it will cause coloration after kneading the synthetic resin. The amine value is preferably 20 or less, preferably 10 or less. Saturated fatty acids with 8 to 22 carbon atoms include simple fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid; mixed fatty acids include coconut oil fatty acids, beef tallow fatty acids, and hydrogenated fatty acids of animal and vegetable oils. It will be done. 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. "1-1 adduct" and "2-1 adduct"
The ratio was determined by measuring the total amine value, partial amine value, and tertiary amine value, and using them and 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 carried out as follows.

[Table] (1) Preparation of measurement plate () Polystyrene plate: For high-impact polystyrene (hereinafter referred to as "HI-PS"),
Add 1.5% by weight of the sample (Nos. 1 to 13 in Table 1) and mix uniformly, then use an extrusion molding machine to create antistatic agent-containing pellets. Molded into 3 mm thick plates at ~230°C. () Polypropylene plate: Add 0.5% by weight of the sample (Nos. 1 to 13 in Table 1) to polypropyne (hereinafter referred to as "PP"), use an extrusion molding machine in the same way as polystyrene to obtain pellets, and Transfer molding was performed at ~210°C to obtain a 3 mm thick plate. (2) Measurement of antistatic effect For the measurement plate, 7 days after molding,
The antistatic effect was determined by measuring the half-life (seconds) using a static honest meter (manufactured by Shishido Shokai) under conditions of 20°C and 40% RH. (3) From the measurement results According to the results in Table 1, the shorter the carbon chain length (R ₁ ), the better the effect, and the sample mixing ratio of 100:0, which is the most effective when only the "1-1 adduct" is used. Highly effective;
As the amount of "2-1 adduct" increases, the effect decreases. The mixing ratio of both from the viewpoint of practical antistatic effect is 100:0 to 82:18 when R ₁ is C ₁₀ to _{C 12} or C ₁₄ to ₁₆ , and 7:25 reduces the effect. ing. If R ₁ is C ₁₈ ~ C ₂₈
100:0 to 95:5 is effective at best, 89:
11, the effectiveness is decreasing. Therefore, R ₁ becomes C ₁₂
When viewed from the viewpoint of ~ _C28 , a mixture in which the mixing ratio of "1-1 adduct" to "2-1 adduct" is in the range of 100:0 to 70:30 is practical.

【table】

[Table] Next, the reaction product of general formula (1) and monoethanolamine and the alkylolamide of general formula (2) are mixed at different ratios (weight), and the mixture is kneaded into a synthetic resin to provide antistatic property. was measured, and the results are shown in Table 2 as a measurement example. The alkylolamide used here was lauroyl diethanolamide, and the resin was kneaded using the method described above.
High-density polyethylene (hereinafter referred to as "HD-PE"),
PP and target, immediately after molding, 2 days later, 7 days later 3
The points were measured. 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 2% (No. 2) had poor effects immediately after molding, and 35% (No. 8) also had poor effects immediately after molding. The mixing ratio of alkanolamide is 3
A range of ~30% is a practical effective range. Examples are shown below. General formula (1) used in the examples
and monoethanolamine (Table 1)
Table 3 shows the content and mixing ratio (weight) of the reaction product No.) and the compound of general formula (2). The table below shows the results measured using the plate obtained by kneading.
4. The kneading conditions etc. are as described above.

【table】

【table】

【table】

Claims (1)

[Claims] 1. 1,2-epoxyalkane represented by general formula (1) (wherein R ₁ represents an alkyl group having 10 to 28 carbon atoms) and monoethanolamine (70 to 97% by weight) and an alkylolamide represented by general formula (3) (However, R ₂ is an alkyl group having 8 to 22 carbon atoms. _{R 3}
is hydrogen, methyl group, (CH ₂ CH ₂ O) nH, n is 1 to
20) from 3 to 30% by weight.