JPH0464356B2 - - 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 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, , even during the short time between molding and next processing.
There is a growing demand for antistatic properties. 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,
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. As an antistatic agent for polyolefins, β obtained by the reaction of olefin oxide and alkanolamine
-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. This is an antistatic agent composition for synthetic resins comprising 3 to 30% by weight of a reaction product (B) obtained by reacting a fatty acid having an alkenyl group with aminoethylethanolamine. 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. The reaction product of 1.2-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 is generally 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 a "1-1 adduct").
) and a compound obtained by reacting two molecules of 1,2-epoxyalkane with two active hydrogen atoms in a monoethanolamine molecule (hereinafter referred to as "2-1 adduct"), The mixing ratio is "1-adduct": "2-1 adduct" = 10:
0 to 7:3 is good, and as much as possible, "1-1 adduct"
It is preferable that there is a large amount of , since the effect is high. In the mixture “2-
1 adduct exceeding 30% is less effective and falls outside the practical range. The mixing ratio of "1-1 adduct" and "2-1 adduct" is determined by measuring the total amino value, partial amino value, and tertiary amine value, and then comparing it with the tertiary amine compound ("2-1 adduct"). Determine from the theoretical molecular weight. 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, and the reaction product is an alkylimidazoline represented by the general formula (2), Compound represented by general formula (3) R ₂ −CONHCH ₂ CH ₂ NHCH ₂ CH ₂ OH ...(3) The ratio of the mixture is determined by the 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, and behenic acid, which can be used alone or in combination. It will be done.
Examples of industrially obtained mixed fatty acids include coconut oil fatty acids, beef fatty acids, and other animal and vegetable oil fatty acids. Reaction product (A) 70-97 obtained as above
% by weight, 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 3-
30% by weight, but in order to obtain a consistent effect, it is preferable to dissolve both reactants and mix them uniformly before preparing the product. The present invention will be explained below using comparative examples and examples.
The compositions of the reaction product (A) and reaction product (B) used in this are shown in Tables 1 and 2.

【table】

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[Table] Next, the reaction product (A) in Table 1 and the reaction product (B) in Table 2 were mixed at different ratios (weight), and the antistatic properties kneaded into the synthetic resin were measured. Table 3 shows the results.
Shown below. The test method is as follows. (1) Preparation of measurement plate (i) Polystyrene plate (hereinafter referred to as “HI-PS”)
): 1.5 for impact-resistant polystyrene
% by weight of the samples (Nos. 1 to 18 in Table 3) were added and mixed uniformly, an extrusion molding machine was used to create antistatic agent-containing pellets, and then an injection molding machine was used to form pellets containing 220 to It was molded into a 3 mm thick plate at 230°C. (ii) ABS plate (hereinafter referred to as "ABS"):
ABS resin is treated in the same way as polystyrene.
An ABS plate was obtained. (iii) High-density polyethylene plate (hereinafter “HD
-PE”): high-density polyethylene resin
Add 0.5% by weight of the sample (Nos. 1 to 18 in Table 3), mix uniformly, pass through an extruder to obtain a pellet, and injection mold it at 200 to 210°C to obtain a 3 mm thick plate. Ta. (iv) Polypropylene plate (hereinafter referred to as "PP"): A polypropylene plate was obtained by treating polypropylene resin in the same manner as a polyethylene plate. (2) Measurement of antistatic effect For the measurement plate, measure the half-life (in seconds) after static electricity immediately after molding, 2 days after molding, 7 days after molding, and 2 months after molding using a static electricity meter (manufactured by Shishido Shokai). was used to measure the antistatic effect. (3) Measurement results Measurement Nos. 1 to 2, 8 to 11, and 17 to 18 in Table 3 are outside the scope of the present invention, while measurement Nos. 3 to 7 and 12 to 16 are within the scope of the present invention. It is something. From those measurement results, (i) the mixing ratio of reaction product (A): reaction product (B) is 97:
Those with a ratio of 3 to 70:30 exhibited excellent antistatic properties from immediately after molding to the second trial. (ii) A mixture of reaction product (A) and reaction product (B) showed better antistatic properties immediately after molding than each of them alone. Table 4 below shows the measurement results according to the examples. The reaction product (A) in Table 1 and the reaction product in Table 2 were added to the sample.
Using (B), the mixing ratio (weight) is (A):(B)=90:
The measurement plate was prepared and the antistatic property was measured using the method described above.

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【table】

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【table】

Claims (1)

[Claims] 1. 1,2-Epoxyalkane represented by general formula (1) (However, R ₁ represents an alkyl group having 10 to 28 carbon atoms) and monoethanolamine. An antistatic agent composition comprising 3 to 30% by weight of a reaction product (B) obtained by reacting a fatty acid having an alkenyl group with aminoethylethanolamine.