JPH0464553B2 - - 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,
Due to its low conductivity, it is difficult to leak, causing various electrostatic 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 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 serious, 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, 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 situation, there have been 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, they are extremely limited each time. 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.)
70 to 97% by weight of the reaction product (A) obtained by reacting with monoethanolamine and an alanine-type amphoteric surfactant represented by general formula (2) [However, R ₂ is an alkyl group having 8 to 28 carbon atoms, an alkenyl group, or a 2-hydroxyalkyl group, M
is H, Na, K, Ca, one type selected from ammonium group of monoethanolamine, ammonium group of diethanolamine, ammonium group of triethanolamine, R ₃ is H, CH ₃ −, −
(CH ₂ CH ₂ O-) _o H (n is 1 to 20), -
CH ₂ CH ₂ COOM (M is the same as above)]
3 to 30% by weight of 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 are used alone or in combination 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 "1-1 adduct": "2-1 adduct" = weight ratio
A ratio of 10:0 to 7:3 is preferable, and the more "1-1 adduct" is used, the more effective it is, and is therefore 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. The mixing ratio of the "1-1 adduct" and "2-1 adduct" is determined by measuring the total amine value, partial amine value, and tertiary amine value, and comparing it with the tertiary amine compound ("2-1 adduct"). Determine from the theoretical molecular weight. The alanine type amphoteric surfactant (hereinafter referred to as "reaction product (B)") was produced as follows. That is, from the reaction of an alkyl or alkenylamine with methyl acrylate, methyl N-alkyl (alkenyl) β-aminopropionate or N
- A method of producing methyl alkyl (alkenyl) β-iminodipropionate and then hydrolyzing it to form it as it is (acid) or into a metal salt or amine salt. In addition, N-hydroxyethyl N-2-hydroxyalkylamine is produced by the reaction of long-chain alkylene oxide and monoethanolamine, which is subjected to an addition reaction with methyl acrylate and then hydrolyzed, and can be used as is (acid) or Examples include a method of forming a metal or amine salt.
Reactions leading to the production of these products are carried out by generally known methods. Examples of the compounds obtained as described above include, but are not limited to, the following examples. C ₁₂ H ₂₅ NHCH ₂ CH ₂ COONa …(a) (C ₁₂ H ₂₅ NHCH ₂ CH ₂ COO) ₂ Ca …(b) C ₁₂ H ₂₅ NHCH ₂ COOH・H ₂ NCH ₂ OH …(c) C ₁₈ H ₃₇ N(CH ₂ CH ₂ COONa) ₂ …(d) Reaction product (A) 70-97 obtained as above
% by weight and 3 to 30% by weight of the reaction product (B), but in order to obtain a constant effect, it is preferable to dissolve both reaction products 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】

[Table] Next, the reaction product (A) in Table 1 and the reaction product (B) in Table 2 were mixed at different ratios (weight), kneaded into a synthetic resin, and the antistatic properties were measured. Table 3 shows the results.
Shown below. The test method is as follows. (1) Preparation of measurement plate () Polystyrene plate (hereinafter referred to as “HI-PS”)
): Add 1.5% by weight of the sample (Nos. 1 to 18 in Table 3) to impact-resistant polystyrene,
After uniformly mixing, an antistatic agent-containing pellet was prepared using an extrusion molding machine, which was then molded into a 3 mm thick plate using an injection molding machine at 220 to 230°C. () ABS plate (hereinafter referred to as (ABS)):
An ABS plate was obtained by processing in the same manner as the ABS resin polystyrene plate. () High-density polyethylene plate (hereinafter referred to as "HD-PE"): 0.5% by weight sample of high-density polyethylene resin (Nos. 1 to 18 in Table 3)
After uniformly mixing, pellets were obtained through extrusion molding, and the pellets were injection molded at 200 to 210°C to obtain a plate with a thickness of 3 mm. () 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 properties For the measurement plate, the half-life (seconds) after static electricity was measured immediately after molding, 2 days after molding, 7 days after molding, and 2 months after molding using a static honest meter (manufactured by Shishido Shokai). The antistatic properties were measured. (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, () the mixing ratio of reaction product (A): reaction product (B) is
Those with a ratio of 97:3 to 70:30 exhibited excellent antistatic properties from immediately after molding to two months later. () 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.

【table】

【table】

【table】

【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.)
70 to 97% by weight of the reaction product (A) obtained by reacting with monoethanolamine and an alanine-type amphoteric surfactant represented by general formula (2) [However, R ₂ is an alkyl group having 8 to 28 carbon atoms, an alkenyl group, or a 2-hydroxyalkyl group, M
is H, Na, K, Ca, one type selected from ammonium group of monoethanolamine, ammonium group of diethanolamine, ammonium group of triethanolamine, R ₃ is H, CH ₃ −, −
(CH ₂ CH ₂ O-) _o H (n is 1 to 20), -
CH ₂ CH ₂ COOM (M is the same as above)]
An antistatic agent composition comprising 3 to 30% by weight.