JPS63339A - Antistatic resin composition - Google Patents

Abstract

PURPOSE:To provide the title compsn. which has persistent antistatic properties and excellent transparency and gives molded products having excellent appearances by blending a specified thermoplastic resin with an N,N- bis-(hydroxyethyl)alkylamine. CONSTITUTION:50-97wt% arom. vinyl compd. (a) (e.g., styrene) is polymerized with 3-50wt% vinyl cyanide compd. (b) (e.g., acrylonitrile) and optionally, not more than 30wt% other copolymerizable vinyl monomer and (non)-diene rubber (c) to obtain a thermoplastic resin (A). 100pts.wt. component A is blended with 0.05-10pts.wt. pref. 0.2-5pts.wt. N,N-bis-(hydroxyethyl)alkylamine (B) having 8-10C alkyl groups composed of at least 40wt% 12C alkyl group.

Description

[Detailed Description of the Invention] Remark 3. Detailed Description of the Invention Background Art and Problems The present invention relates to a thermoplastic resin comprising an aromatic vinyl-vinyl cyanide copolymer (hereinafter referred to as a styrene-acrylonitrile copolymer). (Regarding a 100% fire-resistant resin composition.)

In general, synthetic resin products tend to accumulate static electricity due to friction, etc., and are known to cause various static electricity problems such as adsorption of dust due to charging, shock to the human body due to discharge, and spark generation.

So IF is a way to prevent static electricity? There are methods such as applying the antistatic agent to the molded product or mechanically kneading it into the raw resin during the molding process, but the method of applying it to the surface is quick-acting, but the antistatic agent is removed by friction, washing, etc. falling off,
Since it is difficult to maintain the antistatic effect for a long period of time, the common method of maintaining the antistatic effect for a long period of time is to knead the antistatic agent into the resin itself. The speed at which JiF Therefore, antistatic agents must be selected with these considerations in mind.

It is well known that thermoplastic resins made of styrene-acrylonitrile copolymers have excellent appearance such as transparency, translucence, and surface gloss, and are used in pottery, lighting equipment, automobile parts, etc.
Used for signboards, displays, etc. Antistatic properties are particularly necessary in such applications. When imparting antistatic ability to a thermoplastic resin made of a styrene-acrylonitrile copolymer, among the commonly known antistatic effects, cationic and zwitterionic systems have excellent antistatic effects, but It has the disadvantage of poor stability, and if mixed into a molded product, it will stain and significantly reduce the commercial value. Anionic resins have poor compatibility with resins and are unsuitable for applications requiring transparency. Nonionic types have relatively good thermal stability and good compatibility with resins. However, if we take glycerin monostearate, which is a typical example of a nonionic type known so far, it has a considerable antistatic effect in the adult form at the beginning, but the antistatic effect gradually decreases over time. In addition, components that bleed out onto the resin surface become white powder (whitening phenomenon), which is undesirable. It has been difficult to provide long-lasting good antistatic properties.

Therefore, the present invention provides an antistatic resin composition containing a thermoplastic resin made of a styrene-acrylonitrile copolymer, which has excellent antistatic ability without impairing transparency or transparency or surface appearance. The challenge is to provide.

The above-mentioned problems are as follows: 5. According to the present invention, for 100 parts by weight of a thermoplastic resin made of a styrene-acrylonitrile copolymer,
N,N-bis(hydroxyethyl)alkylamine 0.
The problem is solved by providing an antistatic resin composition characterized in that it contains 0.05 to 10 parts by weight.

Description of specific examples The thermoplastic resins targeted by the present invention can be classified into the following three types: (a) Copolymers of aromatic vinyl compounds and vinyl cyanide compounds (b) Monomers mentioned above Copolymer of the mixture and other copolymerizable vinyl monomers (c) Polymer blend containing the above (a) and (b) In addition, during the production of the above (a) and (b), diene-based Got1 and /Or a non-diene rubber may be present. However, in order to obtain a resin with excellent transparency, it is preferable to use a rubber having a refractive index close to that of the copolymer or a rubber having a small particle size.

Especially in order to obtain a resin composition with excellent transparency.

Preferably, no rubber is present.

As the aromatic vinyl monomer in the present invention, styrene is generally used, but if necessary, α-methylstyrene,
Alkyl group-substituted styrene such as P-methylstyrene and 3,5-dimethylstyrene.

Halogenated styrenes such as α-bromstyrene and P-bromstyrene can be used alone or as a mixture.

Acrylonitrile is generally used as vinyl cyanide f1, but methacriconyl-1-lyl and the like can be used alone or as a mixture.

Other copolymerizable vinyl compounds include methyl methacrylate, ethyl methacrylate, and methyl acrylate.
1-, (meth)acrylic esters such as ethyl acrylate, unsaturated acids such as acrylic acid and methacrylic acid, unsaturated acid anhydrides such as maleic anhydride and itacone anhydride, N
-Methylmaleimide, N-phenylmaleimide, N-0
-Maleimide compounds such as chlorphenylmaleimide and N-cyclohexylmaleimide.

The content of the aromatic vinyl compound in the styrene-acrylonitrile copolymer, which is the thermoplastic resin used in the present invention, is 50 to 97% by weight, or 55 to 90% by weight. If it is less than 50% by weight, the heat resistance to discoloration will be poor, and if it is more than 90% by weight, the heat resistance, mechanical properties, etc. will be poor. The proportion of vinyl cyanide monomer in the copolymer is 3 to 50% by weight, preferably 10 to 45% by weight. If the vinyl cyanide content is less than 3% by weight, the chemical resistance will be poor. If the vinyl cyanide content exceeds 50% by weight, the resulting copolymer has a poor hue and is not often used in fields where transparency is required.

The content of other vinyl compounds is 30% by weight or less, preferably 20% by weight or less.

The alkyl in the N,N-bis(hydroxyethyl)alkylamine is preferably an alkyl having 8 to 18 carbon atoms. Within this range, even better effects can be obtained. More preferably, the alkyl of the N,N-bis(hydroxyethyl)alkylamine is an alkyl having 8 to 18 carbon atoms, and the alkyl having 12 carbon atoms accounts for 35% by weight or more, more preferably 40% by weight or more of the total alkyl. be.

The blending amount of N,N-bis(hydroxyethyl)alkylamine is 0.05 to 1 per 100 parts by weight of the thermoplastic resin.
0 parts by weight, preferably 0.2 to 5 parts by weight. If the amount is too small, there will be no effect; on the other hand, if the amount is too large, the physical properties of the molded product will deteriorate.

N,N-bis(hydroxyethyl)alkylamine is
It can be obtained by adding ethylene oxide to the corresponding alkylamine, such as laurylamine or coconut alkylamine, without a catalyst, but by-products having the formula % can be formed. Preferably, this by-product is 25% or less.

The band'It-preventing resin composition of the present invention is obtained by kneading the thermoplastic resin 11M and N,N-bis(hydroxyethyl)alkylamine in the above-mentioned mixing ratio in a conventional manner.

That is, methods include a method of blending the antistatic agent into a polymer solution of a polymerization system in which a thermoplastic resin is produced, a method of blending an antistatic agent into powder or pellets of a thermoplastic resin, and melt-mixing if necessary.

The 41F antistatic resin composition of the present invention can be applied to automobile parts, electrical parts, household goods, etc. by injection molding, extrusion molding, vacuum molding, irregular molding, foam molding, etc.

It can be molded into various industrial products. At that time, usual additives such as antioxidant 1L agent, ultraviolet absorber, lubricant,
51! Fuel, other antistatic agents, foaming agents, glass fibers, etc. can be added.

Next, the present invention will be explained in more detail with reference to Examples, but these are merely illustrative and do not limit the scope of the present invention.

In addition, in each side below, the part and % are respectively, ! 1!
Parts and weight % are shown.

Example 1 100 parts by weight of styrene-acrylonitrile copolymer resin (Japan Synthetic Rubber Co., Ltd. 11aJsRAs230: Acrylonitrile content 24% by weight) and N,N- in which the proportion of alkyl groups having 12 carbon atoms in the total alkyl groups is 40% Screw(
hydroxyethyl)alkylamine (hereinafter referred to as H)t E
0.3 parts of A) were blended in a Henschel mixer, then pelletized in an extruder at 230°C, and the resulting pellets were molded into a 2.4 nn thick test piece using an injection molding machine at 230°C. did. What are the test conditions?

The antistatic performance was evaluated by the degree of dust adhesion, and the transparency was evaluated by the total light transmittance.

The test method is shown below.

The evaluation results are shown in the table.

[1] Dust adhesion test method The test piece was left indoors, and the state of dust adhesion on the plate surface was visually judged. The evaluation criteria are shown in the table below.

The test was carried out twice, one day and seven days after the test piece was prepared.

[2] Transparency Test Method The test after 1 day and 7 days of molding was evaluated based on the rate of change in total light transmittance with reference to that without the addition of IW antistatic agent.

However, Tt(0)...Test piece without antistatic agent added (
1)...The criteria for evaluating test pieces with the addition of various antistatic agents was the magnitude of the rate of change as shown in the following table.

Example 2 In Example 1, N,N-bis(hydroxyethyl)alkylamine in which the component having 12 carbon atoms accounted for 40% of the total alkyl groups was used as an antistatic agent. .3 parts is N, and the proportion of the C12 component of N-bis(hydroxyethyl)alkylamine in the total alkyl groups is 60%.

The same test as in Example 1 was conducted except that 0.3 part of N-bis(hydroxyethyl)alkylamine was used, and the results are shown in the table.

Example 3 In Example 1, N,N-bis(hydroxyethyl)alkyl was used as an antistatic agent in which the component having 12 carbon atoms of N,N-bis(hydroxyethyl)alkylamine accounted for 40% of the total alkyl groups. 0.3 part of amine, N
, the proportion of the C 12 component of N-bis(hydroxyethyl)alkylamine in the total alkyl group is 90
The same test as in Example 1 was conducted except that 0.3 part of N,N-bis(hydroxyethyl)alkylamine was used, and the results are shown in the table.

Comparative Example 1 1B: A test similar to Example 1 was conducted except that no +r6 inhibitor was added. The results are shown in the table.

Example 4 JSRAS250 manufactured by Japan Synthetic Rubber Co., Ltd. (containing acrylonitrile: h
The same procedure as in Example 1 was carried out except that t29% by weight) was used. The results are shown in the table.

Comparative Example 2 The same test as in Example 1 was conducted, except that 0.3 parts of HEEAO as the antistatic agent in Example 1 was replaced with 0.3 parts of polyoxyethylene alkylamine, which has been commonly used as an antistatic agent. Shown in the table.

Comparative Examples 3-4 HE E AO03 as an antistatic agent in Example 1
In Comparative Example 3, stearic acid monoglyceride, which has conventionally been generally used as an antistatic agent, was 0%
．． 3 parts, Comparative Example 4 contains stearic acid monoglyceride ester + pentaerythritore stearate 0°3, which has been conventionally generally used as an antistatic agent.
The same test as in Example 1 was conducted except that the parts were changed to
The results are shown in the table.

Comparative Example 5 In Example 1, HEEAO,
The same test as in Example 1 was conducted except that 0.3 parts of glycerin fatty acid ester was used instead of 3 parts, and the results are shown in the table.

Effects of the Invention The present invention is an excellent IF antistatic resin composition made of a styrene-acrylonitrile copolymer resin.

Styrene-acrylonitrile copolymer resins give molded products a beautiful appearance and have excellent transparency, so they are used in parts and housings that come into contact with the public eye. When static electricity is generated in a molded product, there are problems such as dust adhering to the surface and static electricity shock, which is a major hindrance to applications that take advantage of the unbalanced + quality.

Generally, as an antistatic agent, a band '1π as mentioned in the comparative example is used.
Antistatic agents are used, but as shown in Comparative Examples 2 to 5, when improving 41F antistatic properties using these 4p antistatic agents, the antistatic effect is not sustainable, and if molded products are left for a long time, dust will accumulate. and significantly deteriorate the appearance. Furthermore, since the resin becomes cloudy, its transparency is significantly reduced, and it cannot be used in applications that require transparency. However, since the resin composition using the antistatic agent of the present invention maintains antistatic properties for a long period of time, dust does not adhere to it for a long period of time, and the resin composition maintains a beautiful state. Furthermore, it is suitable for transparent applications because it does not reduce transparency. The present invention is extremely valuable because it can be used in applications that fully utilize the characteristics of styrene-acrylonitrile copolymer resins due to its excellent antistatic effect and excellent transparency and appearance. be.

Claims (4)

[Claims] (1) Thermoplastic resin 1 obtained by polymerizing monomers containing aromatic vinyl compounds and vinyl cyanide compounds as main components
00 parts by weight, N,N-bis(hydroxyethyl)
An antistatic resin composition comprising 0.05 to 10 parts by weight of an alkylamine. (2) Charging according to claim (1), wherein the thermoplastic resin is a copolymer obtained by copolymerizing 50 to 97% by weight of an aromatic vinyl compound and 3 to 50% by weight of a vinyl cyanide compound. Preventive resin composition. (3) The antistatic resin composition according to claim (1), wherein the alkyl of the N,N-bis(hydroxyethyl)alkylamine is an alkyl having 8 to 18 carbon atoms. (4) The antistatic resin composition according to claim (3), wherein the alkyl group having 12 carbon atoms accounts for at least 40% by weight of all the alkyl groups having 8 to 18 carbon atoms.