JPH07774B2 - Antistatic agent - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to an antistatic agent. More specifically, it relates to an antistatic agent for kneading into an aromatic group-containing thermoplastic resin such as polystyrene or ABS resin.

[0002]

2. Description of the Related Art As an antistatic agent for resins, a polyether ester amide obtained by subjecting a carboxy-terminated amide prepolymer and a polyoxyalkylene glycol to a polycondensation reaction in a molten state has been heretofore known (JP-A-60-2343).
5 and JP-A-60-170646).

[0003]

However, in this polyether ester amide, the antistatic performance is not sufficient unless it is kneaded into the aromatic group-containing thermoplastic resin by at least 15 wt%, and when it is kneaded by 15 wt%, the resin physical properties become poor. Inferiority, poor compatibility with the aromatic group-containing thermoplastic resin, poor heat resistance, etc. are not always satisfactory.

[0004]

Means for Solving the Problems The present inventors have arrived at the present invention as a result of studying a polyetheresteramide having a sufficient antistatic property.

That is, according to the present invention, a polyamide (A) derived from the following compound (a) and an alkali metal salt of 3-sulfoisophthalic acid (b) and having a carboxyl group at both ends, and an alkylene oxide adduct of bisphenols ( An antistatic agent for a thermoplastic resin containing an aromatic group, which comprises a polyether ester amide resin derived from B). Compound (a): (a1) aminocarboxylic acid having 6 or more carbon atoms, (a2) lactam having 6 or more carbon atoms, and (a3) aliphatic diamine having two primary amino groups having 6 or more carbon atoms and 6 carbon atoms One or more selected from the above salts with an aliphatic dicarboxylic acid. Hereinafter, the present invention will be specifically described.

In the present invention, (a1) an aminocarboxylic acid having 6 or more carbon atoms in the compound (a) is ω
-Aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. Examples of the lactam having 6 or more carbon atoms (a2) include ε-caprolactam, enanthlactam, capryllactam, laurolactam and the like. (A
3) Hexamethylenediamine-adipate, hexamethylenediamine-sebacate or a salt of an aliphatic diamine having two primary amino groups having 6 or more carbon atoms and an aliphatic dicarboxylic acid having 6 or more carbon atoms Examples include isophthalate. Two or more of the above examples (a) may be used in combination. Among those exemplified as the compound (a), preferable one is ε-caprolactam, 12
-Aminododecanoic acid and hexamethylenediamine-adipate, particularly preferred is ε-caprolactam.

In the present invention, specific examples of the alkali metal salt of 3-sulfoisophthalic acid (b) include sodium 3-sulfoisophthalate and potassium 3-sulfoisophthalate. Among these, preferred ones are 3-
It is sodium sulfoisophthalate.

In the present invention, bisphenols constituting the alkylene oxide adduct (B) of bisphenols include bisphenol A, bisphenol S, brominated bisphenol A, 4,4-bis (hydroxyphenyl) sulfide and bis (4-). Hydroxyphenyl) sulfoxide, bis (4-hydroxyphenyl) methane,
Bis (4-hydroxyphenyl) ether, bis (4-
(Hydroxyphenyl) amine and the like are preferable, and bisphenol A is preferable. Examples of the alkylene oxide constituting (B) include ethylene oxide (EO) and / or propylene oxide (PO). When EO and PO are used in combination, they may be random addition or block addition. Preferred is EO. The number of moles of alkylene oxide added is usually 2 to 40, preferably 10 to 30. The number average molecular weight of (B) is usually 300.
~ 3000, preferably 700-2000. Number average molecular weight is 3
If it exceeds 000, the antistatic property is insufficient, and if it is less than 300, the impact resistance becomes poor when kneaded into the aromatic group-containing thermoplastic resin, which is not preferable. The compound (a) is used in the range of 5 to 90% by weight as a constitutional unit of the polyetheresteramide resin, and if less than 5% by weight, impact resistance is poor when kneaded into the aromatic group-containing thermoplastic resin, When it is 90% by weight or more, the resulting resin is inferior in antistatic property, which is not preferable. The alkali metal salt of 3-isophthalic acid (b) is 0.5 as a constitutional unit of the polyether ester amide resin.
It is used in the range of up to 20% by weight, and if 20% by weight or more, the impact resistance is poor when kneaded into an aromatic group-containing thermoplastic resin, and if less than 0.5% by weight, the antistatic property of the obtained resin is poor. Not preferable.

The method for producing the polyether ester amide resin may be any of the following production methods and production methods. Production method: (a) and (b) are reacted in a molten state (A)
Is added, and (B) is added to this, and the polymerization reaction of (A) and (B) is performed under high temperature vacuum. Production method: (a) and (b) and (B) are simultaneously charged into a reaction tank, and pressure reaction is performed at high temperature in the presence or absence of water to produce (A) as an intermediate, and then A method of promoting the polymerization reaction of (A) and (B) under normal pressure or reduced pressure.

There is no limitation on the catalyst used in the polymerization reaction of (A) and (B). For example, antimony-based catalysts such as antimony trioxide, tin-based catalysts such as monobutyltin oxide, and titanium such as tetrabutyl titanate. Examples thereof include system catalysts, zirconium catalysts such as tetrabutyl zirconate, metal acetate catalysts such as zinc acetate, and the like.

Aromatic group-containing thermoplastic resins which are effective by kneading the antistatic agent of the present invention include polystyrene, rubber-reinforced styrene, poly (styrene / acrylonitrile) copolymer, styrene / acrylonitrile /
Examples thereof include butadiene copolymer (ABS resin).

Various methods are available for kneading and using the antistatic agent of the present invention in the aromatic group-containing thermoplastic resin. For example, a required amount of the antistatic agent of the present invention is added to a powder of a polymer substance, and the mixture is uniformly mixed to prepare pellets. Alternatively, a solution obtained by previously dissolving the antistatic agent of the present invention in a solvent is used. It is also possible to add the required amount to the powder or pellets of the polymer, then mix uniformly, remove the solvent, and then perform injection molding. It can also be added at the time of polymerizing the monomer in the production of the polymer substance.

[0013]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. Parts in the examples are parts by weight.

Example 1 A stainless separable flask having an internal volume of 3 L was charged with ε-.
113 parts of caprolactam, 27 parts of sodium 3-sulfoisophthalate, 0.3 parts of "Irganox 1098" (antioxidant manufactured by Ciba-Geigy) and 30 parts of water were added, and heated at 220 ° C for 60 minutes in an inert atmosphere. After stirring to obtain a transparent homogeneous solution, 105 parts of a bisphenol A ethylene oxide adduct having a number average molecular weight of 1000 and 0.3 part of tetrabutyl titanate are added, and the temperature is 260 ° C.
Polymerization was conducted for 8 hours under the condition of mmHg or less to obtain a viscous and milky white polymer. The polymer was discharged onto a cooling belt in a gut shape and pelletized to prepare a pellet-shaped polyetheresteramide resin [1]. The solution viscosity of this polyetheresteramide resin [1] is η _sp /C=1.6
It was 0 (m-cresol, 25 ° C., C = 0.8 wt%).

Example 2 A stainless steel separable flask having an internal volume of 3 L was charged with ε-.
Caprolactam 113 parts, bisphenol A ethylene oxide adduct having a number average molecular weight of 1000 105 parts, sodium 5-sulfoisophthalate 27 parts, "Irganox 1098" 0.3 parts, tetrabutyl titanate 0.3 parts and water 30 parts I put them in at the same time. The reaction mixture was placed under an inert atmosphere, heated and stirred at 220 ° C. for 60 minutes to obtain a transparent homogeneous solution, and then at 260 ° C. and 2 mmHg or less.
Polymerization was carried out for a time to obtain a viscous, milky white polymer. A pellet-shaped polyetheresteramide resin [2] was prepared by discharging the polymer in a gut shape onto a cooling belt and pelletizing the polymer. The solution viscosity of this polyether ester amide resin [2] was η _sp /C=1.45 (m-cresol, 25 ° C., C = 0.8 wt%).

COMPARATIVE EXAMPLE 1 Polyethylene glycol 1 having a number average molecular weight of 1,000 instead of 105 parts of bisphenol A ethylene oxide adduct.
A polyetheresteramide resin [3] was prepared in the same manner as in Example 1 except that 05 parts were used. The solution viscosity of this polyetheresteramide resin [3] is η _sp / C =
It was 1.50 (m-cresol, 25 ° C., C = 0.8 wt%).

Comparative Example 2 570 parts of caprolactam, 1000 parts of polyethylene glycol having a number average molecular weight of 1000, 146 parts of adipic acid "Irganox 1098", and 0.3 parts of tetrabutyl titanium were placed in a separable flask made of stainless steel having an internal capacity of 3 L. 0.3 part of acid salt and 36 parts of water were added. The reaction mixture was placed under an inert atmosphere, heated and stirred at 220 ° C. for 60 minutes to form a transparent homogeneous solution, and then polymerized at 260 ° C. for 2 hours under a condition of 2 mmHg or less to obtain a viscous and transparent polymer. The polymer was discharged onto a cooling belt in a gut shape and pelletized to prepare a pelletized polyetheresteramide resin [4]. The solution viscosity of this polyetheresteramide resin [4] was η _sp /C=1.80 (m-cresol, 25 ° C., C = 0.8 wt%).

Examples 3 to 4, Comparative Examples 3 to 4 Injection molding using a polyetheresteramide resin [1] to [4] (cylinder temperature 170 ° C., mold temperature 40)
The test results are shown in Table 1 below. The surface resistivity is 2 mm thick.
Was measured in a 50% RH atmosphere at 25 ° C. for 12 hours. Polyether ester amide resin [1] to [4] is added to ABS resin at 5 wt.
%, 10 wt% and 15 wt% were kneaded and injection molded (cylinder temperature 240 ° C., mold temperature 40 ° C.) to obtain each test piece, and the surface resistivity and Izod impact strength were measured and the results are shown in Table 2 below. Each is shown in Table 3. The surface resistance value is 50% when it is molded into a disc with a thickness of 2 mm.
The humidity was measured for 12 hours at RH and 25 ° C. The Izod impact strength was measured based on the test method ASTM D256. The results are shown in Table 3 below.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

[0022]

The antistatic agent of the present invention exerts an excellent permanent antistatic ability by kneading in a small amount as compared with the prior art, and therefore it is possible to suppress deterioration of physical properties inherent to the resin. It also has excellent compatibility and heat resistance.

Claims (3)

[Claims] 1. A polyamide (A) derived from the following compound (a) and an alkali metal salt of 3-sulfoisophthalic acid (b) and having carboxyl groups at both ends, and an alkylene oxide adduct (B) of bisphenols. An antistatic agent for kneading an aromatic group-containing thermoplastic resin, characterized by comprising a polyether ester amide resin derived from. Compound (a): (a1) aminocarboxylic acid having 6 or more carbon atoms, (a2) lactam having 6 or more carbon atoms, and (a3) aliphatic diamine having two primary amino groups having 6 or more carbon atoms and 6 carbon atoms One or more selected from the above salts with an aliphatic dicarboxylic acid. 2. The antistatic agent according to claim 1, wherein the content of the residue (b) in the polyetheresteramide resin is 0.5 to 20% by weight. 3. The antistatic agent according to claim 1, wherein the polyether ester amide resin is a resin obtained by reacting (A) and (B) at a weight ratio of 30:70 to 70:30.