JPH11236476A - Antistatic styrene-based resin composition and its molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an antistatic styrene-based resin composition excellent in transparency and useful as a packaging material, etc., for electronic parts by making the composition include a styrene-based resin, a specific amine-based compound and a specific quaternary ammonium salt of an alkylbenzenesulfonic acid in a specific proportion therein. SOLUTION: This composition is obtained by adding (A) one or more kinds selected from among three kinds of amine-based compound represented by formulae I to III (R is an 8-15C alkyl) and having hydroxyethyl groups and (B) 0.4-4.0 pts.wt. quaternary ammonium salt of an alkylbenzenesulfonic acid represented by formula IV [R1 is an 8-22C alkyl; R2 to R4 are each a 1-4C (hydroxy)alkyl; R5 is a 1-18C alkyl] to 100 pts.wt. styrene-based resin. The amount of the added component B is 5-70 wt.% based on the total amount of the components A and B. Furthermore, the styrene-based resin is preferably composed of a resin phase and a dispersed phase and the resin phase is preferably a resin composed of 30-70 wt.% styrene-based monomer and 70-30 wt.% (meth)alcylic ester monomer and preferably prepared by the graft copolymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a kneaded styrene resin composition having excellent antistatic performance and transparency,
Also, the present invention relates to a useful material used for storing and transporting electronic parts such as a magazine, a carrier tape or a tray.

[0002]

2. Description of the Related Art In recent years, various electronic components including semiconductors have been manufactured, and when these electronic components are stored and transported, packaging forms such as magazines, carrier tapes or trays have been adopted. Many of the electronic components housed in this way need to be able to be visually confirmed and distinguished from the outside of the package, such as eyes or a camera, and in order to satisfy those purposes, hard vinyl chloride resin, Transparent resins such as polycarbonate have been used. In addition, it is preferable that most of the electronic components avoid contact with static electricity caused by the molded package. In particular, it is considered that a countermeasure against static electricity is indispensable for semiconductor components.
It is preferable that static electricity is not generated even in electronic components other than semiconductor components in order to prevent dust from adhering or to avoid problems due to static electricity generated when products are taken out. For this reason, most of the molded articles for packaging electronic parts that do not like static electricity are subjected to antistatic and conductive treatments according to the purpose. Among them, antistatic is generally 10 ^{10 in} surface resistance.
A performance of Ω or less is required, and most of the methods by applying an antistatic liquid are currently used to effectively provide the performance.

However, this coating method has many disadvantages, such as an increase in the number of coating steps and an increase in coating cost. Therefore, there is a strong demand for kneading-type antistatic devices. However, in spite of such market needs, the method of kneading the antistatic agent has many problems such as a decrease in transparency or occurrence of poor appearance due to bleeding of the antistatic agent. 10 ¹⁰ Ω or less) could not be satisfied.

[0004] On the other hand, environmental problems such as generation of acid gas or dioxin at the time of disposal and incineration of packaging materials,
There is a growing demand for alternatives from PVC to other materials. Also in the field of electronic component packaging materials, transparent styrene-based resins that are low in cost and have excellent moldability have been used. However, it has been considered that a styrene resin has a high glass transition point, so that the kneaded antistatic agent does not easily bleed, or it is generally difficult to obtain high-performance antistatic by kneading. Under such circumstances, the current situation is that the conventional coating type is the mainstream for preventing static charge of the styrenic resin molded product in the electronic component packaging material.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a kneaded styrenic resin composition which overcomes the problems of the prior art and has excellent transparency and excellent antistatic performance. It is in.

[0006]

Means for Solving the Problems The present inventors have added a styrene resin obtained by adding a specific amine compound having a hydroxyethyl group and a quaternary ammonium salt of alkylbenzenesulfonic acid to a styrene resin at a specific ratio. The present inventors have found that the resin composition is transparent, has excellent antistatic properties, and is particularly useful for packaging electronic parts, and has completed the present invention.

That is, the present invention relates to a styrene resin 10
0 or more parts by weight of at least one selected from three kinds of (A) amine compounds represented by the following general formulas (1), (2) and (3) having a hydroxyethyl group, and the following general formula (4)
Wherein (B) a quaternary ammonium salt of alkylbenzenesulfonic acid represented by the formula (1) is added in an amount of 0.4 to 4.0 parts by weight, and the proportion of (B) added is the sum of (A) and (B) A styrene-based resin composition having an antistatic property of from 5 to 70% by weight of the amount thereof, and a molded article thereof.

[0008]

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[0009]

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[0010]

Embedded image (In the above formula, R is an alkyl group having 8 to 15 carbon atoms)

[0011]

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(R ₁ is an alkyl group having 8 to 22 carbon atoms;
₂ , R ₃ and R ₄ are an alkyl or hydroxyalkyl group having 1 to ₄ carbon atoms, and R ₅ is an alkyl group having 1 to 18 carbon atoms) Hereinafter, the details of the present invention will be described. The styrene-based resin used in the present invention is a blended resin-type styrene-based resin composition mainly composed of a block copolymer resin of a styrene-based resin containing no rubber-like elastic material, a vinyl aromatic hydrocarbon and a conjugated diene ( Hereinafter, styrene resin-1);
Styrene containing rubber-like elastic material as dispersed particles-(meth)
There are two types of graft copolymer type styrene resin compositions (hereinafter referred to as styrene resin-2), which are acrylic ester copolymer compositions.

The styrene-based resin-1 contains (a) polystyrene and / or (a ') styrene- (meth) acrylate copolymer in a total amount of 20 to 70% by weight, and (b) A) 80 to 30% by weight of a block copolymer resin of a vinyl aromatic hydrocarbon and a conjugated diene having a vinyl aromatic hydrocarbon content of 65 to 85% by weight, and (c) a vinyl aromatic hydrocarbon content of 20 to 85% by weight.
There is a blend resin of 50% by weight of a block copolymer elastomer of a vinyl aromatic hydrocarbon and a conjugated diene with 0 to 10% by weight.

In addition to (a) and / or (a '), (b) and (c) as a mixed component constituting the styrenic resin-1, a general (d) impact-resistant polystyrene may be impaired if necessary. It can be added in a range that does not exist. The styrene-based resin 2 contains a rubber-like elastic body as dispersed particles, and the resin phase (mother phase) is (a) a styrene monomer 30 to
A transparent styrene- (meth) acrylate-based copolymer resin composition obtained by graft copolymerization comprising 70% by weight and (b) (meth) acrylate monomer 70 to 30% by weight is exemplified. . The average particle diameter of the rubber particles of the dispersed phase is 0.3 to 1.5 μm,
Those containing 20% by weight are preferred, and more preferably 8% by weight.
It is a transparent styrene- (meth) acrylate-based copolymer resin composition containing up to 15% by weight.

As the rubber-like elastic material, any material having rubber-like properties at room temperature may be used. For example, butadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer and the like are used. Styrene butadiene copolymer and styrene butadiene block copolymer. Among them, especially when the styrene content is 10
It is preferably about 45% by weight.

The (A) amine compound used in the present invention comprises:
3 represented by the following general formulas (1), (2) and (3)
It consists of secondary or tertiary amine compounds represented by types (A1), (A2) and (A3) and having a hydroxyethyl group in the formula. One or more of these amine compounds selected from the amine compounds (A1), (A2) and (A3) may be used.

[0017]

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[0018]

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[0019]

Embedded image (In the formulas (1), (2) and (3), R is an alkyl group having 8 to 15 carbon atoms)

[0020]

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(R ₁ is an alkyl group having 8 to 22 carbon atoms;
₂ , R ₃ and R ₄ are an alkyl or hydroxyalkyl group having 1 to ₄ carbon atoms, and R ₅ is an alkyl group having 1 to 18 carbon atoms) (A) the amine compound and (B) the quaternary alkylbenzenesulfonic acid in the present invention The amount of ammonium salt added is
The total amount of (A) and (B) is 0.5 to 4.0% by weight per 100 parts by weight of the styrene resin, and
-3.0 parts by weight is preferred.

When the amount is less than 0.5% by weight, the antistatic effect is not sufficient, and when the amount exceeds 4.0 parts by weight, disadvantages such as a decrease in heat stability or heat deformation are caused, which is not preferable. The mixing ratio of the (A) amine compound and (B) quaternary ammonium salt of alkylbenzenesulfonic acid is as follows:
(B) The quaternary ammonium salt of alkylbenzenesulfonic acid is 5 to 70% by weight, preferably 10 to 50% by weight, based on the total amount of both (A) and (B). If the compounding ratio of the (B) quaternary ammonium alkylbenzenesulfonic acid salt is less than 5% by weight, a sufficient antistatic effect cannot be obtained, and if it exceeds 70% by weight, transparency is greatly reduced, which is not preferable.

In the present invention, examples of the equipment used for producing the composition by adding an antistatic agent to the styrene resin include kneaders which are generally used, such as Banbury, rolls and extruders. In addition, additives such as a plasticizer, a heat stabilizer, a release agent, an ultraviolet absorber, and a dye (pigment) can be added to the styrene resin composition of the present invention as needed.

The antistatic styrenic resin composition of the present invention can be molded by a processing method such as injection molding, extrusion molding, compression molding, or calender molding which is carried out by ordinary plastic molding. And processed products such as injection molded products, extruded sheets and thermoformed products thereof, films, and profiled extrusion molded products.

[0025]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described more specifically with reference to examples. The method for measuring physical properties is shown below. (1) Haze value (%) The haze value (%) was measured with an integrating sphere light transmittance measuring device according to JIS-6714. (2) Surface resistance (Ω) The condition was adjusted for 48 hours at 23 ° C. and 50% RH, and the measurement was performed using a super-insulation meter SM-3000 series manufactured by Toa Denpa Kogyo KK.

[0026]

Example 1 As a styrene resin (styrene resin-1), polystyrene was Styron 6 manufactured by Asahi Kasei Corporation.
85 as 50% by weight, styrene-butadiene block copolymer resin asaflex 810 manufactured by Asahi Kasei Kogyo Co., Ltd. at 45% by weight, and styrene butadiene block copolymer elastomer as Asahi Kasei Kogyo Co., Ltd.
% By weight (hereinafter referred to as styrene resin-1).
a), (A) an amine compound (A)
1) N. 1.5 parts by weight of N-bis (2-hydroxyethyl) alkylamine [Denone 331L manufactured by Marubishi Yuka Co., Ltd.] and (B) AKS-542 manufactured by Takemoto Yushi Co., Ltd. as a quaternary ammonium salt of alkylbenzenesulfonic acid. 0.5
The mixture was melt-kneaded at 210 ° C. with a single screw extruder to obtain a styrene resin composition.

Using the obtained styrene resin composition, 4
A sheet having a thickness of 0.3 mm was prepared using a 0 mmT die sheet extruder. Measure the physical properties of the obtained sheet,
The results are shown in Table 1. [In Table 1, × 10En of the value of the surface resistance (Ω) represents 10 n (n is an integer)].

[0028]

Example 2 A styrene resin composition and a sheet were prepared in the same manner as in Example 1 except that (A2) hydroxyalkyldiethanolamine (Dasper 1000C manufactured by Miyoshi Oil & Fats Co., Ltd.) was used as the amine compound (A). Created. The physical properties of the obtained sheet were measured, and the results were shown in Table 1.
It was shown to.

[0029]

Example 3 Styrene was prepared in the same manner as in Example 1 except that (A3) N-2 hydroxyethyl-N-2 hydroxyalkylamine (Dasper 125B manufactured by Miyoshi Oil & Fats Co., Ltd.) was used as the amine compound (A). The system resin composition and the sheet were obtained, and the physical properties of the sheet were measured. The results are shown in Table 1.

[0030]

Example 4 As a styrene resin (styrene resin-1), 50% by weight of a styrene-butyl acrylate copolymer resin, Asahi Kasei Polystyrene SC004, manufactured by Asahi Kasei Kogyo Co., Ltd., a styrene butadiene block copolymer The resin is Asaflex 810 manufactured by Asahi Kasei Kogyo Co., Ltd.
% By weight, styrene-butadiene block copolymer elastomer manufactured by Asahi Kasei Kogyo Co., Ltd., 5% by weight of tufrene 125 in a total of 100 parts by weight (hereinafter referred to as styrene resin-1b).
Styrene-based composition and a sheet were prepared in the same manner as in Example 1 except that styrene-based composition was used. The physical properties of the obtained sheet were measured, and the results are shown in Table 1.

[0031]

Example 5 A styrene resin composition and a sheet were prepared in the same manner as in Example 4 except that (A2) hydroxyalkyldiethanolamine was used as the amine compound (A). The physical properties of the obtained sheet were measured, and the results are shown in Table 1.

[0032]

Example 6 Two reactors equipped with a stirring group were connected in series, and 43.0% by weight of styrene and 9.0 of butyl acrylate were used.
% Of methyl methacrylate and 38.0% by weight of methyl methacrylate, and 3.0% by weight of ethylbenzene was further added as a solvent. 7.5% by weight of a rubber-like elastic material was dispersed and melted in this mixture. Thereafter, the polymerization reaction was carried out in a continuous polymerization tank in which the inlet temperature was set at 100 ° C and the outlet temperature was set at 150 ° C. Vacuum deaeration to remove unreacted monomers
It was set to 00 ppm or less.

The component ratio of the styrene resin (hereinafter referred to as styrene resin-2a) obtained by the above operation was measured by pyrolysis gas chromatography. As a result, the component ratio of the resin phase (mother phase) was 46.3% by weight of styrene, 7.5% by weight of butyl acrylate, 38% by weight of methyl methacrylate, and the rubber content of the dispersed phase was 8.5. % By weight. Further, when the rubber particle diameter of this dispersed phase was measured with an electron microscope, the average particle diameter was 0.65 μm.

With respect to 100 parts by weight of the styrene resin-2a, (A1) N.I. N
-Bis (2-hydroxyethyl) alkylamine in 1.5
A styrene-based composition and a sheet thereof were prepared in the same manner as in Example 1, except that 0.5 parts by weight of (B) a quaternary ammonium salt of alkylbenzenesulfonic acid (B) was added.
The physical properties of the obtained sheet were measured, and the results are shown in Table 1.

[0035]

Example 7 A sheet was prepared in the same manner as in Example 5, except that (A2) hydroxyalkyldiethanolamine was used as the amine compound (A). The physical properties of the obtained sheet were measured, and the results are shown in Table 1.

[0036]

Example 8 A sheet was prepared in the same manner as in Example 5, except that (A3) N-2-hydroxyethyl-N-2 hydroxyalkylamine was used as the amine compound (A). The physical properties of the obtained sheet were measured, and the results were shown in Table 1.
It was shown to.

[0037]

COMPARATIVE EXAMPLE 1 (B) An amine compound (A) was used without (A) an amine compound without using an alkylbenzene sulfone quaternary ammonium salt.
1) N. A sheet was prepared in the same manner as in Example 1, except that 2.0 parts by weight of N-bis (2-hydroxyethyl) alkylamine was used. Measure the physical properties of the obtained sheet,
The results are shown in Table 1.

[0038]

[Comparative Example 2] (A) An amine compound (A) was prepared without using a quaternary ammonium salt of alkylbenzenesulfonic acid (A).
2) A sheet was prepared in the same manner as in Example 1 except that 2.0 parts by weight of hydroxyalkyldiethanolamine was used. The physical properties of the obtained sheet were measured, and the results are shown in Table 1.

[0039]

[Comparative Example 3] (B) An amine compound (A) was used without using a quaternary ammonium salt of alkylbenzenesulfonic acid.
3) A sheet was prepared in the same manner as in Example 1 except that 2.0 parts by weight of N-2hydroxyethyl-N-2hydroxyalkylamine was used. The physical properties of the obtained sheet were measured, and the results are shown in Table 1.

[0040]

COMPARATIVE EXAMPLE 4 (B) An amine-based compound (A) was used without using a quaternary ammonium salt of alkylbenzenesulfonic acid.
1) N. A sheet was prepared in the same manner as in Example 6, except that 2.0 parts by weight of N-bis (2-hydroxyethyl) alkylamine was used. Measure the physical properties of the obtained sheet,
The results are shown in Table 1.

[0041]

[Comparative Example 5] (B) An amine compound (A) was used without using a quaternary ammonium salt of alkylbenzenesulfonic acid.
2) A sheet was prepared in the same manner as in Example 6, except that 2.0 parts by weight of hydroxyalkyldiethanolamine was used. The physical properties of the obtained sheet were measured, and the results are shown in Table 1.

[0042]

Comparative Example 6 (B) An amine compound (A) was used without using a quaternary ammonium salt of alkylbenzenesulfonic acid.
3) A sheet was prepared in the same manner as in Example 6, except that 2.0 parts by weight of N-2hydroxyethyl-N-2hydroxyalkylamine was used. The physical properties of the obtained sheet were measured, and the results are shown in Table 1.

[0043]

Comparative Example 7 (A) Without using an amine compound,
(B) A sheet was prepared in the same manner as in Example 1 except that 2.0 parts by weight of the alkylbenzenesulfonic acid quaternary ammonium salt was used. The physical properties of the obtained sheet were measured, and the results are shown in Table 1.

[0044]

Comparative Example 8 (A) Without using an amine compound,
(B) A sheet was prepared in the same manner as in Example 6, except that 2.0 parts by weight of the alkyl benzene sulfonic acid quaternary ammonium salt was used. The physical properties of the obtained sheet were measured, and the results are shown in Table 1.

[0045]

Comparative Example 9 A sheet was prepared in the same manner as in Example 1 except that (A) the amine compound and (B) the quaternary ammonium salt of alkylbenzenesulfonic acid were not used. The physical properties of the obtained sheet were measured, and the results were shown in Table 1.
It was shown to.

[0046]

Comparative Example 10 A sheet was prepared in the same manner as in Example 6, except that neither (A) the amine compound nor (B) the quaternary ammonium salt of alkylbenzenesulfonic acid was used. The physical properties of the obtained sheet were measured, and the results are shown in Table 1.

[0047]

[Table 1]

[0048]

The antistatic styrenic resin composition of the present invention is excellent in transparency and antistatic properties as compared with conventional ones, and in particular, as a material for packaging electronic parts, requires less work steps than conventional coating dies. It is a useful material that has advantages such as simplification and reduction in coating cost.

Claims (4)

[Claims] 1. A compound represented by the following general formula (1) or (2) having a hydroxyethyl group in 100 parts by weight of a styrene resin.
One or more selected from the three types of (A) amine compounds represented by (3) and (B) quaternary ammonium alkylbenzenesulfonic acid represented by the following general formula (4) are 0.4 to 4. 0 parts by weight,
The proportion of the added amount of (B) is 5 to the total amount of (A) and (B).
70% by weight of an antistatic styrenic resin composition. Embedded image Embedded image Embedded image (In the above formula, R is an alkyl group having 8 to 15 carbon atoms.) (R ₁ is an alkyl group having 8 to 22 carbon atoms, R ₂ , R ₃ and R ₄ are alkyl or hydroxyalkyl groups having 1 to ₄ carbon atoms, and R ₅ is an alkyl group having 1 to 18 carbon atoms) 2. The styrenic resin according to claim 1,
(A) at least one selected from polystyrene and / or (a ') styrene- (meth) acrylate copolymer at 20 to 70% by weight, and (b) vinyl aromatic hydrocarbon content at 65 to 85% by weight. % Of a block copolymer resin of a vinyl aromatic hydrocarbon and a conjugated diene 80 to 30% by weight
And (c) the content of the vinyl aromatic hydrocarbon is 20 to
A styrene resin composition comprising a blend of 50% by weight of a block copolymer elastomer of a vinyl aromatic hydrocarbon and a conjugated diene with 0 to 10% by weight. 3. The styrenic resin according to claim 1, comprising a resin phase (mother phase) and a dispersed phase, wherein the resin phase (mother phase) comprises (a) 30 to 70% by weight of a styrene monomer. (B) A rubber-like elastic material comprising 70 to 30% by weight of a (meth) acrylic ester monomer and graft-copolymerized and having a dispersed phase having an average particle diameter of 0.3 to 2.0 μm. A styrene-based resin composition, which is contained and has a content of 5 to 20% by weight. 4. A molded article obtained by molding the styrene resin composition according to claim 1.