TW202146569A - Antistatic resin composition, manufacturing method of antistatic resin composition, and packaging material for electronic parts containing a block copolymer (b) and a donor-acceptor-based molecular compound c - Google Patents

Abstract

This invention provides an antistatic resin composition with excellent antistatic properties and excellent transparency. This invention relates to an antistatic resin composition which contains a block copolymer (b) and a donor-acceptor-based molecular compound (c), and the block copolymer (b) is a block copolymer containing 30 to 90% by mass of vinyl aromatic hydrocarbon monomer units and 70 to 10% by mass of conjugated diene monomer units, and has a polymer block mainly composed of vinyl aromatic hydrocarbon monomer units. When the total amount of the block copolymer (b) and the donor-acceptor-based molecular compound (c) is 100% by mass, the content of the donor-acceptor-based molecular compound (c) is more than 0.5 mass% and less than 5 mass%.

Description

Antistatic resin composition, method for producing antistatic resin composition, and packaging material for electronic parts

The present invention relates to an antistatic resin composition, a method for producing the antistatic resin composition, and a packaging material for electronic parts.

In general, vinyl aromatic hydrocarbon-based resins (eg, styrene-based resins) are excellent in moldability, rigidity, transparency, etc., are inexpensive, have a low specific gravity, and are also economically excellent. Therefore, vinyl aromatic hydrocarbon-based resins are Resin-molded molded articles are widely used in various fields as injection molded articles, sheet-like molded articles extruded from T-die, or round or square tubular shaped extrusion molded articles extruded from special-shaped dies.

Among them, carrier tapes used to mount and package electronic components such as integrated circuits (ICs) or large-scale integrated circuits (LSIs) in electronic machines, or tubes used to mount and package connectors and various semiconductor components (also known as magazine stick), and various electronic parts packaging materials such as transport trays for packaging liquid crystal panels, etc. are generally widely used: containing impact-resistant polystyrene or transparent MBS resin (methacrylic acid Sheet-shaped moldings or tubular extrusion moldings of vinyl aromatic hydrocarbon resins such as methyl ester/butadiene/styrene copolymer resin). The above-mentioned electronic parts packaging materials such as carrier tapes, tubes, and conveying trays are required to have various characteristics according to their use forms. It produces burrs, or obtains the formability of uniform thickness without uneven thickness during vacuum forming, or transparency (visibility), which is used to prevent malfunction or destruction of electronic parts caused by static electricity. Antistatic properties, etc., In response to these requirements, various improvement studies have been carried out to improve these properties and obtain a better balance of physical properties.

In particular, as an antistatic material based on a vinyl aromatic hydrocarbon resin, a composition in which conductive carbon such as Ketjen black is blended with a styrene resin has been widely known. The previously proposed styrene-based antistatic material prepared with conductive carbon in a styrene-based resin ^{exhibits a surface resistivity of about 10 5} Ω/□, which shows an extremely low surface resistance that is indispensable in some types of electronic parts However, some electronic components do not necessarily require such a low surface resistivity, and there are also a large number of electronic components with ^{a surface resistivity of about 10 10 Ω/□.} On the other hand, as a disadvantage of the antistatic material prepared with conductive carbon, there is a problem that the color of the molded product is dark and opaque, so the visibility is poor, and it is difficult to confirm the contents in the state of the package. In addition, it is also pointed out that there is a possibility of causing contamination as follows, that is, when the electronic parts are mounted on the formed electronic parts packaging material and actually conveyed, the friction of the contact part between the electronic parts and the packaging material caused by the vibration during conveyance, and Causes the conductive carbon to fall off, and the falling off conductive carbon adheres to electronic parts, etc.

On the other hand, the technical development of a resin composition that exhibits antistatic properties without using conductive carbon has also been performed previously. For example, there is proposed a technique for a resin composition in which a polymer-type conductive polymer having a polyoxyalkylene chain is blended with a thermoplastic resin such as a styrene-based resin (for example, refer to Patent Document 1). However, the refractive index of the high-molecular conductive polymer is generally lower than that of the styrene-based resin as the base resin, and the packaging materials for electronic parts including the resin composition prepared with the high-molecular conductive polymer are due to the same refractive index. The deviation is large, so there is a problem of white turbidity and impaired visibility. Furthermore, in order to exhibit antistatic properties, it is usually necessary to prepare a large amount of high-molecular type conductive polymer at a content of more than 10%. Therefore, due to the structure of the polymer, the elastic modulus is low, and the rigidity of the resin composition decreases. There is a problem that the mechanical properties of the resin composition vary greatly.

Furthermore, as a method for obtaining an antistatic resin composition, a method of adding a surfactant as a general antistatic agent to a thermoplastic resin is also known. However, the antistatic agent of surfactant type exhibits its performance by exuding to the surface of the molded product, so if the surface of the molded product is wiped with water, the antistatic property temporarily decreases, and the surface resistivity increases. subject. Furthermore, since the antistatic agent itself oozes out to the surface of the molded product, there is a concern that it will adhere to the electronic parts as the contents and cause contamination, which is not suitable for the use of electronic parts packaging materials.

Therefore, in recent years, an antistatic resin composition obtained by using a donor-acceptor molecular compound containing an organoboron compound and a nitrogen-containing compound as a novel antistatic agent and adding it to a thermoplastic resin has been proposed (for example, refer to patent Document 2, Non-Patent Document 1). The antistatic agent is introduced into the concept of molecular compound. The antistatic resin composition is different from the previous surfactant type that exudes to the surface of the molded product and exerts an antistatic effect. By combining the electron donor and the acceptor, the charge is exchanged instantaneously, thereby making the charged charge instantaneously Attenuation, thus showing antistatic effect. [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2011-6604 [Patent Document 2] Japanese Patent No. 5734491 [Non-patent literature]

[Non-Patent Document 1] Magazine "Plastics age" April 2018 pp. 47-52

[Problems to be Solved by Invention]

However, the above-mentioned antistatic resin composition using a donor-acceptor molecular compound containing an organoboron compound and a nitrogen-containing compound also has a problem. Resins exhibiting antistatic properties are limited to: PE (Polyethylene, polyethylene) or PP (Polypropylene, polypropylene), so-called crystalline polyolefin resins such as cyclic polyolefins, or polyamides, PET (polyethylene terephthalate, polyolefin resins) Ethylene terephthalate) resin, ABS (acrylonitrile-butadiene-styrene, acrylonitrile-butadiene-styrene) resin, polyvinyl chloride, polyacetal and other hydrocarbons other than hydrocarbons containing more than a certain concentration in the polymer backbone The heteroatom of the so-called polar resin. That is, there is the following problem: even for general-purpose polystyrene (also known as GPPS) or rubber-modified polystyrene (also known as HIPS) or methyl methacrylate/benzene with a methyl methacrylate content of about 20% by mass In the ethylene copolymer resin (also called MS resin), for example, about 4% by mass of the above-mentioned donor-acceptor system molecular compound, which is generally considered to be a sufficient amount, cannot obtain the effect of reducing the surface resistivity, and cannot exhibit antistatic properties.

Therefore, in view of the above-mentioned problems of the prior art, the present invention aims to provide an antistatic resin composition that exhibits excellent antistatic properties and excellent transparency and a method for producing the same, and the antistatic resin composition can be used for general-purpose use. When polystyrene (GPPS), rubber-modified polystyrene (HIPS) containing grafted rubber particles, or styrene-based resin such as styrene-acrylic copolymer resin is used as the base resin, the above-mentioned donors can also be prepared. -In the resin composition of the acceptor molecular compound, the original properties of the donor-acceptor molecular compound are brought out. [Technical means to solve problems]

The inventors of the present invention conducted intensive research and found that by combining a donor-acceptor molecular compound with a specific block copolymer and optimizing the composition, an antistatic resin that can exhibit excellent antistatic properties and transparency can be obtained. composition, thereby completing the present invention. That is, the present invention is as follows.

[1] An antistatic resin composition containing a block copolymer (b) and a donor-acceptor molecular compound (c), wherein the block copolymer (b) contains a vinyl aromatic A block copolymer of a hydrocarbon monomer unit and a conjugated diene monomer unit, having a polymer block mainly composed of a vinyl aromatic hydrocarbon monomer unit, and the vinyl aromatic hydrocarbon monomer unit is 30 to 90% by mass , the conjugated diene monomer unit is 70 to 10% by mass, and the total amount of the above-mentioned block copolymer (b) and the above-mentioned donor-acceptor system molecular compound (c) is 100% by mass, the above-mentioned donor- The content of the acceptor molecular compound (c) is 0.5 mass % or more and 5 mass % or less. [2] The antistatic resin composition according to the above [1], which has a surface resistivity of 1×10 ¹² Ω/□ or less. [3] An antistatic resin composition comprising a vinyl aromatic hydrocarbon resin (a), a block copolymer (b), and a donor-acceptor molecular compound (c), wherein the block Copolymer (b) is a block copolymer containing vinyl aromatic hydrocarbon monomer units and conjugated diene monomer units, and has a polymer block with vinyl aromatic hydrocarbon monomer units as the main body, vinyl aromatic hydrocarbon monomer units. 30 to 90 mass % of the aliphatic hydrocarbon monomer unit, 70 to 10 mass % of the conjugated diene monomer unit, and the total amount of the above vinyl aromatic hydrocarbon resin (a) and the above block copolymer (b) At 100 mass %, the mass ratio of the vinyl aromatic hydrocarbon resin (a) is 81 mass % or less, and the mass ratio of the block copolymer (b) is 19 mass % or more and less than 100 mass %, When the total amount of the vinyl aromatic hydrocarbon resin (a), the block copolymer (b), and the donor-acceptor molecular compound (c) is 100% by mass, the donor-acceptor molecule The content of the compound (c) is 0.5 mass % or more and 5 mass % or less, and the surface resistivity is 1×10 ¹² Ω/□ or less. [4] The antistatic resin composition according to the above [3], wherein the vinyl aromatic hydrocarbon resin (a) is selected from the group consisting of homopolymers (a1) of vinyl aromatic hydrocarbon monomers, vinyl aromatic hydrocarbons Graft copolymers of hydrocarbon monomers (a2) and random copolymers (a3) of vinyl aromatic hydrocarbon monomer units and (meth)acrylic acid and/or (meth)acrylic acid alkyl ester monomer units any one of the group formed. [5] The antistatic resin composition according to the above [3] or [4], wherein in the melt flow rate (MFR) under the conditions of 200° C. and 5 kg load specified in ISO1133, the above vinyl aromatic hydrocarbon is The relationship between the MFR (hereinafter, referred to as MFRa) of the resin (a) and the MFR (hereinafter, referred to as MFRb) of the above-mentioned block copolymer (b) satisfies any one of the following conditions (i) to (iv); (i)> When the sum of said (a) component and said (b) component is made into 100 mass %, said (a) component is more than 0 mass % and 30 mass % or less, and said (b) component is 70 mass % % or more and less than 100 mass %, regardless of the numerical value of MFRa and MFRb, when the sum of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is 100 mass %, the above-mentioned (c) ) components are 0.5 mass % or more and 5 mass % or less; <Condition (ii)> When the sum of the above-mentioned (a) component and the above-mentioned (b) component is 100 mass %, the above-mentioned (a) component is more than 30 mass % % and 50 mass % or less, when the above-mentioned (b) component is less than 70 mass % and 50 mass % or more, when the relationship of MFRa<MFRb・・(Formula 1), the above-mentioned (a) component, the above-mentioned When the total of the component (b) and the component (c) above is 100% by mass, the component (c) above is 0.5% by mass or more and 5% by mass or less, and in the relationship of MFRa≧MFRb・・(Formula 2), When the sum of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is set to 100 mass %, the above-mentioned (c) component is 0.9 mass % or more and 5 mass % or less; When the total of the component (a) and the component (b) above is 100% by mass, the component (a) is more than 50% by mass and 70% by mass or less, and the component (b) is less than 50% by mass and 30% by mass In the case of the above, the relationship of MFRa<MFRb・・(Formula 1) is satisfied, and when the total of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100% by mass, the above-mentioned (c) component It is 0.9 mass % or more and 5 mass % or less; <Condition (iv)> When the sum of said (a) component and said (b) component is made into 100 mass %, said (a) component is more than 70 mass % and 81 mass % or less, when the above-mentioned (b) component is less than 30 mass % and 19 mass % or more, the relationship of MFRa<MFRb・・(Formula 1) is satisfied, and the above-mentioned (a) component, above-mentioned (b) component and When the total of the said (c) component is 100 mass %, the said (c) component is 3 mass % or more and 5 mass % or less. [6] The antistatic resin composition according to the above [4], wherein in the melt flow rate (MFR) under the conditions of 200° C. and 5 kg load specified in ISO1133, the above vinyl aromatic hydrocarbon resin (a3) The relationship between the MFR (hereinafter, referred to as MFRa) and the MFR (hereinafter, referred to as MFRb) of the above-mentioned block copolymer (b) satisfies the following conditions (v) or (vi); When the sum of the said (a3) component and the said (b) component is 100 mass %, the said (a3) component is more than 0 mass % and 20 mass % or less, and the said (b) component is 80 mass % or more and less than 100 mass % In the case of mass %, irrespective of the numerical value of MFRa and MFRb, when the total of the above-mentioned (a3) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100 mass %, (c) is 0.5 mass % or more. 5 mass % or less; <Condition (vi)> When the sum of the above-mentioned (a3) component and the above-mentioned (b) component is 100 mass %, the above-mentioned (a3) component is more than 20 mass % and 50 mass % or less, and the above When the component (b) is less than 80% by mass and 50% by mass or more, MFRa<MFRb is satisfied. (Formula 1) When it is 100 mass %, the said (c) component is 3 mass % or more and 5 mass % or less. [7] The antistatic resin composition according to any one of the above [1] to [6], wherein the above-mentioned donor-acceptor molecular compound (c) is represented by the following general formula (1);

[hua 1]

(In formula (1), R ₁ and R ₂ are independently CH ₃ (CH ₂ ) _n -CO-OCH ₂ (n is an integer of 12 to 22) or HOCH ₂ , and at least one of them is CH ₃ (CH _{2 )} ) _n -CO-OCH ₃ (n is an integer from 12 to 22); R ₃ and R ₄ are independently selected from CH ₃ , C ₂ H ₅ , HOCH ₂ , HOC ₂ H ₄ and HOCH ₂ CH(CH ₃ ) Any one of the group formed; Here, "δ+" in the general formula (1) means that there is polarity in the covalent bond in the molecule, (+) means that the electron donating property of the oxygen atom becomes stronger, ( -) indicates that the electron-withdrawing property of the boron atom becomes stronger, "→" indicates the path of electrons being drawn closer, and "---" indicates the state where the bonding force between atoms is weakened).

[8] A method for producing the antistatic resin composition according to any one of the above [1] to [7], the method comprising: Step (I), that is, using the block copolymer (b) and the molecular compound of the donor-acceptor system (c), the molecular compound of the donor-acceptor system (c) when the total amount of the master batch is set at 100% by mass is: The composition ratio of 5 mass % or more and 20 mass % or less is melt-kneaded to produce a master batch; and Step (II), that is, diluting the master batch by kneading the above master batch with the vinyl aromatic hydrocarbon resin (a) and/or the block copolymer (b). [9] An electronic component packaging material, which is a molded body of the antistatic resin composition according to any one of the above [1] to [7]. [Effect of invention]

According to the present invention, there can be provided an antistatic resin composition, a method for producing the antistatic resin composition, and a packaging material for electronic parts, wherein the antistatic resin composition can be modified even with general-purpose polystyrene (GPPS) or rubber. When combined with styrene resins such as polystyrene (HIPS), methyl methacrylate/styrene copolymer resin (MS resin), etc., it also exhibits excellent antistatic properties and excellent transparency.

Hereinafter, an embodiment of the present invention (hereinafter, referred to as "the present embodiment") will be described in detail. In addition, the following present embodiment is an example for explaining the present invention, and does not mean that the present invention is limited to the following contents, and the present invention can be implemented with various changes within the scope of the gist.

[Antistatic resin composition] (First antistatic resin composition) The first antistatic resin composition of the present embodiment is an antistatic resin composition containing the block copolymer (b) and the donor-acceptor molecular compound (c). The above-mentioned block copolymer (b) is a block copolymer containing vinyl aromatic hydrocarbon monomer units and conjugated diene monomer units, and has a polymer block mainly composed of vinyl aromatic hydrocarbon monomer units, The vinyl aromatic hydrocarbon monomer unit is 30 to 90 mass %, and the conjugated diene monomer unit is 70 to 10 mass %. Further, when the total amount of the block copolymer (b) and the donor-acceptor molecular compound (c) is 100 mass %, the content of the donor-acceptor molecular compound (c) is 0.5 mass % or more 5 mass % or less.

By having the above configuration, even when combined with styrene resins such as general-purpose polystyrene (GPPS), rubber-modified polystyrene (HIPS), methyl methacrylate/styrene copolymer resin (MS resin), etc. , an antistatic resin composition with excellent antistatic performance and excellent transparency can also be obtained.

The first antistatic resin composition of the present embodiment preferably has a surface resistivity of 1×10 ¹² Ω/□ or less. Thereby, excellent antistatic properties can be exerted. The surface resistivity of the first antistatic resin composition is preferably 5×10 ¹¹ Ω/□ or less, more preferably 5×10 ¹⁰ Ω/□ or less. The surface resistivity of the antistatic resin composition can be measured by the method described in the following examples. The surface resistivity of the first antistatic resin composition can be controlled to the above-mentioned value by optimizing the polymer structure of the above-mentioned block copolymer (b) and formulating an appropriate amount of the donor-acceptor system molecular compound (c). Scope. Originally, there is no lower limit of surface resistivity, and it is considered that the lower the surface resistivity, the better the performance. However, the reduction of the surface resistivity is proportional to the cost, so in practice, it is preferable to design 1×10 ⁸ Ω/□ to 1×10 ⁹ Ω/□ as the lower limit.

(Second Antistatic Resin Composition) The second antistatic resin composition of the present embodiment contains vinyl aromatic hydrocarbon resin (a), block copolymer (b), and donor-acceptor system molecules The antistatic resin composition of compound (c). The above-mentioned block copolymer (b) is a block copolymer containing vinyl aromatic hydrocarbon monomer units and conjugated diene monomer units, and has a polymer block mainly composed of vinyl aromatic hydrocarbon monomer units, The vinyl aromatic hydrocarbon monomer unit is 30 to 90 mass %, and the conjugated diene monomer unit is 70 to 10 mass %. When the total amount of the vinyl aromatic hydrocarbon resin (a) and the block copolymer (b) is 100 mass %, the mass ratio of the vinyl aromatic hydrocarbon resin (a) is 81 mass % or less, The mass ratio of the said block copolymer (b) is 19 mass % or more and less than 100 mass %. Furthermore, when the total amount of the vinyl aromatic hydrocarbon resin (a), the block copolymer (b), and the donor-acceptor molecular compound (c) is 100% by mass, the donor-acceptor The content of the system molecular compound is 0.5 mass % or more and 5 mass % or less. Furthermore, the surface resistivity of the second antistatic resin composition is 1×10 ¹² Ω/□ or less.

By having the above-mentioned constitution, it is possible to obtain antistatic resin compositions as various styrene-based resin compositions that exhibit excellent antistatic performance and are also excellent in transparency.

The surface resistivity of the second antistatic resin composition of the present embodiment is 1×10 ¹² Ω/□ or less. Thereby, excellent antistatic properties can be exerted. The surface resistivity of the second antistatic resin composition is more preferably 5×10 ¹¹ Ω/□ or less, and still more preferably 5×10 ¹⁰ Ω/□ or less. The surface resistivity of the antistatic resin composition can be measured by the method described in the following examples. The surface resistivity of the second antistatic resin composition can be controlled by optimizing the composition ratio and polymer structure of the above-mentioned block copolymer (b), and by formulating an appropriate amount of the donor-acceptor system molecular compound (c). is the above numerical range.

The preferable aspect of the said 2nd antistatic resin composition is shown below. The above-mentioned second antistatic resin composition preferably has the MFR of the above-mentioned vinyl aromatic hydrocarbon-based resin (a) in the melt flow rate (MFR) under the conditions of 200° C. and 5 kg load specified in ISO1133 (below, The relationship between the MFR (hereinafter referred to as MFRa) and the block copolymer (b) (hereinafter, referred to as MFRb) satisfies any one of the following conditions (i) to (iv).

<Condition (i)> When the sum of the above-mentioned vinyl aromatic hydrocarbon resin (a) and the block copolymer (b) is 100% by mass, the component (a) is more than 0% by mass and not more than 30% by mass, and the component (b) above is When it is 70 mass % or more and less than 100 mass %, regardless of the numerical value of MFRa and MFRb, when the sum of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is set to 100 mass %, The said donor-acceptor system molecular compound (c) is 0.5 mass % or more and 5 mass % or less.

By satisfying the above-mentioned condition (i), an antistatic resin composition which exhibits excellent antistatic performance and is also excellent in transparency can be obtained. Moreover, since the composition ratio of the block copolymer (b) is high, the effect of being rich in flexibility and having an excellent impact strength can be obtained. In the condition (i), the content of the donor-acceptor system molecular compound (c) is preferably 1 to 5 mass %, more preferably 2 to 4 mass %.

<Condition (ii)> When the sum of the said vinyl aromatic hydrocarbon resin (a) and the block copolymer (b) is made into 100 mass %, the said (a) component is more than 30 mass % and 50 mass % or less, and the said (b) When the component is less than 70% by mass and 50% by mass or more, it shall be MFRa＜MFRb・・(Formula 1) When the relationship between the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100 mass %, the above-mentioned (c) component is 0.5 mass % or more and 5 mass % or less, which is MFRa≧MFRb・・(Formula 2) In the case of the relationship, when the total of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is set to 100 mass %, the above-mentioned (c) component is 0.9 mass % or more and 5 mass % or less.

By satisfying the above-mentioned condition (ii), an antistatic resin composition which exhibits excellent antistatic performance and is also excellent in transparency can be obtained. Moreover, the effect of further improving the rigidity of a resin composition by vinyl aromatic hydrocarbon resin (a) can be acquired. In the condition (ii), the content of the above-mentioned donor-acceptor system molecular compound (c) is preferably 1 to 5 mass %, more preferably 2 to 4 mass %, as long as the above-mentioned (Formula 1) is satisfied. Moreover, when satisfying the said (Formula 2), it is preferable that it is 2-5 mass %, and it is more preferable that it is 2-4 mass %.

<Condition (iii)> When the sum of the said vinyl aromatic hydrocarbon resin (a) and the block copolymer (b) is made into 100 mass %, the said (a) component is more than 50 mass % and 70 mass % or less, and the said (b) When the component is less than 50 mass % and 30 mass % or more, Satisfy MFRa＜MFRb・・(Formula 1) The relationship between the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100% by mass, and the above-mentioned donor-acceptor system molecular compound (c) is 0.9% by mass or more and 5% by mass the following.

By satisfying the above-mentioned condition (iii), an antistatic resin composition which exhibits excellent antistatic performance and is also excellent in transparency can be obtained. In addition, the effect of further enhancing the rigidity of the resin composition derived from the vinyl aromatic hydrocarbon resin (a) can be obtained. In the condition (iii), the content of the above-mentioned donor-acceptor system molecular compound (c) is preferably 2 to 5 mass %, more preferably 3 to 5 mass %.

<Condition (iv)> When the sum of the said vinyl aromatic hydrocarbon resin (a) and the block copolymer (b) is made into 100 mass %, the said (a) component is more than 70 mass % and 81 mass % or less, and the said (b) When the component is less than 30 mass % and 19 mass % or more, Satisfy MFRa＜MFRb・・(Formula 1) When the total of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100% by mass, the content of the above-mentioned donor-acceptor molecular compound (c) is 3% by mass or more and 5% by mass %the following.

By satisfying the above-mentioned condition (iv), an antistatic resin composition which exhibits excellent antistatic performance and is also excellent in transparency can be obtained. Moreover, the effect of raising to the value close to the rigidity which vinyl aromatic hydrocarbon resin (a) originally has can be obtained. In the condition (iv), the content of the above-mentioned donor-acceptor system molecular compound (c) is preferably 3.5 to 5 mass %, more preferably 4 to 5 mass %.

In this specification, the naming of each monomer unit constituting the polymer is based on the name of the monomer from which the monomer unit is derived. For example, the so-called "vinyl aromatic hydrocarbon monomer unit" refers to the structural unit of the polymer produced by the polymerization of vinyl aromatic hydrocarbon monomer as the monomer, the structure of which is derived from the substituted ethyl extension of the substituted vinyl group The two carbons become the molecular structure of the polymer backbone. In addition, the so-called "conjugated diene monomer unit" refers to the structural unit of the polymer produced by the polymerization of the conjugated diene as the monomer, the structure of which is derived from the two carbons of the olefin of the conjugated diene monomer It becomes the molecular structure of the polymer backbone.

In addition, in this specification, the "main body" means that the content of a specific monomer unit is 90 mass % or more. For example, in the block copolymer (b), the "polymer block mainly composed of vinyl aromatic hydrocarbon monomer units" means a block containing 90 mass % or more of vinyl aromatic hydrocarbon monomer units. A polymer block in which the vinyl aromatic hydrocarbon monomer unit is less than 90% by mass and the conjugated diene monomer unit exceeds 10% by mass is defined as a random copolymer block. The random copolymer block may have a completely random structure or may have a tapered structure (the copolymerization composition ratio changes stepwise along the chain).

(mass ratio of block copolymer (b) to donor-acceptor molecular compound (c)) The first antistatic resin composition of the present embodiment includes a block copolymer (b) containing a vinyl aromatic hydrocarbon monomer unit and a conjugated diene monomer unit, and a donor-acceptor system molecular compound (c) . In the said block copolymer (b), the vinyl aromatic hydrocarbon monomer unit is 30-90 mass %, and the conjugated diene monomer unit is 70-10 mass %. When the total of the block copolymer (b) and the donor-acceptor molecular compound (c) is 100 mass %, the content of the donor-acceptor molecular compound (c) is 0.5 mass % or more and 5 mass % %the following.

(Mass ratio of vinyl aromatic hydrocarbon resin (a), block copolymer (b), and donor-acceptor molecular compound (c)) The mass ratio of vinyl aromatic hydrocarbon resin (a) and block copolymer (b) in the second antistatic resin composition of the present embodiment is vinyl aromatic hydrocarbon resin (a)/block copolymer Substance (b)=amount exceeding 0/less than 100-81 or less/19 or more. According to the change of the mass ratio of the vinyl aromatic hydrocarbon resin (a) and the block copolymer (b) in the above mass ratio, according to the size of the respective MFR values (MFRa and MFRb), the donor-acceptor system that expresses the performance is determined. Minimum required amount of molecular compound (c). The vinyl aromatic hydrocarbon resin ( The ratio of a)/block copolymer (b) and/or the content of the donor-acceptor molecular compound (c).

In the antistatic resin composition of the present embodiment, the mass ratio of vinyl aromatic hydrocarbon resin (a) and block copolymer (b) for achieving excellent antistatic performance, that is, antistatic performance performance, and The relative comparative value of MFR is closely related to the minimum required formulation amount of the donor-acceptor molecular compound (c) to achieve antistatic performance. For example, if the block copolymer (b) is not used, even if about 4 mass % of the donor-acceptor molecular compound (c) is added to the vinyl aromatic hydrocarbon resin (a), the antistatic property is not exhibited. . In order to express antistatic performance, when the total of the vinyl aromatic hydrocarbon resin (a) and the block copolymer (b) is 100 parts by mass, the content of the block copolymer (b) must be at least 100 parts by mass. A composition of 19% by mass or more. Moreover, if the block copolymer (b) is 70 mass % or more when the total of the vinyl aromatic hydrocarbon resin (a) and the block copolymer (b) is taken as 100 mass %, the donor-acceptor system The minimum compounding amount of the molecular compound (c) to achieve antistatic performance is 0.5% by mass, and the performance is not dependent on the MFR value of the vinyl aromatic hydrocarbon resin (a) or the block copolymer (b). Its composition is very broad. For example, even if 0.5 mass % of the donor-acceptor molecular compound (c) is added to 99.5 mass % of the block copolymer (b) without using the vinyl aromatic hydrocarbon resin (a), antistatic performance is exhibited. That is, in order for the vinyl aromatic hydrocarbon resin to express antistatic performance, the block copolymer (b) must be present in a certain ratio or more, and it is considered that there is some kind of interaction with the achievement of antistatic performance.

Hereinafter, the vinyl aromatic hydrocarbon resin (a), the block copolymer (b), and the donor-acceptor molecular compound (c), which are constituents of the antistatic resin composition of the present embodiment, will be described in detail.

(Vinyl Aromatic Hydrocarbon Resin (a)) The vinyl aromatic hydrocarbon resin (a) is preferably a homopolymer (a1) selected from vinyl aromatic hydrocarbon monomers represented by general-purpose polystyrene (GPPS); rubber-modified polystyrene (HIPS) ) represents a graft copolymer (a2) obtained by dissolving a synthetic rubber such as polybutadiene or styrene-butadiene rubber in a styrene monomer and performing graft polymerization while stirring; and MS resin as Any of the group consisting of a random copolymer (a3) of the representative vinyl aromatic hydrocarbon monomer unit and (meth)acrylic acid and/or (meth)acrylic acid alkyl ester monomer unit. Compared with (a1) and (a2), the polarity of (a3) is different, so the dispersion form when mixed with the block copolymer (b) is different, so the composition range of the antistatic performance of the antistatic resin composition is different.

The above-mentioned second antistatic resin composition is preferably the MFR of the above-mentioned vinyl aromatic hydrocarbon resin (a3) in the melt flow rate (MFR) under the conditions of 200 ° C and 5 kg load specified in ISO1133 (below, The relationship between the MFR (hereinafter referred to as MFRa) and the block copolymer (b) (hereinafter, referred to as MFRb) satisfies the following conditions (v) or (vi).

<Condition (v)> When the sum of the above-mentioned vinyl aromatic hydrocarbon resin (a3) and the block copolymer (b) is 100% by mass, the component (a3) is more than 0% by mass and not more than 20% by mass, and the component (b) above is When it is 80 mass % or more and less than 100 mass %, regardless of the values of MFRa and MFRb, When the sum of the above-mentioned (a3) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100% by mass, the content of the above-mentioned donor-acceptor molecular compound (c) is 0.5% by mass or more and 5% by mass or less. .

By satisfying the above-mentioned condition (v), an antistatic resin composition which exhibits excellent antistatic performance and is also excellent in transparency can be obtained. Moreover, compared with the composition using (a1) or (a2), the resin composition which is low in haze value and excellent in transparency can be obtained. In the condition (v), the content of the above-mentioned donor-acceptor system molecular compound (c) is preferably 1 to 5, more preferably 2 to 4 mass %.

<Condition (vi)> When the sum of the above vinyl aromatic hydrocarbon resin (a3) and the block copolymer (b) is 100 mass %, the above (a3) component is more than 20 mass % and 50 mass % or less, and the above (b) When the component is less than 80% by mass and more than 50% by mass, Satisfy MFRa＜MFRb・・(Formula 1) The said (c) component is 3 mass % or more and 5 mass % or less, when the sum total of said (a3) component, said (b) component, and said (c) component is made into 100 mass %.

By satisfying the above-mentioned condition (vi), an antistatic resin composition which exhibits excellent antistatic performance and is also excellent in transparency can be obtained. Moreover, compared with the composition using (a1) or (a2), the resin composition which is low in haze value and excellent in transparency can be obtained. In the condition (vi), the content of the above-mentioned donor-acceptor system molecular compound (c) is preferably 3.5 to 5 mass %, more preferably 4 to 5 mass %.

The copolymerization ratio of vinyl aromatic hydrocarbon monomer unit (S) and (meth)acrylic acid and/or (meth)acrylic acid alkyl ester monomer unit (M) in MS resin (a3) is preferably S/M =83/17 to 60/40 (mass %), more preferably S/M=82/18 to 68/32 (mass %), more preferably S/M=82/18 to 78/22 ( quality%). By using the MS resin with this composition ratio, the refractive index is similar to that of the block copolymer (b), and although the dispersion form is not completely compatible, it exhibits a uniform dispersion form in the micron level, and can obtain excellent transparency and mechanical properties. Electrostatic resin composition. On the other hand, when the content of the vinyl aromatic hydrocarbon monomer unit of the component (a3) is less than 60% by mass, the deviation from the refractive index of the block copolymer (b) is large, and the antistatic resin combination The tendency of the material to become cloudy becomes remarkable, and further the deviation of the polarity becomes large, so that the compatibility becomes poor, and the mechanical properties of the antistatic resin composition are remarkably lowered, which is not good. As long as it is a range which does not impair antistatic performance, MS resin (a3) may contain other monomeric units which can be copolymerized as needed.

The vinyl aromatic hydrocarbon monomer constituting the vinyl aromatic hydrocarbon resin (a) is not particularly limited as long as it has an aromatic ring and a vinyl group in the molecule, and examples thereof include styrene and o-methylstyrene. , m-methylstyrene, p-methylstyrene, o-ethylstyrene, p-ethylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, 1,3-dimethylstyrene Styrene, α-methylstyrene, α-methyl-p-methylstyrene, vinylnaphthalene, vinylanthracene, 1,1-stilbene, etc. These vinyl aromatic hydrocarbon monomers may be used alone or in combination of two or more. Among these, styrene is preferable from the viewpoint of industrial availability and economical efficiency.

Among the above vinyl aromatic hydrocarbon-based resins, ( Meth)acrylic acid and/or (meth)acrylate monomer system refers to one or more monomers selected from the group consisting of acrylic acid, methacrylic acid, alkyl acrylate and alkyl methacrylate .

The alkyl ester may be one or more of an alkyl alcohol having 1 to 8 carbon atoms (C1 to C8) and an ester compound of acrylic acid and/or methacrylic acid. Examples of (meth)acrylic acid and/or (meth)acrylic acid ester monomers include, but are not limited to, acrylic acid, methacrylic acid, methyl acrylate, ethyl acrylate, isopropyl acrylate, and n-butyl acrylate. (butyl acrylate), n-amyl acrylate, n-hexyl acrylate and other C1-6 alkyl acrylates, cyclohexyl acrylate and other cycloalkyl acrylates, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate C1-6 alkyl methacrylates such as propyl ester, n-butyl methacrylate, n-pentyl methacrylate, n-hexyl methacrylate, and cyclohexyl methacrylate such as cyclohexyl methacrylate, etc. Among them, from the viewpoint that the softening temperature of the vinyl aromatic hydrocarbon-based resin (a) can be further increased, and as a result, the moldability and thermal deformation resistance of the obtained molded body can be further improved, acrylic acid C1-6 is preferred. Alkyl ester, C1-6 alkyl methacrylate, more preferably C1-4 alkyl acrylate, C1-4 alkyl methacrylate, more preferably methyl acrylate and/or methyl methacrylate, More preferably, it is methyl methacrylate.

In this specification, "random copolymers of vinyl aromatic hydrocarbon monomer units and (meth)acrylic acid and/or (meth)acrylic acid alkyl ester monomer units" (a3) also include vinyl aromatic hydrocarbons In addition to the monomer units and other (meth)acrylic acid and/or (meth)acrylic acid alkyl ester monomer units, there is also a polymer containing a small amount of other monomer units that can be polymerized with these. The amount of other monomer units is preferably 2 mass % or less in the vinyl aromatic hydrocarbon-based resin (a). In the case of the "random copolymer of vinyl aromatic hydrocarbon monomer unit and methyl methacrylate" exemplified as a particularly preferred copolymer, the aspect containing 2 mass % or less of other monomer units also includes in.

The vinyl aromatic hydrocarbon resin (a) can be produced by a known polymerization method. As a well-known polymerization method, a block polymerization, solution polymerization, emulsion polymerization, suspension polymerization etc. are mentioned, for example. In the case where the vinyl aromatic hydrocarbon resin (a) is a homopolymer (a1) of a vinyl aromatic hydrocarbon monomer represented by GPPS, for example, taking a styrene monomer as an example, it can be carried out as follows: Under the coexistence of benzene and in the presence of organic peroxides or without organic peroxides, radical polymerization is carried out only with heat to remove the solvent of ethylbenzene and unreacted styrene monomers to obtain styrene homopolymers ( GPPS).

When the vinyl aromatic hydrocarbon resin (a) is a graft copolymer (a2) of rubber-modified polystyrene represented by HIPS, for example, polybutadiene is dissolved in ethylbenzene and In the mixed solution of styrene monomers, in the presence of organic peroxides, the radical polymerization is carried out while stirring at a suitable temperature, and the ethylbenzene and unreacted styrene monomers in the solvent are removed, thereby obtaining Rubber-modified polystyrene (HIPS). By using the molecular weight of polybutadiene (Muni viscosity or solution viscosity), using styrene-butadiene rubber instead of polybutadiene, etc., or controlling the stirring speed, the size or occlusion shape of the grafted rubber particles can be controlled. Dense.

Furthermore, in the case where the vinyl aromatic hydrocarbon resin (a) is a random copolymer (a3) containing (meth)acrylic acid and/or (meth)acrylic acid alkyl ester monomer units represented by MS resins , industrially usually: in the coexistence of vinyl aromatic hydrocarbon monomers and (meth)acrylic acid and/or (meth)acrylic acid ester, in the same manner as the above example, a method for producing by radical polymerization .

The MFR of the vinyl aromatic hydrocarbon resin (a) varies depending on factors such as the degree of polymerization of the monomer units or the graft ratio, and in addition to these factors, it also varies greatly due to the addition of additives such as mineral oil. The MFR of the vinyl aromatic hydrocarbon resin (a) affects the dispersion state of the components (a) and (b) above, and the dispersion state is important for expressing the antistatic performance of the antistatic resin composition of the present embodiment elements. The above-mentioned conditions (i) to (vi) specify the MFR value of the component (a) in the state containing the additive such as mineral oil, and the MFR value directly affects the performance of the antistatic resin composition of the present embodiment.

In the production method of the vinyl aromatic hydrocarbon-based resin (a), a polymerization solvent such as ethylbenzene, a radical generator such as an organic peroxide, and a chain transfer agent such as an aliphatic mercaptan can be suitably used. Specific examples are described below.

The polymerization solvent is used to keep the viscosity in the reaction system low during the continuous polymerization process. As the organic solvent, for example, but not limited to, alkylbenzenes such as benzene, toluene, ethylbenzene, and xylene. ketones such as acetone or methyl ethyl ketone, aliphatic hydrocarbons such as hexane or cyclohexane, and the like.

In particular, in the case of using a polyfunctional vinyl aromatic hydrocarbon monomer as a polymerization monomer, it is preferable to use a polymerization solvent from the viewpoint of suppressing gelation. By using a polymerization solvent, it is difficult to generate gel, and more careful control in the polymerization process can be achieved, and it is easier to obtain the vinyl aromatic hydrocarbon resin (a) having the desired composition and physical properties.

The amount of the polymerization solvent to be used is not particularly limited, but from the viewpoint of controlling gelation, it is usually preferably 1 to 50 mass %, more preferably 5 to 25 mass % with respect to the entire composition in the polymerization reactor. within the range. By using 1-50 mass % of a polymerization solvent, suppression of gelation and high degree of polymerization process control can be achieved, whereby a vinyl aromatic hydrocarbon resin (a) excellent in industrial productivity and economy can be obtained.

In the polymerization step of the vinyl aromatic hydrocarbon resin (a), a radical agent such as an organic peroxide can be preferably used. Examples of free radical agents include, but are not limited to: 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, 2 ,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane, 1,1-bis(tert-amylperoxy)cyclohexane and other peroxyketals; hydroperoxide Hydrogen peroxides such as cumene and tert-butyl hydroperoxide; alkyl peroxides such as tert-butyl peroxyacetate and tert-amyl peroxy isononanoate; tert-butyl cumyl peroxide Dialkyl peroxides such as oxides, di-tert-butyl peroxide, dicumyl peroxide, and di-tert-hexyl peroxide; tert-butyl peroxyacetate, benzoic acid peroxy Peroxyesters such as tributyl, O,O-tert-butyl-O-isopropyl peroxymonocarbonate; O,O-tert-butyl-O-isopropyl peroxycarbonate, polyether Peroxycarbonates such as tetrakis(tert-butylperoxycarbonate); N,N'-azobis(cyclohexane-1-carbonitrile), N,N'-azobis(2-methylcarbonitrile) Butyronitrile), N,N'-azobis(2,4-dimethylvaleronitrile), N,N'-azobis[2-(hydroxymethyl)propionitrile], etc. These radical agents may be used alone or in combination of two or more.

Furthermore, in the polymerization step of the vinyl aromatic hydrocarbon resin (a), a chain transfer agent can be used to adjust the molecular weight of the vinyl aromatic hydrocarbon resin (a). Examples of the chain transfer agent include, but are not limited to, aliphatic thiol, aromatic thiol, pentaphenylethane, α-methylstyrene dimer, terpinolene, and the like.

The molecular weight of the vinyl aromatic hydrocarbon resin (a) can be controlled by adjusting the monomer concentration, the amount of a radical agent such as an organic peroxide, the presence or absence or amount of a chain transfer agent, and the like. Generally, when the amount of radical generation is reduced, the molecular weight is increased without using a chain transfer agent, and when the amount of radical generation is increased, the molecular weight is reduced by adding a chain transfer agent or increasing the amount.

As vinyl aromatic hydrocarbon resin (a), a commercial item can be used. For example, "PSJ-POLYSTYRENE", a product of PS JAPAN, can be exemplified by GPPS and HIPS. GPPS is transparent and HIPS is milky white. Either brand can be better used, but the following aspects should be noted: According to MFR, the tendency of performance is different. For MS resin, "PSJ-POLYSTYRENE SC004" or "PSJ-POLYSTYRENE MM290" manufactured by PS JAPAN, "Toyo MS MS200", "Toyo MS MS300", and "Toyo MS KS10" manufactured by Toyo Styrene Corporation can be exemplified. and so on as a better brand. These are all similar in refractive index to the block copolymer (b), and it is easy to obtain a transparent composition. Moreover, although the dispersion forms are not completely compatible, they exhibit uniform dispersion at the micron level, and can obtain excellent transparency and mechanical properties. It is an antistatic resin composition, so it can be preferably used.

(block copolymer (b)) The block copolymer (b) is a block copolymer containing a vinyl aromatic hydrocarbon monomer unit and a conjugated diene monomer unit, the vinyl aromatic hydrocarbon monomer unit is 30 to 90% by mass, and the conjugated diene The monomer unit is 70 to 10% by mass, and has at least one polymer block mainly composed of vinyl aromatic hydrocarbon monomer units. The polymer block mainly composed of vinyl aromatic hydrocarbon monomer units constituting the block copolymer (b) means a polymer block containing 90 mass % or more of vinyl aromatic hydrocarbon monomer units. In addition, the conjugated diene monomer unit constituting the block copolymer (b) may be contained as a conjugated diene polymer block containing only a single conjugated diene monomer unit, but also as a conjugated diene monomer unit. It is contained in the copolymer block of olefin monomer unit and vinyl aromatic hydrocarbon monomer unit. In the case of a copolymerization block, various copolymerization block structures such as a uniform random structure or a tapered structure (the composition ratio of the monomers vary along the chain) may be used. In addition, the block copolymer (b) may be a combination of two or more block copolymers having different average molecular weights, or a combination of two types of block copolymers with different copolymerization ratios of vinyl aromatic hydrocarbon monomer units and conjugated diene monomer units. more than one block copolymer. Moreover, the block copolymer (b) may contain another polymerizable monomer unit other than a vinyl aromatic hydrocarbon monomer unit and a conjugated diene monomer unit as needed.

The vinyl aromatic hydrocarbon monomer only needs to have an aromatic ring and a vinyl group in the molecule, for example, but not limited to: styrene, o-methylstyrene, m-methylstyrene, p-methylbenzene Ethylene, o-ethylstyrene, p-ethylstyrene, p-tert-butylstyrene, 2,4-dimethylstyrene, 1,3-dimethylstyrene, alpha-methylstyrene, alpha -Methyl-p-methylstyrene, vinylnaphthalene, vinylanthracene and 1,1-stilbene, etc. These vinyl aromatic hydrocarbon monomers may be used alone or in combination of two or more. Among these, styrene is preferable from the viewpoint of industriality and economy.

The conjugated diene monomer may be any diene as long as it has a pair of conjugated double bonds, for example, but not limited to: 1,3-butadiene, 2-methyl-1,3-butane Diene (isoprene), 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, etc. These conjugated diene monomers may be used alone or in combination of two or more. Among them, 1,3-butadiene and isoprene are preferred from the viewpoint of industrial availability and economical efficiency, and those with higher industrial availability or economical efficiency are preferred. From a viewpoint, 1,3-butadiene is more preferable.

The mass ratio of vinyl aromatic hydrocarbon monomer units and conjugated diene monomer units in the block copolymer (b) is vinyl aromatic hydrocarbon monomer units/conjugated diene monomer units=30/70～ 90/10. By making the ratio of each monomer unit into the said range, favorable antistatic property can be exhibited in the antistatic resin composition of this embodiment combined with the following donor-acceptor system molecular compound (c).

In the block copolymer (b), the range of the ratio of the mass % of the vinyl aromatic hydrocarbon monomer unit/conjugated diene monomer unit is 30/70 to 90/10 as described above. When the ratio of the vinyl aromatic hydrocarbon monomer units constituting the block copolymer (b) is less than 30% by mass, the elastic modulus as a single component is very low, so in order to use the block copolymer ( When the antistatic resin composition of b) is used as a packaging material for electronic parts, it is necessary to prepare a composition mainly containing the vinyl aromatic hydrocarbon resin as the component (a). However, since the ratio of vinyl aromatic hydrocarbon monomer units in the block copolymer (b) itself is low, the compatibility with the vinyl aromatic hydrocarbon resin as the component (a) is poor, and due to this influence, there are The dispersibility of the donor-acceptor system molecular compound (c) also tends to be poor. In the block copolymer (b), by setting the content of vinyl aromatic hydrocarbon monomer units to 30% by mass or more, a practically sufficient elastic modulus can be secured and compatibility with the component (a) is good. In addition, the dispersibility of the following (c) component is also excellent in the antistatic resin composition.

On the other hand, when the ratio of the vinyl aromatic hydrocarbon monomer units constituting the block copolymer (b) exceeds 90% by mass, even if the block copolymer (b) is set to 100% by mass, In the case of the base resin of the electrostatic resin composition, even if the vinyl aromatic hydrocarbon resin (a) is blended at an arbitrary ratio, even if 4 mass % of the donor-acceptor molecular compound (c) is blended, there is a surface resistivity Tendency to be difficult to descend.

The content of vinyl aromatic hydrocarbon monomer units and conjugated diene monomer units in the block copolymer (b) can be quantified by the methods described in the following examples. In addition, the content of these monomer units can be controlled by adjusting the addition amount and ratio of each monomer in the polymerization step of the block copolymer (b).

Although it does not specifically limit as a block copolymer (b), For example, the block copolymer which has the block structure represented by following general formula (1)-(7) is mentioned. S1-B1-S2・・・(1) S1-B/S1-S2・・・(2) S1-B1-S2-B2・・・(3) S1-B/S1-S2-B/S2・・・(4) S1-B/S1-B/S2-S2・・・(5) S1-B1-B/S1-S2・・・(6) S1-B1-S2-B2-S3・・・(7)

In the above general formulas (1) to (7), S1, S2 and S3 respectively represent a polymer block mainly composed of vinyl aromatic hydrocarbon monomer units, and B1 and B2 respectively represent a conjugated diene monomer unit as a polymer block. The polymer block (B) of the main body, B/S1 and B/S2 represent random copolymer blocks ( B/S).

Furthermore, the numbers assigned to S, B and B/S in the above general formulae (1) to (7) are used to identify the polymer block, polymer block (B) and random copolymer block ( The number of B/S), the molecular weight (degree of polymerization) or the copolymerization ratio of the respective blocks with different numbers may be the same or different. In addition, the chain structure of the random copolymer block (B/S) may be a uniform random block or a tapered block (the composition ratio changes slowly along the chain).

Moreover, the block copolymer (b) may be either a linear polymer or a branched polymer. As a method of obtaining a branched polymer, the method of carrying out a coupling reaction of a polymerization terminal, the method of branching from the initial stage of a polymerization using a polyfunctional initiator, etc. are mentioned, for example.

In addition, as a preferable application of the antistatic resin composition of the present embodiment, electronic parts packaging materials can be mentioned, and in view of this application, the block copolymer (b) has a variety of required mechanical properties. It is preferable that at least one or more of the polymer blocks S mainly composed of vinyl aromatic hydrocarbon monomer units are at least two. In addition, in this specification, "the polymer block which mainly consists of vinyl aromatic hydrocarbon monomer units" may be described as "polymer block S".

<The peak molecular weight and molecular weight distribution of the block copolymer (b)> The antistatic resin composition of the present embodiment preferably has at least one molecular weight distribution curve measured by gel permeation chromatography (GPC measurement) in the range of molecular weight 30,000 or more and 300,000 or less. Peak molecular weight derived from block copolymer (b). Thereby, the balance between the mechanical properties and the moldability of the antistatic resin composition of the present invention becomes better. From the same viewpoint, the peak molecular weight derived from the block copolymer (b) is more preferably in the range of 40,000 or more and 250,000 or less, and more preferably in the range of 50,000 or more and 210,000 or less. In addition, the peak molecular weight of the block copolymer (b) can be measured by the method described in the following Example.

<Molecular weight distribution (Mw/Mn) of block copolymer (b)> The molecular weight distribution (Mw/Mn) of the block copolymer (b) is not particularly limited. A block copolymer (b) with a larger molecular weight distribution (Mw/Mn) can be obtained by associating the polymerization-active ends of a part of the polymers by the following coupling agents and the like to have different molecular weight combinations.

Furthermore, by adding an appropriate amount of alcohol such as ethanol in the middle of the polymerization to stop the polymerization of a part of the polymer, a block copolymer (b) which is a mixture of different molecular weights can be obtained. For example, the polymerization of a part of the polymer can be stopped by adding a molar equivalent of alcohol such as ethanol that is less than the molar number of the polymerization initiator in the polymerization system, so that a molecular weight having a plurality of peak molecular weights can be obtained. Block copolymer (b) with larger distribution (Mw/Mn).

<Number average molecular weight (Mn) of polymer block S> The number-average molecular weight (Mn) of the polymer block S mainly composed of vinyl aromatic hydrocarbon monomer units in the block copolymer (b) is preferably 10,000 to 60,000, more preferably 15,000 to 50,000, still more preferably 20,000 to 40,000. By making the number average molecular weight (Mn) of the polymer block S within the above-mentioned range, a molded product (eg, a styrene-based resin sheet) having more excellent mechanical properties and favorable molded appearance in a well-balanced manner can be obtained. The number average molecular weight (Mn) of the polymer block S in the block copolymer (b) can be controlled by adjusting the feeding amount (feeding amount) of the vinyl aromatic hydrocarbon monomer relative to the polymerization initiator.

The block copolymer (b) contains at least one polymer block S mainly composed of vinyl aromatic hydrocarbon monomer units. It is preferable to contain two or more polymer blocks S, and it is more preferable that at least one polymer block S exists at the end of the polymer chain. Regarding the molecular weight of the polymer block S, when two or more are contained, the structure can be controlled independently of each other. In addition, the number average molecular weight (Mn) of the said polymer block S is shown as the total number average molecular weight of all the polymer blocks S in the block copolymer (b). For example, in the case of the block copolymer (b) of the S1-B/S1-S2 structure, the average molecular weight of the polymer block S is the number average molecular weight of the sum of S1 and S2.

The number-average molecular weight of the polymer block S in the block copolymer (b) can be determined by gel permeation chromatography (GPC) by measuring the component S of the polymer block (the vinyl aromatics with an average degree of polymerization of about 30 or less). The above-mentioned polymer block S component is obtained by using osmium tetroxide as a catalyst and using tertiary butyl hydroperoxide to oxidatively decompose the block copolymer (IM KOLTHOFF , et al., J. Polym. Sci. 1, 429 (1946) by the method described in). Specifically, it can be measured by the method described in Examples.

<Molecular weight distribution of polymer block S (Mw/Mn)> The molecular weight distribution (Mw/Mn) of the polymer block S mainly composed of vinyl aromatic hydrocarbon monomer units in the block copolymer (b) is preferably 1.5 to 4.0, more preferably 1.6 to 3.6, and more preferably Preferably, it is 1.7 to 3.2. By making the molecular weight distribution (Mw/Mn) of the polymer block S within the above-mentioned range, the molding processability of the antistatic resin composition of the present embodiment and the block copolymer (b) and the vinyl aromatic hydrocarbon The balance of the dispersibility of the resin (a) becomes better, and there is a tendency to obtain a molded product having a favorable molding appearance, which is less likely to produce flow lines during molding and other defects in molding appearance.

The molecular weight distribution (Mw/Mn) of the polymer blocks S in the block copolymer (b) is the overall average molecular weight distribution of all the polymer blocks S in the block copolymer (b). For example, in the case of the block copolymer (b) of the S1-B/S1-S2 structure, the average molecular weight of the polymer block S is the average molecular weight distribution of S1 and S2. It can be controlled by adjusting the feeding amount (feeding amount) of the vinyl aromatic hydrocarbon monomer relative to the polymerization initiator by making the chain length of each polymer block S present at two or more close to or apart.

As another method for controlling the molecular weight distribution (Mw/Mn) of the polymer block S in the block copolymer (b), for example, in the polymerization step of the polymer block S, adding less than A method of stopping the polymerization of a part of the polymer by using an alcohol such as ethanol in a molar amount of the agent. The polymer block S thereby becomes a mixture comprising two different molecular weights. The molecular weight distribution of the polymer blocks S can also be controlled by thus preparing a block copolymer (b) having two or more polymer blocks S having different chain length distributions. Specifically, the molecular weight distribution (Mw/Mn) of the polymer block S in the block copolymer (b) can be obtained by the method described in the following examples.

<Method for producing block copolymer (b)> A well-known technique can be utilized for the manufacturing method of the block copolymer (b) which comprises the antistatic resin composition of this embodiment. As a representative prior art, a method of block-copolymerizing a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer using an anionic polymerization initiator such as an organolithium compound in a hydrocarbon solvent can be exemplified. For example, Japanese Patent Publication No. 36-19286, Japanese Patent Publication No. 43-17979, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 49-36957, and Japanese Patent Publication No. 57- Manufactured by the method described in Japanese Patent Publication No. 49567 and Japanese Patent Publication No. Sho 58-11446.

The block copolymer (b) can be obtained by copolymerizing a vinyl aromatic hydrocarbon monomer and a conjugated diene monomer in a hydrocarbon solvent. As the hydrocarbon solvent for producing the block copolymer (b), a previously known hydrocarbon solvent can be used. For example, but not limited to: n-butane, isobutane, n-pentane, n-hexane, n-heptane, n-octane and other aliphatic hydrocarbons; cyclopentane, methylcyclopentane, cyclohexane , alicyclic hydrocarbons such as methylcyclohexane, cycloheptane, and methylcycloheptane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene. These hydrocarbon solvents may be used alone or in combination of two or more. Among these, in the case of using an organolithium initiator, n-hexane and cyclohexane are usually used, among which cyclohexane is the most commonly used in industry and can be preferably used.

Although it does not specifically limit as a polymerization initiator, For example, the polymerization initiator which shows anionic polymerization activity with respect to a conjugated diene monomer and a vinyl aromatic hydrocarbon monomer can be preferably used. Specific examples thereof include alkali metal compounds such as aliphatic hydrocarbon alkali metal compounds, aromatic monomeric alkali metal compounds, and organic amine-based alkali metal compounds.

Although it does not specifically limit as an alkali metal used for an alkali metal compound, For example, lithium, sodium, potassium etc. are mentioned. Examples of preferable alkali metal compounds include, but are not limited to, aliphatic and aromatic hydrocarbon lithium compounds having 1 to 20 carbon atoms, compounds containing one lithium per molecule, or compounds containing multiple lithium compounds per molecule. Dilithium compounds, trilithium compounds, and tetralithium compounds of lithium. Specific examples of such alkali metal compounds include, but are not limited to: n-propyllithium, n-butyllithium, 2-butyllithium, 3-butyllithium, hexamethylenedilithium, butadienyldilithium Lithium, isoprenyldilithium, the reaction product of diisopropenylbenzene and 2-butyllithium, and the reaction product of divinylbenzene and 2-butyllithium and a small amount of 1,3-butadiene, etc.

Furthermore, organic alkali metal compounds disclosed in foreign patents such as US Pat. No. 5,708,092, UK Pat. No. 2,241,239, and US Pat. No. 5,527,753 can also be used. These can be used alone or in combination of two or more. Among these, n-butyllithium is preferred.

As the production process of the block copolymer (b), by adjusting the addition ratio of the vinyl aromatic hydrocarbon monomer and the conjugated diene monomer as the polymerization raw materials, the content of the finally obtained block copolymer (b) can be controlled. The content of vinyl aromatic hydrocarbon monomer units and the content of conjugated diene monomer units.

In addition, as an option for the manufacturing process of the block copolymer (b), for example, a process of additionally adding a polymerization initiator from the middle of the polymerization, and having as many as two or more reactive sites by adding a small amount of The process of partially coupling reaction with functional monomers, or the process of continuing polymerization by adding monomers again after adding alcohol, water, etc. which have not reached the active point of polymerization during polymerization. By appropriately selecting such a process, a block copolymer (b) in which a plurality of components having different molecular weights are present can be produced.

As a method for producing a copolymer block comprising vinyl aromatic hydrocarbon monomer units and conjugated diene monomer units, there may be mentioned continuous supply of a mixture of vinyl aromatic hydrocarbon monomers and conjugated diene monomers A method of performing polymerization in a polymerization system, a method of copolymerizing a vinyl aromatic hydrocarbon monomer and a conjugated diene monomer using a polar compound or a randomizer, and the like.

Examples of polar compounds and randomizers include, but are not limited to, ethers such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol dibutyl ether; triethylamine, tetramethylethylenediamine, etc. Amines; thioethers; phosphines; phosphamides; alkylbenzene sulfonates; potassium or sodium alkoxides, etc.

As the polymerization temperature in the polymerization step of the block copolymer (b), the optimum conditions vary depending on the polymer structure, but in the case of anionic polymerization using a polymerization initiator, it is usually -10°C to 150°C , preferably in the range of 40°C to 120°C. In addition, the time required for the polymerization is usually within 48 hours, preferably within a range of 1 hour to 10 hours. In addition, the environment of the polymerization system is preferably replaced with an inert gas such as nitrogen. The polymerization pressure is not particularly limited as long as it is performed within a pressure range sufficient to maintain the monomer and the polymerization solvent as a liquid layer within the above-mentioned polymerization temperature range. Furthermore, it is preferable to take care not to accidentally mix impurities such as water, oxygen, carbon dioxide, etc., which deactivate the polymerization initiator and the active polymer, into the polymerization system.

When the block copolymer (b) contains random copolymer blocks, the mixture of vinyl aromatic hydrocarbon monomer and conjugated diene monomer can be continuously supplied to the polymerization system for polymerization and/or use. A polar compound or randomizing agent copolymerizes a vinyl aromatic hydrocarbon monomer and a conjugated diene monomer, and the like.

In the case of using an organic alkali metal as a polymerization initiator in the production of the block copolymer (b), when stopping the polymerization reaction, a coupling reaction in which two or more molecules are bonded and stopped can be preferably used. Coupling Reaction The following exemplified coupling agents can be added to the polymerization system. In addition, by adjusting the amount of the coupling agent added, only a part of the polymer in the polymerization system can be coupled, and by coexisting the uncoupled polymer and the coupled polymer, a mosaic having two or more peaks in the molecular weight distribution can be produced. segmented copolymer (b).

It does not specifically limit as a coupling agent which can be used suitably for manufacture of a block copolymer (b), For example, the arbitrary coupling agent of bifunctional or more may be mentioned. Specific examples include: tetraglycidyl-m-xylylenediamine, tetraglycidyl-1,3-bisaminomethylcyclohexane, tetraglycidyl-p-phenylenediamine, tetraglycidyldiamine Diphenylmethane, Diglycidylaniline, Diglycidyl-o-toluidine, γ-glycidyloxyethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidyloxy Butyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropyltripropoxysilane, γ-glycidoxypropyltributoxysilane, etc. Silane compounds containing amine groups. Moreover, as other coupling agents, for example, 1-[3-(triethoxysilyl)-propyl]-4-methylpiperazane, 1-[3-(diethoxyethylsilane) yl)-propyl]-4-methylpiperidine, 1-[3-(trimethoxysilyl)-propyl]-3-methylimidazolidine, 1-[3-(diethoxyethyl) Silyl)-propyl]-3-ethylimidazolidine, 1-[3-(triethoxysilyl)-propyl]-3-methylhexahydropyrimidine, 1-[3-(dimethoxysilyl) methylsilyl)-propyl]-3-methylhexahydropyrimidine, 3-[3-(tributoxysilyl)-propyl]-1-methyl-1,2,3,4- tetrahydropyrimidine, 3-[3-(dimethoxymethylsilyl)-propyl]-1-ethyl-1,2,3,4-tetrahydropyrimidine, 1-(2-ethoxyethyl) (2-{3-[3-(trimethoxysilyl)-propyl]-tetrahydropyrimidine-1- Silane compounds containing silyl groups such as ethyl}-ethyl) dimethylamine.

Moreover, as another coupling agent, γ-glycidoxypropyltriphenoxysilane, γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyl Ethyldimethoxysilane, gamma-glycidoxypropylethyldiethoxysilane, gamma-glycidoxypropylmethyldiethoxysilane, gamma-glycidoxypropylmethyl Dipropoxysilane, γ-glycidoxypropylmethyldibutoxysilane, γ-glycidoxypropylmethyldiphenoxysilane, γ-glycidoxypropyldimethylmethyl Oxysilane, γ-glycidoxypropyldiethylethoxysilane, γ-glycidoxypropyldimethylethoxysilane, γ-glycidoxypropyldimethylphenoxy Silane, γ-glycidoxypropyldiethylmethoxysilane, γ-glycidoxypropylmethyldiisopropenyloxysilane, bis(γ-glycidoxypropyl)dimethoxysilane Silane, bis(γ-glycidoxypropyl)diethoxysilane, bis(γ-glycidoxypropyl)dipropoxysilane, bis(γ-glycidoxypropyl)dibutoxy Silane, bis(γ-glycidoxypropyl)diphenoxysilane, bis(γ-glycidoxypropyl)methylmethoxysilane, bis(γ-glycidoxypropyl)methyl Ethoxysilane, bis(γ-glycidoxypropyl)methylpropoxysilane, bis(γ-glycidoxypropyl)methylbutoxysilane, bis(γ-glycidoxy Silane compounds containing glycidyloxy groups such as propyl) methylphenoxysilane and tris(γ-glycidoxypropyl)methoxysilane. Moreover, as another coupling agent, for example, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxy Alkylmethyltrimethoxysilane, γ-methacryloyloxyethyltriethoxysilane, bis(γ-methacryloyloxypropyl)dimethoxysilane, tris(γ-methacrylic acid) Silane compounds containing methacryloyloxy groups such as oxypropyl) methoxysilane. Moreover, as another coupling agent, for example, β-(3,4-epoxycyclohexyl)ethyl-trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-triethoxy Silane, β-(3,4-Epoxycyclohexyl)ethyl-tripropoxysilane, β-(3,4-Epoxycyclohexyl)ethyl-tributoxysilane, β-(3, 4-Epoxycyclohexyl)ethyl-triphenoxysilane, β-(3,4-epoxycyclohexyl)propyl-trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl - Methyldimethoxysilane, β-(3,4-Epoxycyclohexyl)ethyl-ethyldimethoxysilane, β-(3,4-Epoxycyclohexyl)ethyl-ethyldi Ethoxysilane, β-(3,4-Epoxycyclohexyl)ethyl-methyldiethoxysilane, β-(3,4-Epoxycyclohexyl)ethyl-methyldipropoxysilane , β-(3,4-Epoxycyclohexyl)ethyl-methyldibutoxysilane, β-(3,4-Epoxycyclohexyl)ethyl-methyldiphenoxysilane, β-( 3,4-Epoxycyclohexyl)ethyl-dimethylmethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-diethylethoxysilane, β-(3,4- Epoxycyclohexyl)ethyl-dimethylethoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylpropoxysilane, β-(3,4-epoxycyclohexyl) ) ethyl-dimethylbutoxysilane, β-(3,4-epoxycyclohexyl)ethyl-dimethylphenoxysilane, β-(3,4-epoxycyclohexyl)ethyl- Silane compounds containing epoxycyclohexyl such as diethylmethoxysilane and β-(3,4-epoxycyclohexyl)ethyl-methyldiisopropenyloxysilane. As other coupling agents, 1,3-dimethyl-2-imidazolidinone, 1,3-diethyl-2-imidazolidinone, N,N'-dimethylpropionamide, N - Methylpyrrolidone.

Furthermore, in the case where the above-mentioned coupling agent is subjected to an addition reaction with the active terminal of the block copolymer (b), the structure of the active terminal of the block copolymer (b) is not limited in any way. From the viewpoint of the mechanical strength of the electrostatic resin composition, etc., the active terminal of the block mainly composed of the vinyl aromatic hydrocarbon monomer is preferable. The amount of the coupling agent to be used is preferably 0.1 equivalent or more and 10 equivalents or less, more preferably 0.5 equivalent or more and 4 equivalents or less, based on 1 equivalent of the active terminal of the block copolymer (b). The coupling agent may be used alone or in combination of any two or more.

(Donor-Acceptor Molecular Compound (c)) The antistatic resin composition of this embodiment contains a donor-acceptor system compound (c). The so-called donor-acceptor system molecular compound (c) refers to a molecular compound having both a donor and an acceptor. The donor system here refers to an electron-donating group, and the acceptor system refers to an electron-withdrawing group. Specifically, the donor-acceptor molecular compound (c) is preferably an organoboron compound represented by the above-mentioned general formula (1) as a donor component and the following general formula as an acceptor component (1) A compound obtained by mixing each of the organic nitrogen compounds shown on the lower side.

[hua 2]

In the above general formula (1), R ₁ and R ₂ are independently CH ₃ (CH ₂ ) _n -CO-OCH ₂ (n is an integer of 12 to 22) or HOCH ₂ , and at least one of them is CH ₃ (CH 2 ) ₂ ) _n- CO-OCH ₃ (n is an integer of 12-22). R ₃ and R ₄ are each independently any one selected from the group consisting of CH ₃ , C ₂ H ₅ , HOCH ₂ , HOC ₂ H ₄ and HOCH ₂ CH(CH ₃ ). Here, "δ+" in the general formula (1) means that there is polarity in the covalent bond in the molecule, (+) means that the electron-donating property of the oxygen atom becomes stronger, and (-) means that the electron-withdrawing property of the boron atom becomes stronger. Strong, "→" indicates the path of electrons being pulled closer, "---" indicates the state where the bonding force between atoms is weakened.

The donor component containing the above-mentioned organoboron compound moiety represented on the upper stage side of the above-mentioned general formula (1) has at least one linear hydrocarbon group having 12 to 22 carbon atoms, and also contains the above-mentioned general formula (1) on the lower stage side. The acceptor component of the above-mentioned organic nitrogen compound part is that one N-substituent is a group bound to the end of a straight-chain hydrocarbon group having 12 to 22 carbon atoms via an amide bond, and the remaining two N-substituents are Tertiary amine of hydrocarbon group or hydroxy hydrocarbon group with 1 to 3 carbon atoms.

There are several brands of donor-acceptor molecular compounds manufactured and sold by BORON LABORATRY, especially the trade name "BIOMICELLE BN-105" is a representative example.

The donor-acceptor molecular compound (c) used in the antistatic resin composition of the present embodiment is added to a resin to prepare a composition, thereby exhibiting an antistatic effect and exhibiting antistatic properties. The performance of the donor-acceptor molecular compound (c) is affected by the antistatic performance of the compound (c) depending on the polymer type or composition ratio of the prepared resin composition, the melt viscosity of each component, and the like. From the viewpoint of the performance of antistatic properties, the suitable composition range of the donor-acceptor system molecular compound (c), especially the lower limit value thereof, is based on the vinyl aromatic hydrocarbon resin (a) and the block copolymer (b) The mass ratio and the MFR value of each component vary.

That is, the antistatic resin composition of this embodiment satisfies any one of the following conditions (i) to (iv). <Condition (i)> When the sum of the above-mentioned (a) component and the above-mentioned (b) component is taken as 100% by mass, the above-mentioned (a) component is more than 0% by mass and 30% by mass or less, and the above-mentioned (b) component is 70% by mass or more and not more than 70% by mass. When it reaches 100% by mass, Regardless of the numerical values of MFRa and MFRb, when the total of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is 100% by mass, the above-mentioned (c) component is 0.5% by mass or more and 5% by mass or less. . <Condition (ii)> When the sum of the said (a) component and the said (b) component is made into 100 mass %, the said (a) component is more than 30 mass % and 50 mass % or less, and the said (b) component is less than 70 mass % and In the case of 50% by mass or more, it shall be MFRa＜MFRb・・(Formula 1) When the relationship between the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100 mass %, the above-mentioned (c) component is 0.5 mass % or more and 5 mass % or less, which is MFRa≧MFRb・・(Formula 2) In the case of the relationship, when the total of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is set to 100 mass %, the above-mentioned (c) component is 0.9 mass % or more and 5 mass % or less. <Condition (iii)> When the sum of the above-mentioned (a) component and the above-mentioned (b) component is taken as 100 mass %, the above-mentioned (a) component is more than 50 mass % and 70 mass % or less, and the above-mentioned (b) component is less than 50 mass % and In the case of 30% by mass or more, Satisfy MFRa＜MFRb・・(Formula 1) When the total of the said (a) component, the said (b) component, and the said (c) component is made into 100 mass %, the said (c) component is 0.9 mass % or more and 5 mass % or less. <Condition (iv)> When the sum of the above-mentioned (a) component and the above-mentioned (b) component is taken as 100% by mass, the above-mentioned (a) component is more than 70% by mass and 81% by mass or less, and the above-mentioned (b) component is less than 30% by mass and 19% by mass or more, Satisfy MFRa＜MFRb・・(Formula 1) When the total of the said (a) component, the said (b) component, and the said (c) component is made into 100 mass %, the said (c) component is 4 mass % or more and 5 mass % or less.

In this way, as the composition ratio of the block copolymer (b) increases, the MFR value (MFRb) of the block copolymer (b) is higher than the MFR value (MFRa) of the vinyl aromatic hydrocarbon resin (a). In this case, it was confirmed that the reduction of the surface resistivity was achieved by adding a smaller amount of the donor-acceptor molecular compound (c), and there was a tendency that the antistatic property was likely to be exhibited.

(Other additives can be formulated in the antistatic resin composition) The antistatic resin composition of this embodiment can contain arbitrary additives within the range which does not impair the effect of this embodiment. As an additive, it can be used in the formulation of resin or rubber-like polymer, such as but not limited to: calcium carbonate, magnesium carbonate, silicon dioxide, zinc oxide, carbon black and other inorganic fillers; Higher alcohols such as stearyl alcohol, fatty acids such as palmitic acid, stearic acid, and behenic acid, fatty acid metal salts such as zinc stearate, calcium stearate, magnesium stearate, magnesium behenate, and hydrogenated magnesium ricinoleate ; Lubricants and mold release agents such as fatty amides such as mustardamide and ethylene distearylamine; softeners and plasticizers such as paraffin oil, processing oil, organopolysiloxane, mineral oil, etc.; hindered phenol Heat stabilizers and antioxidants of phosphorus-based and phosphorus-based systems: hindered amine-based light stabilizers; benzotriazole-based UV absorbers: flame retardants; organic fibers, glass fibers, carbon fibers, metal whiskers and other reinforcing agents; organic pigments, Inorganic pigments, organic dyes and other colorants.

[Manufacturing method of antistatic resin composition] The method for producing the antistatic resin composition of the present embodiment is not particularly limited. For example, the following method may be exemplified: adding ethylene to the block copolymer (b) and the donor-acceptor molecular compound (c) The aromatic hydrocarbon-based resin (a) is dry blended at room temperature, then heated, melted and kneaded by a twin-screw extruder, and the heated and melted antistatic resin composition is extruded from a die nozzle in a linear shape to make it The granulated composition was obtained by granulating again through a cooling bath. In the case of heat-melting kneading, there is no particular limitation as long as it is a kneader for thermoplastic resins that can be heated and melted. mixers such as mixers or twin-shaft extruders. Moreover, not only the strand cutting method using a cooling bath, but also a thermal cutting method, an underwater cutting method, or the like can be preferably used according to the purpose.

In order to fully utilize the antistatic property which the donor-acceptor system molecular compound (c) has, it is preferable to manufacture an antistatic resin composition by the following manufacturing method. That is, the antistatic resin composition of the present embodiment is obtained through the following steps (I) and (II), and the step (I) is to combine the block copolymer (b) with the donor-acceptor system molecular compound (c). ) The composition ratio of the donor-acceptor system molecular compound (c) is melt-kneaded so that the composition ratio of the molecular compound (c) is 5% by mass to 20% by mass, to produce a master batch with a high concentration of the component (c), and step (II) is to mix the above-mentioned master batch. It is kneaded with vinyl aromatic hydrocarbon resin (a) and/or block copolymer (b) to dilute the master batch.

By adopting the production method through the above-mentioned master batch, the dispersibility of the donor-acceptor molecular compound (c) in the antistatic resin composition is remarkably improved, and the desired effect can be efficiently expressed with a smaller addition amount. With the reduced surface resistivity, the balance of mechanical properties and antistatic properties of the obtained antistatic resin composition becomes optimal. For the antistatic resin composition of this embodiment, it is important to use a resin kneader to sufficiently disperse the donor-acceptor molecular compound (c) in the resin matrix containing the component (b), or to contain the component (a) ) and the resin matrix of the component (b), the recommended production method is: after temporarily preparing a high concentration master batch, the desired antistatic resin composition is obtained by diluting it.

[Electronic parts packaging material] The molded body of the antistatic resin composition of this embodiment is preferable as an electronic component packaging material. As an electronic component packaging material, a carrier tape, a conveyance tray, a material tube, etc. are mentioned, for example. The electronic parts packaging material of this embodiment may be single-layered or multi-layered in its wall thickness direction. From the viewpoint of economy, among the electronic parts packaging material of this embodiment, the antistatic of this embodiment is generally used. The synthetic resin composition is limited to the front layer or the front and back layers of electronic parts packaging materials. On the surface layer portion on the side in contact with the electronic component product, a multilayer sheet having a layer containing the antistatic resin composition of the present embodiment of several tens of microns is formed, and thereafter, vacuum forming or compression forming is performed to form a container. Recesses (also known as grooves or embossing) in electronic components. For electronic parts packaging materials used for stacking such as conveying trays, the back side is also in contact with electronic parts products, so it is generally preferable to use not only the front layer but also the back layer of the electronic parts provided with the antistatic resin composition of the embodiment packaging material.

Even if the antistatic resin composition of the present embodiment adds the donor-acceptor molecular compound (c), the transparency of the base resin containing the components (a) and (b) is not greatly impaired. By selecting the composition of the component (a) and the component (b) to be used, a packaging material for electronic parts with good transparency can be obtained.

The thickness of the electronic component packaging material of the present embodiment or the thickness of each layer that constitutes it is not particularly limited, and may be appropriately designed depending on the situation according to the electronic components to be the object of the packaging material. When the electronic component packaging material of the present embodiment is an extrusion molded product, the overall wall thickness is preferably 50 μm to 4 mm, more preferably 0.1 mm to 2.0 mm, and more preferably 0.1 mm to 1.5 mm. mm, and more preferably 0.2 mm to 1.2 mm. When the end use is a carrier tape, it tends to be thin, and on the other hand, when it is a conveyance tray, it tends to be thick. The thickness of the layer containing the antistatic resin composition in contact with the electronic component product is preferably 5 μm to 1 mm, more preferably 10 μm to 0.1 mm, and still more preferably 15 μm to 50 μm. When secondary processing such as vacuum molding or compression molding is performed from the raw material sheet, there are also parts where the embossed side surface and the like are stretched to become thinner, so the layer containing the antistatic resin composition in the raw material sheet is preferred. It has a certain degree of thickness in advance.

The electronic parts packaging material of the present embodiment can be mixed with at least one layer of the intermediate layer to realize the circulation within the step, and the material obtained by pulverizing the corner material of the sheet can be used. In this case, it is usually a method of blending a new material and a recycled material at an arbitrary ratio, but the recycled material may be used alone. The recycled material is preferably a similar composition produced from the same production line, but different resin compositions produced from other series may also be blended within the scope of not impairing the effect of the present embodiment.

In addition, the electronic component packaging material of the present embodiment may be subjected to surface treatment such as printing, discharge treatment such as corona discharge or glow discharge, and acid treatment on the surface thereof without departing from the gist of the present invention.

[Characteristics of Electronic Parts Packaging Material] (Surface Resistivity) The surface resistivity of the antistatic resin composition and the electronic parts packaging material obtained by molding the antistatic resin composition is 1×10 ¹² Ω/□ or less. The surface resistivity of a resin composition or a molded product containing only components (a) and (b) without compounding the donor-acceptor molecular compound (c) generally exhibits an ^{insulator with a surface resistivity of 1×10 16} Ω/□ or more. The effect that the surface resistivity can be 1×10 ¹² Ω/□ or less is achieved by preparing the donor-acceptor molecular compound (c). However, if it is the vinyl aromatic hydrocarbon resin as the component (a) alone, even if the donor-acceptor molecular compound (c) is formulated, it is difficult to bring out its performance, and the block copolymer as the component (b) is used. existence is indispensable. The surface resistivity of electronic parts packaging material does not depend on the molding method or the shape of the product, and is only determined by the resin composition of the surface part that is in contact with the electronic parts. Therefore, the surface resistivity of the electronic component packaging material is the same value as the surface resistivity of the antistatic resin composition directly in contact with the electronic component, and there is interchangeability. The surface resistivity can be measured by the method described in the Examples, for example, it can be measured using the simple-type surface resistivity meter "ST-3" by SIMCO JAPAN Co., Ltd. product. Preferably, the sample is formed into a sheet shape, and the measurement is performed after standing (for example, 24 hours) in a constant temperature chamber at 23° C. and a humidity of 50%. The surface resistivity of the extruded sheet samples can be the average of the measured values in the direction of extrusion (MD) and the direction perpendicular to extrusion (TD) for each of the front and back sides.

(fog value) The antistatic resin composition and the electronic component packaging material of the present embodiment may be preferably visible depending on the type of components to be packaged, etc., and by having transparency, it can be adapted to a wide range of applications. For example, there are not many cases where visibility is required for conveying tray applications, but there are many cases where visibility is required for carrier tape applications, and transparency is preferable. The transparency shown in the examples is represented by the haze value measured by using a 1 mm-thick flat plate produced by injection molding the antistatic resin composition in accordance with ISO14782. The area of haze value with visibility (electronic parts whose contents can be seen through the packaging material) is 20% or less, and the smaller the haze value, the closer to zero, the higher the visibility. The fog value of the contents can be clearly seen below 4.0%, and if the fog value is below 2.0%, even the outline of the contents can be seen.

In order to reduce the haze value of the antistatic resin composition of the present embodiment and improve transparency, each component monomer of the vinyl aromatic hydrocarbon resin (a) and the block copolymer (b) needs to have transparency. , and the refractive indices of the vinyl aromatic hydrocarbon resin (a) and the block copolymer (b) are close to each other. Specifically, when the difference in refractive index is 0.004 or less, the transparency becomes good, and the haze value can be 4.0% or less.

The haze value of the antistatic resin composition of the present embodiment is the value measured by the injection plate as described above, and the actual electronic parts packaging material is often formed by extrusion molding. The dispersion state of the structure, or the polishing state of the roll temperature, the gap between the rolls, or the mirror surface of the roll surface, etc., the extrusion surface changes, and the haze value also changes. Furthermore, in the case of a multilayer molded sheet including a surface layer and an intermediate layer, the transparency of the electronic component packaging material itself is affected by the transparency of each layer. [Example]

Hereinafter, the present embodiment will be described in more detail by way of specific examples and comparative examples. In addition, this embodiment is not limited by the following examples at all.

(Vinyl aromatic hydrocarbon resin (a) and donor-acceptor molecular compound (c) used in Examples and Comparative Examples) The vinyl aromatic hydrocarbon resins (a)-1 to 8 and the donor-acceptor system molecular compound (c-1) were obtained and used by commercially available ones. These manufacturers, brand names, and categories are disclosed in the following [Table 1], and the MFR value (referred to as MFRa in Table 1) of the component (a) is also listed in the table.

[Table 1] (a) Ingredient or (c) Ingredient (a)-1 (a)-2 (a)-3 (a)-4 (a)-5 (a)-6 (a)-7 (c)-1 manufacturer PS JAPAN PS JAPAN PS JAPAN PS JAPAN PS JAPAN Toyo Styrene Toyo Styrene BORON LABORATRY brand name SGP10 HF77 475D SC004 MM290 MS200NT KS10 BIOMICELLE BN-105 category (a1) GPPS (a1) GPPS (a2) HIPS (a3) MS resin (a3) MS resin (a3) MS resin (a3) MS resin Donor-Acceptor Molecular Compounds Melt flow rate MFRa (200℃*5 kg) 1.9 7.5 2.0 6.5 0.7 1.6 18 -

(Melt flow rate (MFRa) of vinyl aromatic hydrocarbon resin (a)) The MFR of the component (a) used the value disclosed as a physical property table. The measurement standard is based on ISO1133, and is measured at a temperature of 200° C. and a load of 5 kgf. The same criteria and the same conditions as the MFRb of the block copolymer (b) described below are used.

(block copolymer (b)) [Production Examples 1 to 8] Regarding the block copolymer (b), each of the block copolymers (b)-1 to 8 was produced according to the following production examples.

[Production Example 1] In a nitrogen atmosphere, 0.08 parts by mass of n-butyllithium and 0.015 parts by mass of tetramethylmethylene diamine were added to a cyclohexane solution containing 20 parts by mass of styrene at a concentration of 25% by mass, and the mixture was heated at 80°C. Aggregate for 20 minutes. Next, a cyclohexane solution containing 14 parts by mass of 1,3-butadiene and 10 parts by mass of styrene at a concentration of 25% by mass was continuously added to the polymerization solution for 30 minutes, and polymerized at 80°C. Next, a cyclohexane solution containing 16 parts by mass of 1,3-butadiene and 10 parts by mass of styrene at a concentration of 25% by mass was continuously added to the polymerization solution for 30 minutes, and polymerized at 80°C. Next, a cyclohexane solution containing 30 parts by mass of styrene at a concentration of 25 mass % was added to the polymerization solution, and the solution was polymerized at 80° C. for 30 minutes.

Then, in order to completely stop the polymerization, ethanol was added to the reactor in an equal molar amount with respect to n-butyllithium, and 2-tertiary butyl acrylate was added as a heat stabilizer with respect to 100 parts by mass of the block copolymer. 0.4 part by mass of base-6(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl ester, and then the solvent was removed, whereby the block copolymer (b)-1 was recovered .

[Manufacturing example 2] In a nitrogen atmosphere, 0.08 parts by mass of n-butyllithium was added to a cyclohexane solution containing 31 parts by mass of styrene at a concentration of 25% by mass, and the mixture was polymerized at 80° C. for 20 minutes. Next, a cyclohexane solution containing 21 parts by mass of 1,3-butadiene and 20 parts by mass of styrene at a concentration of 25% by mass was continuously added to the polymerization solution for 30 minutes, and polymerized at 80°C. Next, a cyclohexane solution containing 2 parts by mass of 1,3-butadiene and 6 parts by mass of styrene at a concentration of 25% by mass was continuously added to the polymerization solution for 30 minutes, and polymerized at 80°C. Next, a cyclohexane solution containing 20 parts by mass of styrene at a concentration of 25 mass % was added to the polymerization solution, and the solution was polymerized at 80° C. for 30 minutes.

Then, in order to completely stop the polymerization, ethanol was added to the reactor in an equal molar amount with respect to n-butyllithium, and 2-tertiary butyl acrylate was added as a heat stabilizer with respect to 100 parts by mass of the block copolymer. 0.3 parts by mass of base-6(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl ester, and then the solvent was removed, whereby block copolymer (b)-2 was recovered .

[Production Example 3] In a nitrogen atmosphere, 0.08 parts by mass of n-butyllithium was added to a cyclohexane solution containing 8 parts by mass of styrene at a concentration of 25% by mass, and the mixture was polymerized at 80° C. for 20 minutes. Next, a cyclohexane solution containing 14 parts by mass of styrene at a concentration of 25% by mass was continuously added to the polymerization solution for 15 minutes, and polymerized at 80°C. Next, a cyclohexane solution containing 22 parts by mass of 1,3-butadiene at a concentration of 25% by mass was continuously added to the polymerization solution for 15 minutes, and polymerized at 80°C. Next, a cyclohexane solution containing 29 parts by mass of styrene at a concentration of 25 mass % was added to the polymerization solution, and the solution was polymerized at 80° C. for 30 minutes.

Then, in order to stop a part of the polymerization, 0.5 times mol of ethanol with respect to n-butyllithium was added to the reactor, and after stirring the polymerization solution for 10 minutes, styrene 27 containing 25% by mass of styrene was added to the polymerization solution. A mass part of the cyclohexane solution was polymerized at 80°C for 30 minutes. Then, in order to completely stop the polymerization, 0.5 times moles of ethanol with respect to n-butyllithium was added to the reactor, and 2-tertiary butyl acrylate was added as a heat stabilizer with respect to 100 parts by mass of the block copolymer. 0.4 parts by mass of base-6(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl ester, and then the solvent was removed, whereby block copolymer (b)-3 was recovered .

[Production Example 4] In a nitrogen atmosphere, 0.08 parts by mass of n-butyllithium and 0.015 parts by mass of tetramethylmethylene diamine were added to a cyclohexane solution containing 60 parts by mass of styrene at a concentration of 25% by mass, and the mixture was heated at 80°C. Aggregate for 20 minutes. Next, a cyclohexane solution containing 30 parts by mass of 1,3-butadiene and 10 parts by mass of styrene at a concentration of 25% by mass was continuously added to the polymerization solution for 30 minutes, and polymerized at 80°C.

Then, in order to completely stop the polymerization, ethanol was added to the reactor in an equal molar amount with respect to n-butyllithium, and 2-tertiary butyl acrylate was added as a heat stabilizer with respect to 100 parts by mass of the block copolymer. 0.3 part by mass of base-6(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl ester, and then the solvent was removed, whereby block copolymer (b)-4 was recovered .

[Manufacturing example 5] In a nitrogen atmosphere, 0.08 parts by mass of n-butyllithium and 0.015 parts by mass of tetramethylmethylene diamine were added to a cyclohexane solution containing 40 parts by mass of styrene at a concentration of 25% by mass, and the mixture was heated at 80°C. Aggregate for 20 minutes. Next, a cyclohexane solution containing 15 parts by mass of 1,3-butadiene and 10 parts by mass of styrene at a concentration of 25% by mass was continuously added to the polymerization solution for 30 minutes, and polymerized at 80°C. Next, a cyclohexane solution containing 35 parts by mass of styrene at a concentration of 25 mass % was added to the polymerization solution, and the solution was polymerized at 80° C. for 30 minutes.

Then, in order to completely stop the polymerization, ethanol was added to the reactor in an equal molar amount with respect to n-butyllithium, and 2-tertiary butyl acrylate was added as a heat stabilizer with respect to 100 parts by mass of the block copolymer. 0.2 parts by mass of base-6(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl ester, and then the solvent was removed, whereby block copolymer (b)-5 was recovered .

[Manufacturing example 6] In a nitrogen atmosphere, 0.08 parts by mass of n-butyllithium was added to a cyclohexane solution containing 42 parts by mass of styrene at a concentration of 25% by mass, and the mixture was polymerized at 80° C. for 20 minutes. Next, a cyclohexane solution containing 8 parts by mass of 1,3-butadiene at a concentration of 25% by mass was continuously added to the polymerization solution for 10 minutes, and polymerized at 80°C. Next, a cyclohexane solution containing 50 parts by mass of styrene at a concentration of 25 mass % was added to the polymerization solution, and the solution was polymerized at 80° C. for 30 minutes.

Then, in order to completely stop the polymerization, ethanol was added to the reactor in an equal molar amount with respect to n-butyllithium, and 2-tertiary butyl acrylate was added as a heat stabilizer with respect to 100 parts by mass of the block copolymer. 0.2 parts by mass of base-6(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl ester, and then the solvent was removed, whereby block copolymer (b)-6 was recovered .

[Manufacturing example 7] In a nitrogen atmosphere, 0.08 parts by mass of n-butyllithium was added to a cyclohexane solution containing 16 parts by mass of styrene at a concentration of 25% by mass, and the mixture was polymerized at 80° C. for 20 minutes. Next, a cyclohexane solution containing 68 parts by mass of 1,3-butadiene at a concentration of 25 mass % was added to the polymerization solution for 10 minutes, and polymerized at 80°C. Next, a cyclohexane solution containing 16 parts by mass of styrene at a concentration of 25 mass % was added to the polymerization solution, and the solution was polymerized at 80° C. for 30 minutes.

Then, in order to completely stop the polymerization, ethanol was added to the reactor in an equal molar amount with respect to n-butyllithium, and 2-tertiary butyl acrylate was added as a heat stabilizer with respect to 100 parts by mass of the block copolymer. 0.5 parts by mass of base-6(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl ester, and then the solvent was removed, whereby block copolymer (b)-7 was recovered .

[Production Example 8] In a nitrogen atmosphere, 0.08 parts by mass of n-butyllithium was added to a cyclohexane solution containing 9 parts by mass of styrene at a concentration of 25% by mass, and the mixture was polymerized at 80° C. for 15 minutes. Next, a cyclohexane solution containing 75 parts by mass of 1,3-butadiene and 7 parts by mass of styrene at a concentration of 25% by mass was continuously added to the polymerization solution for 30 minutes, and polymerized at 80°C. Next, a cyclohexane solution containing 9 parts by mass of styrene at a concentration of 25 mass % was added to the polymerization solution, and the solution was polymerized at 80° C. for 30 minutes.

Then, in order to completely stop the polymerization, ethanol was added to the reactor in an equal molar amount with respect to n-butyllithium, and 2-tertiary butyl acrylate was added as a heat stabilizer with respect to 100 parts by mass of the block copolymer. 0.5 part by mass of base-6(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl ester, and then the solvent was removed, whereby block copolymer (b)-8 was recovered .

(Contents of vinyl aromatic hydrocarbon monomer units (styrene units) and conjugated diene monomer units (butadiene units) in each block copolymer (b)-1 to 8) For each of the block copolymers obtained in the above-mentioned Production Examples 1 to 8, the copolymerization ratio of styrene and 1,3-butadiene as each monomer component and the addition during polymerization were confirmed by the analytical method shown below. whether there is a difference in the ratios. An ultraviolet-visible spectrophotometer manufactured by Shimadzu Corporation was used as an analysis device. Specifically, about 30 mg of each of the block copolymers (b) 1 to 8 (accurately weighed up to a unit of 0.1 mg) was dissolved in 100 mL of chloroform, and the polymer solution was filled in a quartz tank and placed in a UV-visible Spectrophotometer, scan the ultraviolet wavelength 260 ~ 290 nm. Using the characteristic that the aromatic ring of styrene exhibits light absorption in this wavelength region, each block copolymer (b) was obtained from the absorption peak height value obtained by measurement and using a calibration curve prepared with a known sample The composition ratio (mass %) of styrene contained in it. The peak wavelength derived from styrene occurs at 269.2 nm. As a result, it was confirmed that there was no difference between the addition ratio of styrene at the time of polymerization and the composition ratio of styrene in the block copolymer. On the other hand, the butadiene composition ratio (mass %) was obtained by subtracting the styrene composition ratio (mass %) from 100.

(weight average molecular weight Mw, number average molecular weight Mn, molecular weight distribution Mw/Mn, peak molecular weight and molecular weight peak number of each block copolymer (b)-1-8) The weight average molecular weight (Mw), number average molecular weight (Mn), molecular weight distribution (Mw/Mn), peak molecular weight and molecular weight peak number of the above-mentioned block copolymers (b)-1-8 were determined by gel permeation chromatography ( GPC) apparatus, and measured according to the following measurement conditions.

(measurement conditions) GPC device: HLC-8220 manufactured by Tosoh Corporation Column: Connect 2 SuperMultiporeHZ-M made by Tosoh Corporation in series Column temperature: 40℃ Liquid delivery volume: 0.2 mL/min Detector: Refractometer (RI)

Furthermore, using tetrahydrofuran as a solvent, about 10 mg of the target polymer for molecular weight measurement was dissolved in 20 mL of tetrahydrofuran, and the mixture was filtered to remove insoluble matter to obtain a sample for GPC measurement.

The specific measurement method is as follows. First, a calibration curve was prepared using 9-point standard polystyrene samples of known molecular weights with different molecular weights. The weight-average molecular weight (Mw) of the standard polystyrene with the highest molecular weight was 1,090,000, and the weight-average molecular weight (Mw) of the standard polystyrene with the lowest molecular weight was 1,050. Next, a sample for measurement was prepared in the above-mentioned manner using each block polymer whose molecular weight was measured.

After confirming that the temperature in the tank containing the column has become constant, the solution sample is injected and the measurement is started. After the measurement, statistical processing of the obtained molecular weight distribution curve was performed, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were calculated. The molecular weight distribution (Mw/Mn) is a value obtained by dividing the obtained weight average molecular weight (Mw) by the number average molecular weight (Mn). In addition, the peak molecular weight and the number of molecular weight peaks were determined based on the above-mentioned molecular weight distribution curve.

(Weight Average Molecular Weight (Mw), Number Average Molecular Weight (Mn) and Molecular Weight Distribution (Mw/Mn) of Polymer Block S of Each Block Copolymer (b)-1-8) Next, the molecular weight measurement of the polymer block S comprising only vinyl aromatic monomer units constituting each of the block copolymers (b)-1 to 8 was performed. Specifically, about 20 mg of the polymer was dissolved in about 10 mL of chloroform using an Erlenmeyer flask, 20 mL of an osmic acid solution was added, and the conjugated diene portion was decomposed by heating at about 90° C. for 30 minutes. After heating with water, the conical flask was cooled with running water, and about 200 mL of methanol was quietly poured into the decomposed polymer solution, so that the components insoluble in the solvent were analyzed. The precipitated solid content only contains the polymer block S of vinyl aromatic monomer units, and the styrene monomer that does not form a block or the styrene with a lower degree of polymerization is still dissolved in methanol/tert-butyl alcohol/ chloroform mixed solution. This precipitate was suction-filtered using a glass filter, washed with pure methanol, and vacuum-dried to isolate only the polymer block S from the block copolymer (b).

Here, the above-mentioned osmic acid solution refers to 1 g of osmium oxide (VIII) and the trade name "PERBUTYL H (chemical name tert-butyl hydroperoxide, purity 69" commercially available from NOF Co., Ltd. %)" 2 kg dissolved in 3 L of tert-butyl alcohol and mixed.

About 10 mg of the polymer block S thus obtained was dissolved again in 20 mL of tetrahydrofuran, and the measurement was carried out with a GPC apparatus. The measurement conditions and methods are based on the measurement conditions and methods of the molecular weight of the block copolymer (b) described above.

(Melt flow rate (MFRb) of block copolymer (b)) According to the standard ISO1133, the measurement is carried out under the conditions of a temperature of 200°C and a load of 5 kgf.

Monomer feed composition and ratio of vinyl aromatic monomer unit to conjugated diene monomer unit at the time of each production of the block copolymers (b)-1 to 8 obtained by each of Production Examples 1 to 8 (mass %), the molecular weight information based on the GPC measurement result, and the melt flow rate are shown in the following [Table 2].

[Table 2] Production Example/Block Copolymer (b)- 1 2 3 4 5 6 7 8 Structure of block copolymer (b) S1-B/S1-B/S2-S2 S1-B/S1-B/S2-S2 B1-S1-B2-S2 S1-B/S1 S1-B/S1-S2 S1-B1-S2 S1-B1-S2 S1-B/S1-S2 Amount of vinyl aromatic monomer and conjugated diene monomer added (mass ratio) 20-14/10-16/10-30 31-21/20-2/6-20 8-14-22-56 60-30/10 40-15/10-35 42-8-50 16-68-16 9-75/7-9 Content of vinyl aromatic monomer units (mass %) 70 77 70 70 85 92 32 25 Conjugated diene monomer unit content (mass %) 30 twenty three 30 30 15 8 68 75 Weight average molecular weight Mw (ten thousand) 11.8 11.6 12.2 10.6 10.8 11.0 6.7 8.4 Number average molecular weight Mn (ten thousand) 9.0 8.5 7.1 8.8 9.1 8.1 5.4 8.1 Molecular weight distribution Mw/Mn 1.32 1.36 1.72 1.20 1.18 1.35 1.24 1.04 Peak molecular weight (10,000) 12.1 11.9 16.1/7.3 10.9 11.1 11.4 6.7 8.6 Molecular weight peak number 1 1 2 1 1 1 1 1 (Add ethanol halfway through) not added not added Add to not added not added not added not added not added Polymer block (S) number average molecular weight Mn (ten thousand) 2.6 3.3 2.9 7.7 4.0 4.2 1.1 0.6 Polymer block (S) molecular weight distribution Mw/Mn 1.7 2.0 2.6 1.1 1.6 1.4 1.2 1.2 Melt flow rate MFRb (200℃*5 kg) 6.5 6.9 6.2 9.0 5.8 4.9 15 18

[Manufacturing method of antistatic resin composition] The vinyl aromatic hydrocarbon resins (a)-1 to 7 and the donor-acceptor molecular compounds (c-1) shown in the above [Table 1] and the above [Production Examples 1 to 8] were used The block copolymers (b)-1 to 8 were produced as antistatic resin compositions by the method described below. First, component (a), component (b), and component (c) are dry-blended at room temperature in a desired composition ratio. After that, it was put into the hopper of a twin-screw extruder TEX30α (L/D=42) manufactured by Nippon Steel Works, and melt-kneaded at a cylinder temperature of 210°C. In addition, only when using the preparation composition of (a)-5, it implemented at the cylinder temperature of 230 degreeC. In order to fully exert the antistatic properties of the above-mentioned (c) component, the above-mentioned (c) component must be highly microdispersed in the above-mentioned (b) component. 44) or the case of directly producing the antistatic resin composition without producing the high-concentration master batch (Examples 1 to 34, Comparative Examples 1 to 24), all of which are from the initial processing of the individual components , that is, in the melt-kneading step of the constituent components, a kneader with high kneading property, specifically, a twin-screw extruder is used.

On the other hand, when a master batch containing a high concentration of component (c) is used as a base material, an antistatic resin composition is produced by diluting the master batch with the component (a) and/or the component (b) ( In the case of Examples 35 to 44), in the dilution step, the master batch was diluted by using a uniaxial extruder with a lower kneading property, and an antistatic resin composition in the form of pellets was produced. Thereafter, a desired molded product is produced by injection molding, or the master batch is diluted using a uniaxial extruder equipped with a T-die to produce a sheet-like antistatic resin composition of a desired thickness. When the component (c) is temporarily prepared as a master batch in which the component (c) is highly dispersed, it is confirmed that the antistatic performance can be sufficiently exhibited even if the subsequent dilution processing is performed under slow kneading conditions.

In the case of carrying out the dilution process of the high-concentration masterbatch (Examples 35 to 44), the single-shaft extruder VS40-28V manufactured by TANABE PLASTICS MACHINERY (L/D=28; It has a compression-kneading zone) to produce an antistatic resin composition in the form of particles. In addition, about the machine which implements the following extrusion sheet molding, the sheet-shaped antistatic resin composition which has a desired thickness was manufactured using the sheet extrusion molding machine described below.

[Characteristics of antistatic resin composition] (Extrusion molding of antistatic resin composition and measurement of surface resistivity) As described above, the particles of the antistatic resin composition (Examples 1 to 34, Comparative Examples 1 to 24) containing the molecular compound of the donor-acceptor system as the component (c) are highly microdispersed, or the The master batch of the component (c) of the concentration was used as a base material and diluted with the component (a) and/or the component (b) (Examples 35 to 44), and an extruded sheet was produced by a uniaxial T-die extruder. The T-die sheet forming system uses a sheet extrusion machine FS40-36V+TS400 (single screw, with Dulmage) manufactured by Chibei Co., Ltd., screw diameter 40 mm, L/D=36, T Mold width 400 mm, mirror roll), at a cylinder temperature of 210 °C and a roll temperature of 70 °C, adjusting the screw speed and the roller pulling speed to produce a single-layer sheet with a thickness of 0.20 mm. In addition, only when using the preparation composition containing (a)-5, it implemented at the cylinder temperature of 230 degreeC, and the roll temperature of 80 degreeC. When evaluating the surface resistivity, the single-layer sheet was measured, and the production of the measurement sheet was carried out by single-layer extrusion. Both ends of the extruded sheet were trimmed by about 30 mm to obtain a raw sheet with a width of 220 mm.

The surface resistivity in the examples and comparative examples is that after the antistatic resin composition formed into a sheet was left for 24 hours in a constant temperature room at 23°C and a humidity of 50%, a simple type manufactured by SIMCO JAPAN Co., Ltd. was used. The surface resistivity meter "ST-3" was used for measurement. The surface resistivity of the extruded sheet samples was the average of the measured values in the extrusion direction (MD) and the extrusion perpendicular direction (TD) for each of the front and back sides.

(Injection molding and haze value of antistatic resin composition) For evaluation of the haze value of the antistatic resin composition, a flat plate obtained by injection molding was used. The injection molding was performed using a hybrid injection molding machine FNX110III-18A (clamping pressure 110 tons) manufactured by Nissei Plastics Co., Ltd. The mold used was 1 mm thick, 100 mm short side, 150 mm long side and 150 mm short side. For a mirror-polished flat mold with a film gate on the side, at a cylinder temperature of 210°C and a mold temperature of 50°C, the injection pressure was increased by 5% for the short shot point to obtain a flat molded body with a thickness of 1 mm. The molding cycle was performed with injection for 7 seconds and cooling for 25 seconds. In addition, only (a)-5 mix|blended composition was implemented at the cylinder temperature of 230 degreeC.

The 1 mm-thick molded product obtained by the above injection molding was cut out to an appropriate size, and as a test piece for measurement, the haze value (unit: %) was evaluated using a haze meter HZ-1 manufactured by Suga Test Instruments. In addition, when the haze value exceeds 40%, as clearly stated in ISO14782, accurate measurement cannot be performed, so the results of Examples and Comparative Examples are described as "more than 40 (opaque)".

[Examples 1 to 34, Comparative Examples 1 to 24] The vinyl aromatic hydrocarbon resins (a)-1 to 7 and the donor-acceptor molecular compound (c)-1 shown in the above [Table 1] were used , and the block copolymers (b)-1 to 8 of the above production examples 1 to 8 shown in the above [Table 2] were melt-kneaded using the above-mentioned twin-screw extruder, and each resin was obtained by single-stage processing For the composition, the surface resistivity of the sheet-like antistatic resin composition with a thickness of 0.25 mm obtained by the above-mentioned uniaxial T-die extruder was measured, and a 1 mm thick sheet-like composition obtained by the above-mentioned injection molding machine was used. The flat plate measures the haze value. The measurement results are shown in the following [Table 3] and [Table 4]. In addition, in the table, when the surface resistivity is 1×10 ¹² Ω/□ or less, the actual measured value is recorded, and on the other hand, when the ^{surface resistivity is not 1×10 12} Ω/□ or less, it is recorded. It is "Out" to indicate that it is outside the range of surface resistivity that can exhibit antistatic properties.

[table 3] Vinyl aromatic hydrocarbon resin (a) block copolymer (b) MFR comparison Donor-Acceptor Molecular Compound (c) Surface resistance Ω/□ fog value % Example 1 Type of polymer - (b)-2 - (c)-1 1.0×10 ¹⁰ 1.0 Blending ratio (mass %) 0 96.1 3.9 Example 2 Type of polymer - (b)-2 - (c)-1 7.9×10 ⁹ 0.9 Blending ratio (mass %) 0 98.0 2.0 Example 3 Type of polymer - (b)-2 - (c)-1 2.2×10 ¹⁰ 0.8 Blending ratio (mass %) 0 99.0 1.0 Example 4 Type of polymer - (b)-2 - (c)-1 7.9×10 ¹⁰ 0.7 Blending ratio (mass %) 0 99.5 0.5 Comparative Example 1 Type of polymer - (b)-2 - (c)-1 Out 0.6 Blending ratio (mass %) 0 99.8 0.2 Example 5 Type of polymer (a)-1 (b)-2 - (c)-1 1.3×10 ¹¹ 1.3 Blending ratio (mass %) 28.9 70.6 0.5 Example 6 Type of polymer (a)-2 (b)-2 - (c)-1 1.6×10 ¹¹ 1.2 Blending ratio (mass %) 28.9 70.6 0.5 Example 7 Type of polymer (a)-1 (b)-2 a<b (c)-1 2.8×10 ¹⁰ 2.1 Blending ratio (mass %) 31.4 63.8 4.8 Example 8 Type of polymer (a)-1 (b)-2 a<b (c)-1 3.2×10 ¹⁰ 1.9 Blending ratio (mass %) 31.7 64.4 3.9 Example 9 Type of polymer (a)-1 (b)-2 a<b (c)-1 2.8×10 ¹⁰ 1.8 Blending ratio (mass %) 32.0 65.0 3.0 Example 10 Type of polymer (a)-1 (b)-2 a<b (c)-1 5.6×10 ¹⁰ 1.7 Blending ratio (mass %) 32.4 65.7 1.9 Example 11 Type of polymer (a)-1 (b)-2 a<b (c)-1 7.1×10 ¹⁰ 1.6 Blending ratio (mass %) 32.7 66.3 1.0 Example 12 Type of polymer (a)-1 (b)-2 a<b (c)-1 7.1×10 ¹⁰ 1.6 Blending ratio (mass %) 33.0 66.5 0.5 Comparative Example 2 Type of polymer (a)-1 (b)-2 a<b (c)-1 Out 1.6 Blending ratio (mass %) 32.9 66.9 0.2 Example 13 Type of polymer (a)-2 (b)-2 a>b (c)-1 1.0×10 ¹⁰ 1.5 Blending ratio (mass %) 32.7 66.3 1.0 Comparative Example 3 Type of polymer (a)-2 (b)-2 a>b (c)-1 Out 1.3 Blending ratio (mass %) 32.8 66.7 0.5 Example 14 Type of polymer (a)-1 (b)-2 a<b (c)-1 2.5×10 ¹⁰ 2.0 Blending ratio (mass %) 62.5 33.7 3.8 Example 15 Type of polymer (a)-1 (b)-2 a<b (c)-1 1.0×10 ¹¹ 1.8 Blending ratio (mass %) 63.7 34.3 2.0 Example 16 Type of polymer (a)-1 (b)-2 a<b (c)-1 3.2×10 ¹⁰ 1.6 Blending ratio (mass %) 64.4 34.7 0.9 Example 17 Type of polymer (a)-1 (b)-2 a<b (c)-1 6.3×10 ⁹ 1.6 Blending ratio (mass %) 69.3 30.0 1.0 Example 18 Type of polymer (a)-1 (b)-2 a<b (c)-1 7.9×10 ¹⁰ 1.9 Blending ratio (mass %) 76.9 19.1 4.0 Comparative Example 4 Type of polymer (a)-1 (b)-2 a<b (c)-1 Out 1.6 Blending ratio (mass %) 78.4 19.6 2.0 Comparative Example 5 Type of polymer (a)-1 (b)-2 a<b (c)-1 Out 1.8 Blending ratio (mass %) 81.9 14.1 4.0 Example 19 Type of polymer (a)-1 (b)-3 a<b (c)-1 2.0×10 ¹¹ 2.9 Blending ratio (mass %) 63.7 34.3 2.0 Example 20 Type of polymer (a)-1 (b)-3 a<b (c)-1 1.3×10 ¹¹ 2.7 Blending ratio (mass %) 64.3 34.7 1.0 Comparative Example 6 Type of polymer (a)-2 (b)-2 a>b (c)-1 Out 1.5 Blending ratio (mass %) 66.3 32.7 1.0 Example 21 Type of polymer (a)-1 (b)-4 a<b (c)-1 2.5×10 ¹¹ 15 Blending ratio (mass %) 64.3 34.7 1.0 Example 22 Type of polymer (a)-1 (b)-5 a<b (c)-1 1.0×10 ¹¹ 1.8 Blending ratio (mass %) 64.3 34.7 1.0 Example 23 Type of polymer (a)-1 (b)-5 a<b (c)-1 1.6×10 ¹⁰ 1.7 Blending ratio (mass %) 32.7 66.3 1.0

[Table 4] Vinyl aromatic hydrocarbon resin (a) block copolymer (b) MFR comparison Donor-Acceptor Molecular Compound (c) Surface resistance Ω/□ fog value % Comparative Example 7 Type of polymer (a)-1 (b)-6 a<b (c)-1 Out 1.6 Blending ratio (mass %) 32.7 66.3 1.0 Comparative Example 8 Type of polymer - (b)-6 - (c)-1 Out 0.8 Blending ratio (mass %) 0 99 1.0 Example 24 Type of polymer (a)-1 (b)-7 a<b (c)-1 2.5×10 ¹¹ over 40 (opaque) Blending ratio (mass %) 63.7 34.3 2.0 Example 25 Type of polymer (a)-1 (b)-7 a<b (c)-1 1.3×10 ¹¹ over 40 (opaque) Blending ratio (mass %) 64.3 34.7 1.0 Comparative Example 9 Type of polymer (a)-1 (b)-7 a<b (c)-1 Out over 40 (opaque) Blending ratio (mass %) 78.4 19.6 2.0 Comparative Example 10 Type of polymer (a)-1 (b)-8 a<b (c)-1 Out over 40 (opaque) Blending ratio (mass %) 68.0 28.0 4.0 Comparative Example 11 Type of polymer (a)-1 (b)-8 a<b (c)-1 Out over 40 (opaque) Blending ratio (mass %) 63.7 34.3 2.0 Example 26 Type of polymer (a)-3 (b)-1 a<b (c)-1 7.1×10 ¹⁰ over 40 (opaque) Blending ratio (mass %) 32.7 66.3 1.0 Example 27 Type of polymer (a)-3 (b)-2 a<b (c)-1 1.3×10 ¹¹ over 40 (opaque) Blending ratio (mass %) 63.7 34.3 2.0 Example 28 Type of polymer (a)-3 (b)-7 a<b (c)-1 1.3×10 ¹¹ over 40 (opaque) Blending ratio (mass %) 73.5 24.5 2.0 Example 29 Type of polymer (a)-4 (b)-1 a>b (c)-1 1.6×10 ¹⁰ 0.9 Blending ratio (mass %) 19.8 79.2 1.0 Comparative Example 12 Type of polymer (a)-4 (b)-1 a>b (c)-1 Out 1.1 Blending ratio (mass %) 38.5 57.5 4.0 Comparative Example 13 Type of polymer (a)-4 (b)-1 a>b (c)-1 Out 1.1 Blending ratio (mass %) 57.5 38.5 4.0 Example 30 Type of polymer (a)-5 (b)-2 a<b (c)-1 1.3×10 ¹¹ 1.0 Blending ratio (mass %) 19.8 79.2 1.0 Example 31 Type of polymer (a)-5 (b)-2 a<b (c)-1 7.1×10 ¹⁰ 1.3 Blending ratio (mass %) 38.5 57.5 4.0 Comparative Example 14 Type of polymer (a)-5 (b)-2 a<b (c)-1 Out 1.3 Blending ratio (mass %) 57.5 38.5 4.0 Example 32 Type of polymer (a)-6 (b)-1 a<b (c)-1 1.0×10 ¹¹ 1.1 Blending ratio (mass %) 19.8 79.2 1.0 Example 33 Type of polymer (a)-6 (b)-1 a<b (c)-1 3.2×10 ¹⁰ 1.4 Blending ratio (mass %) 38.5 57.5 4.0 Comparative Example 15 Type of polymer (a)-6 (b)-1 a<b (c)-1 Out 1.4 Blending ratio (mass %) 57.5 38.5 4.0 Example 34 Type of polymer (a)-7 (b)-1 a>b (c)-1 1.6×10 ¹¹ 1.0 Blending ratio (mass %) 19.8 79.2 1.0 Comparative Example 16 Type of polymer (a)-7 (b)-1 a>b (c)-1 Out 1.3 Blending ratio (mass %) 38.5 57.5 4.0 Comparative Example 17 Type of polymer (a)-7 (b)-1 a>b (c)-1 Out 1.3 Blending ratio (mass %) 57.5 38.5 4.0 Comparative Example 18 Type of polymer (a)-1 - - (c)-1 Out 0.9 Blending ratio (mass %) 95.1 0 4.9 Comparative Example 19 Type of polymer (a)-2 - - (c)-1 Out 0.9 Blending ratio (mass %) 95.1 0 4.9 Comparative Example 20 Type of polymer (a)-3 - - (c)-1 Out over 40 (opaque) Blending ratio (mass %) 95.1 0 4.9 Comparative Example 21 Type of polymer (a)-4 - - (c)-1 Out 0.9 Blending ratio (mass %) 95.1 0 4.9 Comparative Example 22 Type of polymer (a)-5 - - (c)-1 Out 1.0 Blending ratio (mass %) 95.1 0 4.9 Comparative Example 23 Type of polymer (a)-6 - - (c)-1 Out 1.0 Blending ratio (mass %) 95.1 0 4.9 Comparative Example 24 Type of polymer (a)-7 - - (c)-1 Out 1.0 Blending ratio (mass %) 95.1 0 4.9

[Production Examples 9 to 14] The block copolymer (b), the donor-acceptor molecular compound (c) and the vinyl aromatic hydrocarbon resin (a) are used, and the component (c) is 5 when the total amount of the master batch is 100% by mass In the aspect of not less than mass % and not more than 20 mass %, according to the blending ratio shown in the following [Table 5], it is melt-kneaded with the above-mentioned twin-screw extruder to produce a master batch containing the high-concentration component (c).

[table 5] Vinyl aromatic hydrocarbon resin (a) block copolymer (b) Donor-Acceptor Molecular Compound (c) Production Example 9 Type of polymer - (b)-2 (c)-1 Blending ratio (mass %) 0 94 6 Manufacturing Example 10 Type of polymer - (b)-2 (c)-1 Blending ratio (mass %) 0 80 20 Manufacturing Example 11 Type of polymer (a)-1 (b)-2 (c)-1 Blending ratio (mass %) 30 60 10 Production Example 12 Type of polymer (a)-1 (b)-2 (c)-1 Blending ratio (mass %) 27 53 20 Production Example 13 Type of polymer (a)-3 (b)-7 (c)-1 Blending ratio (mass %) 30 60 10 Production Example 14 Type of polymer (a)-1 - (c)-1 Blending ratio (mass %) 90 0 10

[Examples 35 to 44] The master batch was prepared by blending the vinyl aromatic hydrocarbon resin (a) and/or the block copolymer (b) into the master batch containing the high-concentration component (c) produced in the above [Production Examples 9 to 14]. In the method of diluted two-stage processing, a sheet-like resin composition with a thickness of 0.25 mm was obtained by the above-mentioned uniaxial T-die extruder, and the surface resistivity of the sheet-like resin composition was measured. Moreover, the haze value was measured using the flat plate of 1 mm thickness obtained by the said injection molding machine. The production examples of the master batches used in combination are shown in the following [Table 6].

[Table 6] High concentration masterbatch Vinyl aromatic hydrocarbon resin (a) block copolymer (b) Surface resistance Ω/□ fog value % same composition for comparison Example 35 Type of polymer Production Example 9 (a)-1 (b)-2 6.3×10 ⁹ 1.7 Example 9 (2.8×10 ¹⁰ ) Blending ratio (mass %) 50.0 32.0 18.0 Example 36 Type of polymer Production Example 9 (a)-2 (b)-2 7.9×10 ⁹ 1.4 Example 13 (1.0×10 ¹⁰ ) Blending ratio (mass %) 16.7 32.7 50.6 Example 37 Type of polymer Manufacturing Example 10 (a)-1 (b)-2 1.3×10 ¹⁰ 1.6 Example 15 (1.0×10 ¹¹ ) Blending ratio (mass %) 10.0 63.7 26.3 Example 38 Type of polymer Manufacturing Example 10 (a)-1 (b)-2 1.6×10 ¹⁰ 1.8 Example 19 (7.9×10 ¹⁰ ) Blending ratio (mass %) 20.0 76.9 3.1 Example 39 Type of polymer Manufacturing Example 11 (a)-1 (b)-2 2.8×10 ¹⁰ 1.5 Example 11 (7.1×10 ¹⁰ ) Blending ratio (mass %) 10.0 29.7 60.3 Example 40 Type of polymer Manufacturing Example 11 (a)-1 (b)-2 1.0×10 ¹⁰ 1.8 Example 14 (2.5×10 ¹⁰ ) Blending ratio (mass %) 38.0 51.1 10.9 Example 41 Type of polymer Production Example 12 (a)-1 (b)-2 1.3×10 ¹⁰ 2.0 Example 7 (2.8×10 ¹⁰ ) Blending ratio (mass %) 24.0 24.9 51.1 Example 42 Type of polymer Production Example 12 (a)-1 (b)-2 2.5×10 ¹⁰ 1.7 Example 10 (5.6×10 ¹⁰ ) Blending ratio (mass %) 9.5 29.8 60.7 Example 43 Type of polymer Production Example 13 (a)-3 (b)-7 3.2×10 ¹⁰ over 40 (opaque) Example 28 (1.3×10 ¹¹ ) Blending ratio (mass %) 20 67.5 12.5 Example 44 Type of polymer Production Example 14 (a)-1 (b)-2 1.0×10 ¹¹ 1.6 Example 11 (7.1×10 ¹⁰ ) Blending ratio (mass %) 20 13.7 66.3

The [Example 35] shown in the above [Table 6] is an antistatic resin composition produced by two-stage processing via a master batch, but it is different from the [Example 9] shown in the above [Table 3]. The final composition is identical to itself. Similarly, [Example 36] and [Example 13], [Example 37] and [Example 15], [Example 38] and [Example 19], [Example 39] and [Example 44] with [Example 11], [Example 40] with [Example 14], [Example 41] with [Example 7], [Example 42] with [Example 10], [Example 43] with [Example 7] The respective final compositions of Example 28] are themselves the same antistatic resin compositions.

In the case of the two-stage processing of the master batch, the transparency has an improvement of about 0.1 (%) or the same haze value. Regarding the surface resistivity, it can be seen that in any of the examples, a lower surface resistivity is exhibited in the case of the two-stage processing of the master batch. In the case of a two-stage process in which a high-concentration master batch of the component (c) is temporarily prepared and then diluted with the component (a) and/or the component (b), the surface resistivity is further reduced, and as a result, more excellent antistatic properties can be produced. resin composition. In other words, it can be seen that the compounding amount of the component (c) required to express the same surface resistivity can also be reduced, and both mechanical properties and economical efficiency can be achieved.

In addition, by comparing Example 44 and Examples 35 to 43, it is clear that by making the block copolymer (b) and the donor-acceptor molecular compound (c) essential components in the preparation of the master batch, the surface resistivity The effect of lowering is excellent. Specifically, in the case of producing a high-concentration master batch using only the vinyl aromatic hydrocarbon resin (a) and the donor-acceptor molecular compound (c) without using the block copolymer (b), the comparison [implementation The three examples of Example 11], [Example 39] and [Example 44] can clarify the following results: the improvement effect of surface resistivity by the master batch method was not obtained, and the single-stage kneading did not change.

According to the above results, the antistatic resin compositions of Examples exhibited desired surface resistivity. ^{On the other hand, Comparative Examples 1 to 24 revealed that the surface resistivity did not reach 1×10 12} Ω/□ or less even if a large amount of the donor-acceptor molecular compound (c) was originally prepared to exhibit antistatic properties. It is difficult to obtain the antistatic resin composition of the present invention.

In addition, when comparing the production method of obtaining the antistatic resin composition in one stage, and the production of a high-concentration masterbatch in which the components (b) and (c) are essential components, the component (a) is used as a basis. And/or the component (b) is diluted to obtain the manufacturing method of the antistatic resin composition, it can be seen that: in the comparison of the above-mentioned examples with identical final compositions, the latter is produced by passing through a high-concentration masterbatch. The surface resistivity of the antistatic resin composition obtained by the two-stage processing is further reduced, and there is a good tendency. The reason for this is that the dispersion of the molecular compound of the donor-acceptor system as the component (c) is further finely dispersed, and the effect of addition is improved.

[Example 45] The antistatic resin composition obtained in the above Example 40 was used as the front and back layers of 40 μm thickness, and was used in the core layer in the vinyl aromatic hydrocarbon resin (a)-3 90 mass % at 10 mass % The composition obtained by blending the block copolymer (b)-1 at a ratio of 1 to 2 was formed into a 0.3 mm thick multilayer extruded sheet using a multilayer sheet extruder equipped with a T die. The T-die multi-layer sheet was formed by using a multi-layer sheet extrusion machine GT-40-28-A+UT-25-28-H (single screw, with Maddock (Maddock) manufactured by Research Laboratory of Plastics Technology Co., Ltd. ) kneading, screw diameter 40 mm (core layer) + 25 mm (front and back layers), L/D = 28, T-die width 400 mm, with a wrinkled roller), at a cylinder temperature of 210°C and a roller temperature of 70°C , adjust the screw speed and the roller pulling speed, thereby making the above-mentioned 0.3 mm thick multi-layer extruded sheet. The formed sheet was heated at 110° C. and press-molded to obtain a conveyance tray capable of accommodating electronic components. Regarding the obtained tray for transporting electronic parts, it was confirmed that the surface resistivity was as high as 10 to the 10th power, and it had antistatic properties excellent in antistatic properties, moderate rigidity and thermal deformation resistance, front and back layers and cores. The layer-to-layer adhesion strength is also good, so that it is firmly attached without peeling from the end face, and has excellent strength that is not easily broken even if it is deliberately bent, so it can be preferably used for practical use.

In this embodiment, especially for the styrene-based resin matrix, the selectivity of the performance of the matrix resin composition of the donor-acceptor molecular compound and the composition diagram of the resin showing antistatic properties have been clarified. [Industrial Availability]

The antistatic resin composition of the present invention exhibits a surface resistivity of 1×10 ¹² Ω/□ or less, thereby exhibiting good antistatic properties, and further, as a donor-acceptor system for substances exhibiting antistatic properties The influence of the molecular compound on the processability, mechanical properties, and optical properties of the resin composition is minimal, so when the resin composition itself has transparency, the antistatic resin composition also maintains transparency, and thus the flexural strength It is also excellent in mechanical properties such as two types of three-layer extruded multi-layer sheets, and also has excellent interlayer adhesion strength, and is industrially applicable as a material for packaging molded products of electronic parts. Moreover, the antistatic resin composition of this invention has industrial applicability as a material of the packaging material of electronic parts, such as a carrier tape, a material tube, and the tray for electronic parts conveyance.

Claims (10)

An antistatic resin composition containing block copolymer (b), and Donor-acceptor system molecular compound (c), and The above-mentioned block copolymer (b) is a block copolymer containing vinyl aromatic hydrocarbon monomer units and conjugated diene monomer units, and has a polymer block mainly composed of vinyl aromatic hydrocarbon monomer units, The vinyl aromatic hydrocarbon monomer unit is 30 to 90 mass %, and the conjugated diene monomer unit is 70 to 10 mass %, When the total amount of the block copolymer (b) and the donor-acceptor molecular compound (c) is 100 mass %, the content of the donor-acceptor molecular compound (c) is 0.5 mass % or more 5 mass % or less. The antistatic resin composition according to claim 1, which has a surface resistivity of 1×10 ¹² Ω/□ or less. An antistatic resin composition comprising a vinyl aromatic hydrocarbon resin (a), a block copolymer (b), and a donor-acceptor molecular compound (c), wherein the block copolymer ( b) is a block copolymer containing vinyl aromatic hydrocarbon monomer units and conjugated diene monomer units, having a polymer block with vinyl aromatic hydrocarbon monomer units as the main body, vinyl aromatic hydrocarbon monomer units The body unit is 30 to 90 mass %, the conjugated diene monomer unit is 70 to 10 mass %, and the total amount of the vinyl aromatic hydrocarbon resin (a) and the block copolymer (b) is 100. In the case of mass %, the mass ratio of the vinyl aromatic hydrocarbon resin (a) is 81 mass % or less, and the mass ratio of the block copolymer (b) is 19 mass % or more and less than 100 mass %. When the total amount of the aromatic hydrocarbon-based resin (a), the block copolymer (b), and the donor-acceptor molecular compound (c) is 100% by mass, the donor-acceptor molecular compound (c) ) is 0.5 mass % or more and 5 mass % or less, and the surface resistivity is 1×10 ¹² Ω/□ or less. The antistatic resin composition according to claim 3, wherein the above vinyl aromatic hydrocarbon resin (a) is selected from Homopolymers of vinyl aromatic hydrocarbon monomers (a1), A graft copolymer of vinyl aromatic hydrocarbon monomer (a2), and Any of the group consisting of vinyl aromatic hydrocarbon monomer units and random copolymers (a3) of (meth)acrylic acid and/or (meth)acrylic acid alkyl ester monomer units. The antistatic resin composition of claim 3, wherein in the melt flow rate (MFR) under the conditions of 200°C and 5 kg load specified in ISO1133, The relationship between the MFR (hereinafter, referred to as MFRa) of the vinyl aromatic hydrocarbon-based resin (a) and the MFR (hereinafter, referred to as MFRb) of the block copolymer (b) is satisfied Any of the following conditions (i) to (iv); <Condition (i)> When the sum of the above-mentioned (a) component and the above-mentioned (b) component is taken as 100% by mass, the above-mentioned (a) component is more than 0% by mass and 30% by mass or less, and the above-mentioned (b) component is 70% by mass or more and not more than 70% by mass. When it reaches 100% by mass, Regardless of the numerical values of MFRa and MFRb, when the total of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is 100% by mass, the above-mentioned (c) component is 0.5% by mass or more and 5% by mass or less. ; <Condition (ii)> When the sum of the said (a) component and the said (b) component is made into 100 mass %, the said (a) component is more than 30 mass % and 50 mass % or less, and the said (b) component is less than 70 mass % and In the case of 50% by mass or more, it shall be MFRa＜MFRb・・(Formula 1) When the relationship between the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100 mass %, the above-mentioned (c) component is 0.5 mass % or more and 5 mass % or less, which is MFRa≧MFRb・・(Formula 2) In the case of the relationship, when the sum of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100 mass %, the above-mentioned (c) component is 0.9 mass % or more and 5 mass % or less; <Condition (iii)> When the sum of the above-mentioned (a) component and the above-mentioned (b) component is taken as 100 mass %, the above-mentioned (a) component is more than 50 mass % and 70 mass % or less, and the above-mentioned (b) component is less than 50 mass % and In the case of 30% by mass or more, it is satisfied MFRa＜MFRb・・(Formula 1) When the total of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100 mass %, the above-mentioned (c) component is 0.9 mass % or more and 5 mass % or less; <Condition (iv)> When the sum of the said (a) component and the said (b) component is made into 100 mass %, the said (a) component exceeds 70 mass % and 81 mass % or less, and the said (b) component is less than 30 mass % and In the case of more than 19% by mass, it is satisfied MFRa＜MFRb・・(Formula 1) When the total of the said (a) component, the said (b) component, and the said (c) component is made into 100 mass %, the said (c) component is 3 mass % or more and 5 mass % or less. The antistatic resin composition of claim 4, wherein in the melt flow rate (MFR) under the conditions of 200°C and 5 kg load specified in ISO1133, The relationship between the MFR (hereinafter, referred to as MFRa) of the vinyl aromatic hydrocarbon-based resin (a) and the MFR (hereinafter, referred to as MFRb) of the block copolymer (b) is satisfied Any of the following conditions (i) to (iv); <Condition (i)> When the sum of the above-mentioned (a) component and the above-mentioned (b) component is taken as 100% by mass, the above-mentioned (a) component is more than 0% by mass and 30% by mass or less, and the above-mentioned (b) component is 70% by mass or more and not more than 70% by mass. When it reaches 100% by mass, Regardless of the numerical values of MFRa and MFRb, when the total of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is 100% by mass, the above-mentioned (c) component is 0.5% by mass or more and 5% by mass or less. ; <Condition (ii)> When the sum of the said (a) component and the said (b) component is made into 100 mass %, the said (a) component is more than 30 mass % and 50 mass % or less, and the said (b) component is less than 70 mass % and In the case of 50% by mass or more, it shall be MFRa＜MFRb・・(Formula 1) When the relationship between the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100 mass %, the above-mentioned (c) component is 0.5 mass % or more and 5 mass % or less, which is MFRa≧MFRb・・(Formula 2) In the case of the relationship, when the sum of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100 mass %, the above-mentioned (c) component is 0.9 mass % or more and 5 mass % or less; <Condition (iii)> When the sum of the above-mentioned (a) component and the above-mentioned (b) component is taken as 100 mass %, the above-mentioned (a) component is more than 50 mass % and 70 mass % or less, and the above-mentioned (b) component is less than 50 mass % and In the case of 30% by mass or more, it is satisfied MFRa＜MFRb・・(Formula 1) When the total of the above-mentioned (a) component, the above-mentioned (b) component and the above-mentioned (c) component is taken as 100 mass %, the above-mentioned (c) component is 0.9 mass % or more and 5 mass % or less; <Condition (iv)> When the sum of the above-mentioned (a) component and the above-mentioned (b) component is taken as 100% by mass, the above-mentioned (a) component is more than 70% by mass and 81% by mass or less, and the above-mentioned (b) component is less than 30% by mass and In the case of more than 19% by mass, it is satisfied MFRa＜MFRb・・(Formula 1) When the total of the said (a) component, the said (b) component, and the said (c) component is made into 100 mass %, the said (c) component is 3 mass % or more and 5 mass % or less. The antistatic resin composition of claim 4, wherein in the melt flow rate (MFR) under the conditions of 200°C and 5 kg load specified in ISO1133, The relationship between the MFR (hereinafter, referred to as MFRa) of the above-mentioned vinyl aromatic hydrocarbon resin (a3) and the MFR (hereinafter, referred to as MFRb) of the above-mentioned block copolymer (b) is satisfied Conditions (v) or (vi) below; <Condition (v)> When the sum of the above-mentioned (a3) component and the above-mentioned (b) component is 100% by mass, the above-mentioned (a3) component is more than 0% by mass and 20% by mass or less, and the above-mentioned (b) component is 80% by mass or more and not more than 80% by mass. When it reaches 100% by mass, regardless of the values of MFRa and MFRb, When the sum of the above-mentioned (a3) component, the above-mentioned (b) component, and the above-mentioned (c) component is taken as 100 mass %, (c) is 0.5 mass % or more and 5 mass % or less; <Condition (vi)> When the sum of the above-mentioned (a3) component and the above-mentioned (b) component is taken as 100 mass %, the above-mentioned (a3) component is more than 20 mass % and 50 mass % or less, and the above-mentioned (b) component is less than 80 mass % and In the case of more than 50% by mass, it is satisfied MFRa＜MFRb・・(Formula 1) The said (c) component is 3 mass % or more and 5 mass % or less, when the sum total of said (a3) component, said (b) component, and said (c) component is made into 100 mass %. The antistatic resin composition according to any one of claims 1 to 7, wherein the above-mentioned donor-acceptor molecular compound (c) is represented by the following general formula (1);

(In formula (1), R ₁ and R ₂ are independently CH ₃ (CH ₂ ) _n -CO-OCH ₂ (n is an integer of 12 to 22) or HOCH ₂ , and at least one of them is CH ₃ (CH _{2 )} ) _n -CO-OCH ₃ (n is an integer from 12 to 22); R ₃ and R ₄ are independently selected from CH ₃ , C ₂ H ₅ , HOCH ₂ , HOC ₂ H ₄ and HOCH ₂ CH(CH ₃ ) Any one of the group formed; Here, "δ+" in the general formula (1) means that there is polarity in the covalent bond in the molecule, (+) means that the electron donating property of the oxygen atom becomes stronger, ( -) indicates that the electron-withdrawing property of the boron atom becomes stronger, "→" indicates the path of electrons being drawn closer, and "---" indicates the state where the bonding force between atoms is weakened). A manufacturing method of the antistatic resin composition according to any one of claims 1 to 8, the method comprising: Step (I), that is, using the block copolymer (b) and the molecular compound of the donor-acceptor system (c), the molecular compound of the donor-acceptor system (c) when the total amount of the master batch is set at 100% by mass is: The composition ratio of 5 mass % or more and 20 mass % or less is melt-kneaded to produce a master batch; and Step (II), that is, diluting the master batch by kneading the above master batch with the vinyl aromatic hydrocarbon resin (a) and/or the block copolymer (b). An electronic component packaging material, which is a molded body of the antistatic resin composition according to any one of claims 1 to 8.