CN107849340B - Antistatic resin composition - Google Patents

Abstract

The invention provides an antistatic resin composition which is excellent in antistatic property, particularly in antistatic persistence, heat resistance and transparency and free from the problem of gas emission. The antistatic resin composition comprises 100 parts by mass of a polyester resin (A) having the following characteristics (a1) and (a2) and 7 to 25 parts by mass of a polyether ester resin (B) having a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group. (a1) The total of the structural units derived from the polycarboxylic acid is defined as 100 mol%, and the total of the structural units derived from the polycarboxylic acid contains 90 to 100 mol% of the structural unit derived from terephthalic acid and 0 to 10 mol% of the structural unit derived from isophthalic acid. (a2) The total of the structural units derived from the polyol is defined as 100 mol%, and the structural units derived from 1, 4-cyclohexanedimethanol comprise 50 to 90 mol% and 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol comprise 10 to 50 mol%.

Description

Antistatic resin composition

technical field

The present invention relates to antistatic resin compositions. More specifically, it relates to a polyester-based resin composition having antistatic properties.

Background technique

Precision electronic components such as semiconductor wafers, semiconductor elements, and integrated circuits may be damaged in function (so-called electrostatic damage) due to a small amount of electrification. Therefore, trays, packaging materials, storage tools, and external storage tools for transporting them are required. The volume resistance value of the material used for the packaging member and the like is 10 ⁹ to 10 ¹⁰ Ω·cm. In addition, the above-mentioned packaging material is required to have transparency (haze value of 50% or less) at least to the extent that the presence of the contents can be visually confirmed, and it is preferable to have an identification capable of visually inspecting the product and confirming the attachment of the contents. Transparency (haze value less than or equal to 15%) of markings and the like. In addition, it is required to have heat resistance to cope with the following situations: when manufacturing precision electronic components, heat generated by drying processes, etc.; when manufacturing articles incorporating precision electronic components, heat generated by drying processes; Parts) For example, the ambient temperature during transportation, storage, and actual use of in-vehicle equipment such as audio equipment and information communication equipment; and the heat generated during operation of the above-mentioned equipment, so heat resistance at a temperature of at least 80°C is required. .

Since thermoplastic resins have many excellent properties, many techniques for setting the volume resistance value of thermoplastic resins to 10 ⁹ to 10 ¹⁰ Ω·cm have been proposed and have been put into practical use, so that whether or not electrical insulating properties are generally Higher materials can be used in fields related to precision electronic components.

As the above technique, for example, resin compositions of thermoplastic resins and ionic surfactants such as alkylsulfonates and alkylbenzenesulfonates, particularly alkyl(aryl)sulfonate-based surfactants have been proposed (for example, patent References 1 and 2). However, this technique reduces the resistance value by exuding a low-molecular-weight surfactant from the surface of the molded product. Therefore, there is a problem that the antistatic property decreases (the resistance value increases) due to wiping or washing the surface surfactant with water. as well as the problem of generating emanating gases.

As the above-mentioned technique, for example, it has been proposed to include a thermoplastic resin having antistatic properties (for example, polyetheresteramide (Patent Document 3), a main chain copolymer composed of polyamide, a branched chain polymer composed of polyalkylene ether and thermoplastic resin) A graft polymer composed of a polyester block polymer (Patent Document 4), a specific polyamideimide elastomer (Patent Document 5), a specific polyethylene glycol, a specific unhindered diisocyanate, and a specific The resin composition of the reaction product of the aliphatic chain extender ethylene glycol (Patent Document 6, etc.). However, in these techniques, in order to obtain sufficient antistatic properties, it may be necessary to mix a large amount of a thermoplastic resin having antistatic properties. In addition, the heat resistance and transparency cannot be satisfied. In addition, these thermoplastic resins having antistatic properties have the property of promoting the degradation and lowering of the molecular weight of polyester-based resins, and the presence of resin compositions of polyester-based resins and these thermoplastic resins having antistatic properties, for example, tends to cause burrs in injection-molded articles. , sink marks and other poor forming problems.

In addition, as the thermoplastic resin having the above-mentioned antistatic properties, the use of polyetherester (for example, a poly(oxyalkylene) diol having a specific molecular weight, a diol having 2 to 8 carbon atoms, and a diol having 4 to 20 carbon atoms) has been proposed. Polyetheresters obtained by condensation of polyvalent carboxylic acids and the like (Patent Document 7), polycondensation of poly(oxyalkylene) diols having specific molecular weights, such as aromatic dicarboxylic acids having 4 to 20 carbon atoms, and diols having 4 to 10 carbon atoms The obtained polyether ester (Patent Document 8), an aromatic dicarboxylic acid having 6 to 20 carbon atoms containing a specific amount of an aromatic dicarboxylic acid substituted with a specific sulfonate group, and a poly(oxyalkylene) having a specific molecular weight Polyether esters obtained by polycondensation of diols and diols having 2 to 10 carbon atoms (Patent Document 9), and poly(oxyalkylene) diols having specific molecular weights such as aromatic dicarboxylic acids having 4 to 20 carbon atoms, and carbon Polyetherester obtained by polycondensation of diols of numbers 4 to 10 (Patent Document 10, etc.). However, the antistatic properties of polyetherester alone are insufficient.

Therefore, it has been proposed to use ionic surfactants together (eg, paragraph 0031 of Patent Document 7, Patent Document 11). However, these techniques have problems in that water washing and wiping lead to lowering of antistatic properties and generation of diffused gas.

Therefore, Patent Document 12 proposes to use, as a base resin, a polyester-based resin that takes at least 5 minutes from a molten state to crystallization for half an hour. However, the heat resistance of the base resin is not high due to this characteristic.

An antistatic resin composition that is excellent in antistatic properties, particularly antistatic persistence, heat resistance, and transparency, and does not have the problem of outgassing, has not yet been proposed.

prior art literature

Patent Literature

Patent Document 1: Japanese Patent Application Laid-Open No. 5-222241

Patent Document 2: Japanese Patent Laid-Open No. 62-230835

Patent Document 3: Japanese Patent Laid-Open No. 62-273252

Patent Document 4: Japanese Patent Application Laid-Open No. 5-97984

Patent Document 5: Japanese Patent Application Laid-Open No. 3-255161

Patent Document 6: Japanese Patent Application Laid-Open No. 5-222289

Patent Document 7: Japanese Patent Application Laid-Open No. 6-57153

Patent Document 8: Japanese Patent Application Laid-Open No. 8-283548

Patent Document 9: Japanese Patent Application Laid-Open No. 10-219095

Patent Document 10: Japanese Patent Laid-Open No. 2006-022232

Patent Document 11: Japanese Patent Application Laid-Open No. 8-283548

Patent Document 12: Japanese Patent Laid-Open No. 2009-001618

SUMMARY OF THE INVENTION

The subject of this invention is to provide the antistatic resin composition which is excellent in antistatic property, especially antistatic durability, heat resistance, and transparency, and does not have a problem of gas emission. Another subject of the present invention is to provide an antistatic resin composition that has a volume resistivity of 10 ⁹ to 10 ¹⁰ Ω·cm and can maintain the antistatic properties, heat resistance, transparency, and molding properties even after washing and wiping with water. Excellent performance, and there is no problem of outgassing.

The inventors of the present invention have found through earnest studies that the above-mentioned problems can be achieved by a resin composition of a specific polyester-based resin and a specific polyetherester.

That is, the antistatic resin composition of the present invention contains:

100 parts by mass of polyester-based resin (A) having the following properties (a1) and (a2); and

7 to 25 parts by mass of a polyetherester resin (B) having a structural unit derived from a sulfonate group-substituted aromatic polycarboxylic acid,

(a1) When the sum of the structural units derived from polyvalent carboxylic acid is taken as 100 mol %, 90 to 100 mol % of structural units derived from terephthalic acid and 0 to 10 mol % of isophthalic acid-derived structural units are included. Structural units,

(a2) When the sum of the structural units derived from polyols is taken as 100 mol %, 50 to 90 mol % of structural units derived from 1,4-cyclohexanedimethanol and 10 to 50 mol % of structural units derived from 2 , 2,4,4-tetramethyl-1,3-cyclobutanediol structural unit.

The second invention is the antistatic resin composition according to the first invention, wherein the component (B) is a polyetherester resin, comprising:

Derived from the group consisting of terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyl-4,4'-dicarboxylic acid and their ester-forming derivatives Structural units of one or more selected aromatic dicarboxylic acids (b1);

A structural unit derived from a sulfonate group-substituted aromatic polycarboxylic acid represented by the following chemical formula (1) and/or its ester-forming derivative (b2);

Structural units derived from polyalkylene glycol (b3) having a number average molecular weight of 200 to 50,000; and

A structural unit derived from a diol (b4) having 2 to 10 carbon atoms,

However, when the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is taken as 100 mol%, 70 to 98 mol% of the component derived from the component is included. The structural unit of (b1) and 2 to 30 mol% of the structural unit derived from the component (b2),

The content of the structural unit derived from the component (b1), the content of the structural unit derived from the component (b2), the content of the structural unit derived from the component (b3), and the content of the structural unit derived from the component (b4) ), the content of the structural unit derived from the component (b3) is 10 to 60 mass % when the sum of the content of the structural unit is taken as 100 mass %.

Chemical formula 1

In Chemical Formula 1,

Ar represents a group having an aromatic ring structure substituted with at least three hydrogen atoms;

R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms;

M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion.

3rd invention The antistatic resin composition of 1st invention or 2nd invention further contains 0.5-5 mass parts of ionic surfactant (C) with respect to 100 mass parts of said component (A).

A fourth invention is the antistatic resin composition according to any one of the first to third inventions, wherein the volume resistivity is 10 ⁹ to 10 ¹⁰ Ω·cm.

A fifth invention is an article comprising the antistatic resin composition according to any one of the first to fourth inventions.

A sixth invention is a precision electronic device comprising the antistatic resin composition according to any one of the first to fourth inventions.

The antistatic resin composition of the present invention is excellent in antistatic properties, particularly antistatic persistence, heat resistance, and transparency, and does not have a problem of gas emission. As a preferred antistatic resin composition of the present invention, the volume resistivity is 10 ⁹ to 10 ¹⁰ Ω·cm, the above antistatic properties can be maintained even when washed with water and wiping, and it is excellent in heat resistance, transparency, and moldability, and is not There is a stray gas problem. It can be used as a pallet for transportation of precision electronic components such as semiconductor wafers, semiconductor elements and integrated circuits, packaging materials, storage and storage tools, and materials for outer packaging components, and outer packaging components for precision electronic equipment assembled with precision electronic components.

Description of drawings

FIG. 1 is a measurement example of ¹ H-NMR of a polyester resin.

Detailed ways

The antistatic resin composition of the present invention contains 100 parts by mass of a polyester-based resin (A) having the following properties (a1) and (a2), and 7 to 25 parts by mass of a sulfonate group-derived aromatic resin The polyetherester resin (B) of the structural unit of a polyhydric carboxylic acid.

(a1) When the sum of the structural units derived from polyvalent carboxylic acid is taken as 100 mol %, 90 to 100 mol % of structural units derived from terephthalic acid and 0 to 10 mol % of isophthalic acid-derived structural units are included. Structural units.

(a2) When the sum of the structural units derived from polyols is taken as 100 mol %, 50 to 90 mol % of structural units derived from 1,4-cyclohexanedimethanol and 10 to 50 mol % of structural units derived from 2 , 2,4,4-tetramethyl-1,3-cyclobutanediol structural unit.

(A) Polyester resin:

The component (A) is a polyester-based resin containing (a1) 90 to 100 mol % of structural units derived from terephthalic acid, taking the sum of the structural units derived from polyvalent carboxylic acid as 100 mol %, and 0 to 10 mol % of the structural units derived from isophthalic acid; (a2) taking the sum of the structural units derived from polyols as 100 mol %, it contains 50 to 90 mol %, preferably 55 to 85 mol %, and more Preferably 60 to 80 mol% of structural units derived from 1,4-cyclohexanedimethanol and 10 to 50 mol%, preferably 15 to 45 mol%, more preferably 20 to 40 mol% of structural units derived from 2,2,4 , 4-tetramethyl-1,3-cyclobutanediol structural unit. Among them, polycarboxylic acids include their ester-forming derivatives. That is, terephthalic acid includes its ester-forming derivatives. Likewise, isophthalic acid includes its ester-forming derivatives. Among them, polyols include their ester-forming derivatives. That is, 1,4-cyclohexanedimethanol includes its ester-forming derivatives. Likewise, 2,2,4,4-tetramethyl-1,3-cyclobutanediol includes its ester-forming derivatives.

As said component (A), the structural unit derived from other polyhydric carboxylic acid other than terephthalic acid and isophthalic acid may be contained in the limit which does not violate the objective of this invention. Examples of the above-mentioned other polyvalent carboxylic acids include phthalic acid, naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, diphenyl-3, Aromatic polycarboxylic acids such as 3'-dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid and anthracene dicarboxylic acid; 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid Carboxylic acids and alicyclic polycarboxylic acids such as 1,4-cyclohexanedicarboxylic acid; malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid aliphatic polycarboxylic acids such as acids; and their ester-forming derivatives, and the like. As the above-mentioned other polyvalent carboxylic acid, one or more of them can be used.

As the component (A), within a limit that does not violate the object of the present invention, other than 1,4-cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclohexane may be contained Structural units derived from other polyols other than butanediol. Examples of the other polyhydric alcohols described above include ethylene glycol, diethylene glycol, trimethylene glycol, tetramethylene glycol, neopentyl glycol, polyethylene glycol, 1,2-propylene glycol, 1,2-propylene glycol, 3-Propanediol, polypropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyldiol Alcohol, dodecanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, Aliphatic polyols such as glycerin and trimethylolpropane; xylene glycol, 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)propane, bis(4-hydroxyphenyl) Aromatic polyols such as sulfones, bisphenol A, oxyalkylene adducts of bisphenol A; and their ester-forming derivatives, and the like. As the above-mentioned polyols, one or more of them can be used.

Since the glass transition temperature of the component (A) is relatively high (usually 90°C or higher, preferably 100°C or higher, more preferably 110°C or higher), the antistatic resin composition of the present invention is excellent in heat resistance. In addition, the component (A) is highly transparent, has amorphous or low crystallinity, and has good miscibility with the component (B), so the antistatic resin composition of the present invention is excellent in transparency.

In this specification, using a Diamond DSC type differential scanning calorimeter from PerkinElmer, Inc., the heat of fusion of the second melting curve (the melting curve measured in the last heating process) measured by the following temperature program Polyester resins below 10J/g are defined as amorphous, polyester resins exceeding 10J/g and below 60J/g are defined as low crystallinity, and the temperature program is: after holding the sample at 320°C for 5 minutes , cooled to -50°C at a temperature drop rate of 20°C/min, held at -50°C for 5 minutes, and heated to 320°C at a temperature increase rate of 20°C/min.

In this specification, using a Diamond DSC type differential scanning calorimeter from PerkinElmer Co., Ltd., the glass transition process appearing in the curve measured for the last heating process of the following temperature program, according to the graph of ASTM D3418 2. The glass transition temperature of the intermediate point calculated by the drawing is used as the glass transition temperature. The temperature program is: the sample is heated to 200°C at a heating rate of 50°C/min, and after holding at 200°C for 10 minutes, the temperature is 20°C/min. The cooling rate was cooled to 50°C, held at 50°C for 10 minutes, and then heated to 200°C at a heating rate of 20°C/min.

The ratio of the structural unit derived from each component in the said polyester-type resin can be calculated|required using ¹³ C-NMR and ¹ H-NMR. A measurement example of ¹ H-NMR is shown in FIG. 1 .

For example, 20 mg of a sample can be dissolved in 0.6 mL of chloroform-d ₁ solvent, and a ¹³ C-NMR spectrum can be measured using a 125 MHz nuclear magnetic resonance apparatus under the following conditions.

Chemical shift reference chloroform-d ₁ : 77ppm

Measurement Mode Single Pulse Proton Broadband Decoupling

Pulse width 45° (5.00μsec)

Points 64K

Observation range 250ppm (-25～225ppm)

Repeat time 5.5 seconds

Accumulated times 256 times

Measuring temperature 23℃

Window function exponential (BF: 1.0Hz)

For example, 20 mg of a sample can be dissolved in 0.6 mL of chloroform-d ₁ solvent, and a ¹ H-NMR spectrum can be measured using a 400 MHz nuclear magnetic resonance apparatus under the following conditions.

Chemical shift reference chloroform: 7.24ppm

Measurement Mode Single Pulse

Pulse width 45° (5.14μsec)

Points 16k

Measuring range 15ppm (-2.5～12.5ppm)

Repeat time 7.8 seconds

Accumulated 64 times

Measuring temperature 23℃

Window function exponential (BF: 0.18Hz)

You can refer to pages 496 to 503 of the "Handbook of Polymer Analysis (first printing of the first edition on September 20, 2008, edited by the Japan Society for Analytical Chemistry, Polymer Analysis Research Conference, Asakura Shoten Co., Ltd.)", "Independent The NMR database (http://polymer.nims.go.jp/NMR/) of the material information site of the Administrative Agency for Substances and Materials Research Institute” carries out peak assignment, and calculates the amount of each component in the above-mentioned component (a) based on the peak area ratio. Proportion. In addition, measurement of ¹³ C-NMR and ¹ H-NMR can be carried out at an analytical institution such as Mitsui Chemicals Analysis Center Co., Ltd.

(B) Polyetherester resin:

The component (B) is a polyetherester resin having a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group. From the viewpoint of antistatic property and transparency, the component (B) preferably contains:

Derived from the group consisting of terephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, and their ester-forming derivatives Structural units of one or more aromatic dicarboxylic acids (b1) selected from;

A structural unit represented by the following chemical formula (1) derived from an aromatic polycarboxylic acid substituted with a sulfonate group and/or an ester-forming derivative (b2) thereof;

Structural units derived from polyalkylene glycol (b3) having a number average molecular weight of 200 to 50,000; and,

A structural unit derived from a diol (b4) having 2 to 10 carbon atoms,

However, when the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is taken as 100 mol%, 70 to 98 mol% of the component derived from the component is included. The structural unit of (b1) and 2 to 30 mol% of the structural unit derived from the component (b2), the content of the structural unit derived from the component (b1), the structure derived from the component (b2) If the sum of the content of the unit, the content of the structural unit derived from the component (b3), and the content of the structural unit derived from the component (b4) is taken as 100% by mass, the structural unit derived from the component (b3) The content is 10 to 60% by mass.

Chemical formula 1

In chemical formula (1), Ar represents a group having an aromatic ring structure substituted with at least three hydrogen atoms, and R1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aromatic ring having 6 to 12 carbon atoms. group, M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion.

When the component (B) contains terephthalic acid, 2,6-naphthalene dicarboxylic acid, 2,7-naphthalene dicarboxylic acid, biphenyl-4,4'-dicarboxylic acid, and their When the structural unit of one or more kinds of aromatic dicarboxylic acids (b1) selected from the group consisting of ester derivatives is formed, heat resistance is more favorable, and therefore, it is a preferable aspect.

When the component (B) contains a structural unit represented by the above-mentioned chemical formula (1) derived from an aromatic polycarboxylic acid substituted with a sulfonate group and/or its ester-forming derivative (b2), antistatic properties It is more favorable, therefore, it is a preferred solution.

For Ar in the above chemical formula (1), Ar is a group having an aromatic ring structure substituted with at least three hydrogen atoms. As Ar in the above-mentioned chemical formula (1), for example, a group having a benzene ring structure in which at least three hydrogen atoms are substituted and a group having a naphthalene ring structure in which at least three hydrogen atoms are substituted are exemplified. It is not limited to the substitution of three hydrogen atoms by the three substituents specified in the above-mentioned chemical formula (1), and one or more hydrogen atoms may be substituted by substituents such as an alkyl group, a phenyl group, a halogen group, and an alkoxy group. The substitution position is not limited and can be arbitrarily selected. Ar in the above chemical formula (1) is preferably a group having a benzene ring structure substituted with three hydrogen atoms from the viewpoint of polymerizability, mechanical properties, and color tone.

R1 in the above chemical formula (1) is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Preferred are alkyl groups having 1 to 3 carbon atoms, such as a hydrogen atom, a methyl group, an ethyl group, and a propyl group. Among them, a methyl group and an ethyl group are preferable from the viewpoints of polymerizability, mechanical properties, and color tone of R1 in the above-mentioned chemical formula (1).

R2 in the above chemical formula (1) is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms. Preferred are alkyl groups having 1 to 3 carbon atoms, such as a hydrogen atom, a methyl group, an ethyl group, and a propyl group. Among them, a methyl group and an ethyl group are preferable from the viewpoints of polymerizability, mechanical properties, and color tone of R2 in the above-mentioned chemical formula (1).

R1 and R2 in the above chemical formula (1) may have the same structure or different structures. R1 and R2 in the above-mentioned chemical formula (1) are independent of each other, and may have any structure within the above-mentioned range.

M ⁺ in the above chemical formula (1) is a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion. In addition, when M ⁺ in the above-mentioned chemical formula (1) is polyvalent, there is a corresponding number of sulfonic acid groups (the part other than M ⁺ in the above-mentioned chemical formula (1)). For example, when M ⁺ in the above chemical formula (1) is a divalent metal ion, there are two sulfonic acid groups (the parts other than M ⁺ in the above chemical formula (1)) corresponding to one metal ion.

Examples of the metal ions include sodium ions, potassium ions, and alkali metal ions such as lithium ions; alkaline earth metal ions such as calcium ions and magnesium ions; and zinc ions. As said tetraalkylphosphonium ion, a tetrabutylphosphonium ion, a tetramethylphosphonium ion, etc. are mentioned. As said tetraalkylammonium ion, a tetrabutylammonium ion, a tetramethylammonium ion, etc. are mentioned. Among them, as M ⁺ in the above chemical formula (1), alkali metal ions, tetrabutylammonium ions, and tetrabutylphosphonium ions are preferred from the viewpoint of polymerizability, mechanical properties, antistatic properties, and color tone. More preferred are alkali metal ions and tetrabutylphosphonium ions.

As the component (b2), that is, the aromatic polycarboxylic acid substituted with a sulfonate group represented by the above-mentioned chemical formula (1) and/or its ester-forming derivative, for example, isophthalic acid-4-sulfonic acid can be mentioned. Sodium, Sodium Isophthalate-5-sulfonate, Potassium Isophthalate-4-sulfonate, Potassium Isophthalate-5-sulfonate, Sodium Terephthalate-2-sulfonate, Terephthalate Potassium formic acid-2-sulfonate, zinc isophthalate-4-sulfonate, zinc isophthalate-5-sulfonate, zinc sulfo-terephthalate-2-sulfonate, isophthalate-4 -sulfonic acid tetraalkylphosphonium salt, isophthalic acid-5-sulfonic acid tetraalkylphosphonium salt, isophthalic acid-4-sulfonic acid tetraalkylammonium salt, isophthalic acid-5-sulfonic acid tetraoxane base ammonium salt, terephthalic acid-2-sulfonic acid tetraalkylphosphonium salt, terephthalic acid-2-sulfonic acid tetraalkylammonium salt, 2,6-naphthalenedicarboxylic acid-4-sodium sulfonate, 2 ,7-Naphthalenedicarboxylic acid-4-sodium sulfonate, 2,6-naphthalenedicarboxylic acid-4-potassium sulfonate, 2,6-naphthalene-4-sulfonic acid zinc salt, 2,6-naphthalene Dicarboxylic acid-4-sulfonic acid tetraalkylphosphonium salts, 2,7-naphthalenedicarboxylic acid-4-sulfonic acid tetraalkylphosphonium salts, their dimethyl esters, their diethyl esters, and the like.

Among them, as the component (b2), from the viewpoint of polymerizability, mechanical properties, and color tone, dimethyl isophthalate-4-sodium sulfonate, dimethyl isophthalate-5-sodium sulfonate, Dimethyl isophthalate-4-potassium sulfonate, dimethyl isophthalate-5-potassium sulfonate, dimethyl terephthalate-2-sodium sulfonate, and dimethyl terephthalate- Potassium 2-sulfonate.

As the component (B), when the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is taken as 100 mol %, the content is 70 to 98 mol %. , preferably 71 to 97 mol %, more preferably 73 to 95 mol %, further preferably 75 to 91 mol % of the structural unit derived from the component (b1), including 2 to 30 mol %, preferably 3 to 29 mol %, 5-27 mol% is more preferable, and 9-25 mol% of the structural unit derived from the said component (b2) is more preferable.

When the component (B) contains the structural unit derived from the component (b1) and the structural unit derived from the component (b2) within the above range, the antistatic property of the antistatic resin composition of the present invention is further improved good. In addition, good antistatic properties can be maintained even when washing and wiping with water are performed. In addition, it has sufficient molecular weight and crystallinity, and has good handleability.

When the component (B) contains a structural unit derived from a polyalkylene glycol (b3) having a number-average molecular weight of 200 to 50,000, the antistatic property is more favorable, which is a preferable aspect.

As the component (b3), that is, polyalkylene glycol having a number average molecular weight of 200 to 50,000, for example, polyethylene glycol, polypropylene glycol, and ethylene glycol as a main monomer (usually 60 mol% or more, preferably 80 mol% or more) and a copolymer using propylene glycol or the like as a comonomer, and an alkylene glycol such as ethylene glycol and propylene glycol as the main monomer and a small amount (usually 10 mol% or less, preferably 5 mol% or less, It is more preferably 1 mol% or less.) A copolymer of an aromatic polyol as a comonomer, a mixture thereof, and the like.

The number average molecular weight of the component (b3) may be 200 to 50,000, preferably 500 to 30,000, and more preferably 1,000 to 20,000, from the viewpoint of antistatic property, dispersibility, and heat resistance.

The content of the structural unit derived from the component (b3) in the component (B) may be 10 to 60% by mass, preferably 15 to 55% by mass, from the viewpoints of antistatic properties, handleability, and heat resistance. , more preferably 20 to 50% by mass. Among them, the content of the structural unit derived from the component (b1), the content of the structural unit derived from the component (b2), the content of the structural unit derived from the component (b3), and the content of the structural unit derived from the component ( The sum of the contents of the structural units of b4) is 100% by mass.

When the component (B) contains a structural unit derived from ethylene glycol (b4) having 2 to 10 carbon atoms, the antistatic property, handleability, and heat resistance are more favorable, which is a preferable aspect.

Examples of the diol having 2 to 10 carbon atoms as the component (b4) include ethylene glycol, propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,4-butanediol, Fats such as ,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, 1,2-cyclohexanediol, and 1,4-cyclohexanediol ethylene glycol; ethylene glycol having ether bonds such as diethylene glycol; and ethylene glycol having thioether bonds such as thiodiethanol. As the component (b4), 1,6-hexanediol, ethylene glycol, and diethylene glycol are preferable from the viewpoint of antistatic property, crystallinity, and handleability. As the component (b4), one or more of them can be used.

As the component (B), according to JIS K7367-1:2002, a DIN Ubbelohde viscometer (capillary diameter: 0.63 mm) and a mixed solvent of phenol/tetrachloroethane (mass ratio 60/40) of the specification Fig. 2 were used , the reduced viscosity measured at a concentration of 1.2g/dl and a temperature of 35°C is preferably 0.2cm ³ /g or more, more preferably 0.25cm ³ /g or more, in terms of antistatic properties, heat resistance and mechanical properties, More preferably, 0.3 cm ³ /g or more, on the other hand, may be 1.8 cm ³ /g or less from the viewpoint of antistatic properties.

The method for obtaining the component (B) using the components (b1) to (b4) is not particularly limited, and any method can be used. For example, the components (b1) to (b4) can be heated and melted to 150 to 300° C. in the presence of a transesterification catalyst, and subjected to a polycondensation reaction to obtain the component (B).

The above-mentioned transesterification catalyst is not particularly limited, and any transesterification catalyst can be used. Examples of the transesterification catalyst include antimony compounds such as antimony trioxide; tin compounds such as stannous acetate, dibutyltin oxide, and dibutyltin diacetate; titanium compounds such as tetrabutyl titanate; and zinc such as zinc acetate. Compounds; calcium compounds such as calcium acetate; alkali metal salts such as sodium carbonate and potassium carbonate, etc. Among them, tetrabutyl titanate is preferable. As the above-mentioned transesterification catalyst, one or more of them can be used.

The usage-amount of the said transesterification catalyst is not specifically limited, However, It is 0.01-0.5 mol% normally with respect to 1 mol of said component (b1), Preferably it is 0.03-0.3 mol%.

Moreover, it is preferable to use various stabilizers, such as antioxidant, at the time of the said polycondensation reaction.

The polycondensation reaction is preferably carried out at 150 to 250°C, preferably 150 to 200°C for about 1 to 20 hours while evaporating the distillate, and then the temperature is raised to 180 to 300°C, preferably 200 to 280°C, more preferably 220°C ~260°C, and then for about 1 to 20 hours. The ingredient (B) can be set to have a reduced viscosity in a preferred range.

As an example of the said component (B) on the market, "ELECUTR02 (trade name)" of Takemoto Oil Co., Ltd., etc. are mentioned.

The compounding amount of the component (B) may be 7 parts by mass or more, preferably 9 parts by mass or more, and more preferably 12 parts by mass or more, from the viewpoint of antistatic properties relative to 100 parts by mass of the component (A). . On the other hand, from the viewpoints of gas emission resistance and transparency, it may be 25 parts by mass or less, preferably 22 parts by mass or less, and more preferably 20 parts by mass or less.

(C) Ionic surfactant (optional ingredient):

In the antistatic resin composition of the present invention, as described above, sufficient antistatic properties can be found even without using an ionic surfactant, but the use of an ionic surfactant is not excluded. The antistatic resin composition of the present invention may contain an ionic surface active agent when the antistatic resin composition is used, for example, in applications in which antistatic properties are particularly important in the initial stage, or in applications in which the necessity of gas emission and bleeding is less considered. agent.

In the case of using the component (C) ionic surfactant, the compounding amount may be any component and is not particularly limited, but may be 0.5 to 5 parts by mass relative to 100 parts by mass of the component (A). .

As said component (C), the organic sulfonic-acid type surfactant which consists of an organic sulfonic acid and a base is mentioned, for example.

Examples of the above-mentioned organic sulfonic acid include alkanes having 6 to 18 carbon atoms in the alkyl group, such as octylbenzenesulfonic acid, dodecylbenzenesulfonic acid, dibutylbenzenesulfonic acid, and dinonylbenzenesulfonic acid. benzenesulfonic acid; and alkylnaphthalenesulfonic acids whose alkyl groups have 2 to 18 carbon atoms, such as dimethylnaphthalenesulfonic acid, diisopropylnaphthalenesulfonic acid, and dibutylnaphthalenesulfonic acid. Among them, dodecylbenzenesulfonic acid and dimethylnaphthalenesulfonic acid are preferable. As the above-mentioned organic sulfonic acid, one or more of them can be used.

Examples of the base include alkali metals such as lithium, sodium, and potassium; phosphonium compounds such as tetrabutylphosphonium, tributylbenzylphosphonium, triethylhexadecylphosphonium, and tetraphenylphosphonium; and tetrabutylphosphonium. ammonium, tributylbenzylammonium chloride, and ammonium compounds such as triphenylbenzylammonium, etc. Among them, sodium, potassium, tetramethylphosphonium, tetraethylphosphonium, tetrahexylphosphonium, tetraoctylphosphonium, tetrabutylphosphonium, tributylbenzylphosphonium, triethylhexadecylphosphonium, and tetraphenylphosphonium are preferred phosphonium. As the above-mentioned bases, one or more of them can be used.

As the component (C), it is preferable that the above-mentioned base is a phosphonium compound from the viewpoint of the suppressing effect of emitted gas and antistatic property, and examples thereof include tetrabutylphosphonium dodecylbenzenesulfonate and the like.

The volume resistivity of the antistatic resin composition of the present invention is preferably 10 ¹⁰ Ω·cm or less, and more preferably 10 ⁹ to 10 ¹⁰ Ω·cm. More preferably, the volume resistivity is 10 ⁹ to 10 ¹⁰ Ω·cm, and the above-mentioned antistatic properties can be maintained even when washing with water and wiping are performed.

In this specification, the volume resistivity is a value measured according to the following experiment (2).

The amount of emitted gas of the antistatic resin composition of the present invention is preferably 2 μg/g or less, and more preferably 1 μg/g or less. For normal use, it can be used well if the amount of emitted gas is 2 μg/g or less. Even in applications that require a relatively low amount of emitted gas, such as precision electronic equipment, it can be used well by setting the amount of emitted gas to 1 μg/g or less. In this specification, the amount of diffused gas is the amount (μg) of diffused gas generated from 1 g of the sample measured according to the following experiment (5).

In the antistatic resin composition of the present invention, in addition to the above-mentioned components, surface active agents other than the components (A) and the thermoplastic resin of the component (B) and the component (C) may be contained as necessary. agents, heat stabilizers, antioxidants, hydrolysis inhibitors, metal passivators, UV absorbers, antistatic agents, lubricants, and colorants.

The antistatic resin composition of the present invention preferably contains a heat stabilizer and an antioxidant. It is possible to prevent molding problems such as coloring and burning when molding large molded products. In the antistatic resin composition of the present invention, a metal deactivator is preferably contained. Also in the case of a member used in contact with metal, corrosion and discoloration of the contact portion can be prevented.

Examples of the aforementioned antioxidant include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, 4,4- Phenolic antioxidants such as dihydroxydiphenyl and tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, phosphite antioxidants, thioether antioxidants, and the like. Among them, phenol-based antioxidants and phosphite-based antioxidants are preferred.

The antistatic resin composition of the present invention can be produced by melt-kneading the component (A), the component (B), and optional components in any order or simultaneously. The method of melt-kneading is not particularly limited, and known methods can be used. For example, a single-screw extruder, a twin-screw extruder, a roll, a mixer, or various kneaders can be used. When using a stirrer or a kneader, for example, it is preferable to perform melt-kneading at a discharge temperature of 240 to 260°C. In the case of using a twin-shaft kneader, for example, it is preferable to perform melt-kneading under the conditions that the rotational speed of the stirring blade is 50 to 500 rpm and the kneading temperature is 240 to 260°C.

The antistatic resin composition of the present invention can be molded into an arbitrary molded product by a known molding method. Examples of the above-mentioned molding methods include ordinary injection molding, insert molding, two-color molding, sandwich molding, gas injection, profile extrusion, two-color extrusion, overlay molding, and sheeting, Film extrusion molding, etc.

Example

Hereinafter, the present invention will be described by way of examples, but the present invention is not limited thereto.

Measurement methods

(1) Formability:

Using an injection molding machine with a mold closing force of 120 tons, an injection molded plate with a length of 64.4 mm, a width of 64.4 mm, and a thickness of 3 mm was molded under the conditions of a barrel temperature of 240 to 260°C, a mold temperature of 50°C, and a cooling time of 5 minutes. The obtained board was visually observed and evaluated according to the following criteria.

○: Sink marks and warpage are not recognized.

×: Sink marks or warpage were confirmed, or sink marks and warpage were confirmed

(2) Volume resistivity (antistatic property):

The measurement was carried out by the double ring probe method (ring probe method) in accordance with the ASTM D257 specification (1987 edition). That is, the injection-molded plate obtained by the method of the above experiment (1) was used as a test piece, and the state was adjusted in a laboratory at a temperature of 23±2° C. and a relative humidity of 50±5% for 40 hours or more, and then using Mitsubishi Chemical Co., Ltd. The company's resistivity meter "HIRESTA UPMCP-HT450 type (trade name)", Mitsubishi Chemical Corporation's double ring probe (as a ring, the main electrode outer diameter is 0.59cm, the guard electrode inner diameter is 1.1cm) "URS PROBE (trade name)" )" and the calculation platform "UFL (trade name)" of Mitsubishi Chemical Corporation, and the measurement was performed under the conditions of an applied voltage of 500 V and a measurement time of 60 seconds. One test piece was measured at two measurement positions, and three test pieces were measured, and the average value of the total six measurement values was taken as the volume resistivity of the sample.

In addition, the measuring method and the theory of the resistivity can be referred to the website of Mitsubishi Chemical Corporation (http://www.mccat.co.jp/3seihin/genri/ghlup2.htm) and the like.

(3) Volume resistivity after water cleaning (antistatic durability 1):

The injection molded plate obtained by the method of the above experiment (1) was washed with gauze (medical type 1 gauze from Kawamoto Sangyo Co., Ltd.) in a water tank filled with distilled water at 25°C for 10 minutes, and the water was wiped off with a clean paper. , dried for more than 24 hours in a laboratory with a temperature of 23±2° C. and a relative humidity of 50±5%, and the volume resistivity was measured according to the method of the above experiment (2).

(4) Volume resistivity after wiping (antistatic durability 2):

The injection molded plate obtained by the method of the above experiment (1) was placed on a friction test machine of JISL0849, and a stainless steel sheet covered with 4 pieces of gauze (medical type 1 gauze of Kawamoto Sangyo Co., Ltd.) was attached to the friction terminal of the friction test machine. Plate (10mm in length, 10mm in width, 1mm in thickness), set the length and width of the stainless steel plate in contact with the test piece, carry a load of 350g, and rub the test piece under the conditions that the moving distance of the rubbing terminal is 60mm, and the speed is 1 back and forth/second After wiping down and back 300 times, the volume resistivity of the wiping portion of the test piece was measured according to the method of the above experiment (2).

(5) The amount of dissipated gas:

The measurement can be performed using a thermal desorption gas chromatography mass spectrometer from PerkinElmer.

(5-1) Capturing diffuse gas by thermal desorption method:

The resin composition was frozen and pulverized to form a pulverized product of 2 mm or less, and 0.1 g of the pulverized product obtained by the above method was placed in the sample tray of the collection unit of the above device, heated at 120° C. for 10 minutes, and the generated volatile substances were used. Helium was used as a carrier gas and was trapped in a cooled trap tube maintained at 5°C.

(5-2) Quantification of volatile substances (emitted gas):

The cooling and trapping tube in which the volatile substances were trapped by the above (5-1) was heated to 300°C at a temperature increase rate of 40°C/sec, and the desorbed gas was supplied to the gas chromatography mass spectrometry unit of the above-mentioned apparatus to generate quantify the amount. At this time, a certain amount of positive positive decane), using the test line prepared in the same manner as the above-mentioned method.

(6) Haze value (transparency):

Using an injection molding machine with a mold closing force of 120 tons, under the conditions of a barrel temperature of 240 to 260°C, a mold temperature of 50°C, and a cooling time of 5 minutes, an injection molded sheet with a length of 60 mm, a width of 60 mm, and a thickness of 0.5 mm was molded according to JIS K. 7136:2000, the haze value of the obtained molded sheet was measured using the turbidity meter "NDH2000 (trade name)" of Nippon Denshoku Kogyo Co., Ltd. The evaluation was performed according to the following criteria.

◎: Less than 5%

○: 5% or more, less than 50%

×: Over 50%

(7) Thermal deformation temperature (heat resistance):

According to ASTMD648-07, an injection molding machine with a mold closing force of 120 tons was used to mold a test piece with a length of 127 mm, a height of 13 mm, and a thickness of 6 mm under the conditions of a barrel temperature of 240-260 °C, a mold temperature of 50 °C, and a cooling time of 5 minutes. Using this test piece, measurement was performed under the conditions of a distance between fulcrums of 100.0 mm (B method), a load of 1.82 MPa, and a temperature increase rate of 2°C.

raw materials used

(A) Polyester resin:

(A-1) Polyester-based resin containing 100 mol % of structural units derived from terephthalic acid, taking the sum of the structural units derived from polyvalent carboxylic acid as 100 mol %, and containing 100 mol % of structural units derived from polyhydric alcohol The sum of the structural units is taken as 100 mol %, and 77 mol % of structural units derived from 1,4-cyclohexanedimethanol and 23 mol % of structural units derived from 2,2,4,4-tetramethyl-1, Structural unit of 3-cyclobutanediol. The glass transition temperature is 108° C., and the heat of fusion is 0 J/g (there is no obvious melting peak in the second melting curve of DSC).

(A-2) Polyester-based resin containing 100 mol % of structural units derived from terephthalic acid, taking the sum of the structural units derived from polyvalent carboxylic acid as 100 mol %, and containing terephthalic acid-derived structural units The sum of the structural units is taken as 100 mol %, and 64 mol % of structural units derived from 1,4-cyclohexanedimethanol and 36 mol % of structural units derived from 2,2,4,4-tetramethyl-1, Structural unit of 3-cyclobutanediol. The glass transition temperature was 119° C., and the heat of fusion was 0 J/g (no obvious melting peak appeared in the second melting curve of DSC).

(A') Comparative resin:

(A'-1) Polyester-based resin containing 100 mol % of structural units derived from terephthalic acid, taking the sum of the structural units derived from polyvalent carboxylic acid as 100 mol %, and containing 100 mol % of structural units derived from polyhydric alcohol The sum of the structural units of 100 mol % contains 34 mol % of structural units derived from 1,4-cyclohexanedimethanol and 66 mol % of structural units derived from ethylene glycol. The glass transition temperature was 81° C., and the heat of fusion was 0 J/g (no obvious melting peak appeared in the second melting curve of DSC).

(A'-2) The polycarbonate resin "IUPILON3000 (trade name)" of Mitsubishi Engineering Plastics Corporation. The glass transition temperature is 143°C.

(B) Polyetherester resin:

(B-1) A polyetherester resin obtained according to the contents of paragraph 0063 and Reference Example 1 of Japanese Patent Laid-Open No. 8-283548. The component (b1) is dimethyl terephthalate, the component (b2) is dimethyl isophthalate-5-sodium sulfonate, and the component (b3) is polyethylene glycol (number average molecular weight 20000), the component (b4) is 1,4-butanediol. Taking the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) as 100 mol %, the structural unit derived from the component (b1) is set to 75 mol%, and the structural unit derived from the component (b2) was set to 25 mol%. The content of the structural unit derived from the component (b1), the content of the structural unit derived from the component (b2), the content of the structural unit derived from the component (b3), and the content of the structural unit derived from the component ( When the sum of the content of the structural units of b4) was 100 mass %, the content of the structural units derived from the component (b3) was 11 mass %.

(B-2) A polyetherester resin obtained according to the contents of paragraph 0064 and Reference Example 2 of Japanese Patent Application Laid-Open No. 8-283548. The component (b1) is dimethyl terephthalate, the component (b2) is dimethyl isophthalate-5-sodium sulfonate, and the component (b3) is polyethylene glycol (number average molecular weight 20000), the component (b4) is 1,4-butanediol. Taking the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) as 100 mol %, the structural unit derived from the component (b1) is set to 85 mol%, the structural unit derived from the component (b2) was set to 15 mol%. The content of the structural unit derived from the component (b1), the content of the structural unit derived from the component (b2), the content of the structural unit derived from the component (b3), and the content of the structural unit derived from the component (b4) ), the content of the structural unit derived from the component (b3) is 20 mass % as the sum of the content of the structural unit is 100 mass %.

(B-3) A polyetherester resin obtained according to the contents of paragraph 0065 and Reference Example 3 of Japanese Patent Laid-Open No. 8-283548. The component (b1) is dimethyl terephthalate, the component (b2) is dimethyl isophthalate-5-sodium sulfonate, and the component (b3) is polyethylene glycol (number average molecular weight 20000), the component (b4) is 1,4-butanediol. Taking the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) as 100 mol %, the structural unit derived from the component (b1) is set to 75 mol%, the structural unit derived from the component (b2) was set to 25 mol%. The content of the structural unit derived from the component (b1), the content of the structural unit derived from the component (b2), the content of the structural unit derived from the component (b3), and the content of the structural unit derived from the component ( When the sum of the content of the structural units of b4) is 100 mass %, the content of the structural units derived from the component (b3) is 20 mass %.

(B-4) The polyetherester resin obtained by the content of the 0066 paragraph of Unexamined-Japanese-Patent No. 8-283548, Reference Example 4. The component (b1) is dimethyl terephthalate, the component (b2) is dimethyl isophthalate-5-sodium sulfonate, and the component (b3) is polyethylene glycol (number average molecular weight 4000), the component (b4) is 1,4-butanediol. Taking the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) as 100 mol %, the structural unit derived from the component (b1) is set to 75 mol%, the structural unit derived from the component (b2) was set to 25 mol%. The content of the structural unit derived from the component (b1), the content of the structural unit derived from the component (b2), the content of the structural unit derived from the component (b3), and the content of the structural unit derived from the component ( When the sum of the content of the structural units of b4) is 100 mass %, the content of the structural units derived from the component (b3) is 20 mass %.

(B’) Comparative polyetherester resin:

(B'-1) Polyetheresteramide resin "PELESTAT 6321NC (trade name)" of Sanyo Chemical Co., Ltd. It does not have a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group.

(C) Ionic surfactant

(C-1) Sodium dodecylbenzenesulfonate from Kanto Chemical Co., Ltd.

Examples 1 to 11, Examples 1C to 7C

的同向双轴混炼机，将表1～3中任一表所示的配合比的配合物在设定温度240～260℃进行熔融混炼，得到树脂组合物。进行上述实验(1)～(7)。表1～3中表示结果。use

A co-rotating twin-shaft kneader was used to melt and knead the compound with the mixing ratio shown in any one of Tables 1 to 3 at a set temperature of 240 to 260° C. to obtain a resin composition. The above experiments (1) to (7) were carried out. The results are shown in Tables 1 to 3.

Table 1

Table 2

table 3

The resin composition of the present invention is excellent in moldability, antistatic properties, antistatic durability, low gas emission properties, transparency, and heat resistance.

Claims (8)

1. An antistatic resin composition, comprising:

100 parts by mass of a polyester-based resin (A) having the following characteristics (a1) and (a 2); and

7 to 25 parts by mass of a polyether ester resin (B) having a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group,

(a1) the total of the structural units derived from the polycarboxylic acid is defined as 100 mol%, and the total of the structural units derived from the polycarboxylic acid is defined to contain 90 to 100 mol% of the structural unit derived from terephthalic acid and 0 to 10 mol% of the structural unit derived from isophthalic acid,

(a2) the total of the structural units derived from the polyol is defined as 100 mol%, and the structural units derived from 1, 4-cyclohexanedimethanol comprise 50 to 90 mol% and 2,2,4, 4-tetramethyl-1, 3-cyclobutanediol comprise 10 to 50 mol%.

2. The antistatic resin composition according to claim 1,

the component (B) is a polyetherester resin comprising:

a structural unit derived from at least one aromatic dicarboxylic acid (b1) selected from the group consisting of terephthalic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, biphenyl-4, 4' -dicarboxylic acid, and ester-forming derivatives thereof;

a structural unit derived from an aromatic polycarboxylic acid substituted with a sulfonate group and/or an ester-forming derivative thereof (b2) represented by the following chemical formula (1);

a structural unit derived from a polyalkylene glycol (b3) having a number average molecular weight of 200 to 50000; and

a structural unit derived from a C2-10 diol (b4),

wherein the sum of the content of the structural unit derived from the component (b1) and the content of the structural unit derived from the component (b2) is defined as 100 mol%, and the sum includes 70 to 98 mol% of the structural unit derived from the component (b1) and 2 to 30 mol% of the structural unit derived from the component (b2),

the sum of the content of the structural unit derived from the component (b1), the content of the structural unit derived from the component (b2), the content of the structural unit derived from the component (b3) and the content of the structural unit derived from the component (b4) was defined as 100% by mass,

the content of the structural unit derived from the component (b3) is 10 to 60 mass%,

chemical formula 1

In the chemical formula 1, the first and second,

ar represents a group having an aromatic ring structure substituted for at least three hydrogen atoms;

r1 and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an aryl group having 6 to 12 carbon atoms;

M⁺represents a metal ion, a tetraalkyl phosphonium ion or a tetraalkyl ammonium ion.

3. The antistatic resin composition according to claim 1 or 2,

the composition further contains 0.5 to 5 parts by mass of an ionic surfactant (C) per 100 parts by mass of the component (A).

4. The antistatic resin composition according to claim 1 or 2,

volume resistivity is 10⁹～10¹⁰Ω·cm。

5. The antistatic resin composition according to claim 1 or 2,

further contains 0.5 to 5 parts by mass of an ionic surfactant (C) per 100 parts by mass of the component (A), and has a volume resistivity of 10⁹～10¹⁰Ω·cm。

6. The antistatic resin composition according to claim 1 or 2,

an antistatic resin composition is used, an injection molding piece with the thickness of 0.5mm is molded by using an injection molding machine with the mold closing force of 120 tons under the conditions of the cylinder temperature of 240-260 ℃, the mold temperature of 50 ℃ and the cooling time of 5 minutes, and the obtained molding piece is prepared according to the following steps of JIS K7136: the haze value measured by 2000 is 5% or more and less than 50%.

7. A molded article comprising the antistatic resin composition according to any one of claims 1 to 6.

8. A precision electronic device comprising the antistatic resin composition according to any one of claims 1 to 6.

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