JP2016047876A - Antistatic polycarbonate resin composition and molded article comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition which has heat resistance and lasting antistatic properties while maintaining transparency and the like inherent in a polycarbonate resin, and to provide a molded article comprising the same.SOLUTION: The antistatic polycarbonate resin composition contains, based on 100 pts.wt. of a polycarbonate resin (A), 8-40 pts.wt. of a polyether ester (B) comprising a specific carboxylic acid component and a specific glycol component and 0.05-1.0 pt.wt. of an organometallic salt compound (C). The molded article comprises the antistatic polycarbonate resin composition.SELECTED DRAWING: None

Description

  The present invention is a polycarbonate resin composition in which a specific polymer and a metal salt of an organic compound are used in combination with a polycarbonate resin, while maintaining the transparency inherent in the polycarbonate resin and excellent in heat resistance and sustained antistatic properties. And a molded article comprising the same.

  Polycarbonate resins are excellent in impact resistance, heat resistance, transparency, and the like, and are widely used in various fields such as electrical / electronic, optical, building materials, medical, food, and vehicles. However, products using plastics such as polycarbonate resin generally have a feature that charged static electricity is difficult to dissipate due to its high electrical insulation. Therefore, there is a possibility that it may lead to problems such as dust adhesion, electrostatic breakdown and malfunction during use of the product, and there has been a demand for imparting continuous antistatic performance to the polycarbonate resin.

  As a conventional method for imparting antistatic performance to a polycarbonate resin while maintaining transparency, a method of blending a diglycerin fatty acid ester with a polycarbonate resin (Patent Document 1) or a method of blending a phosphonium sulfonate (Patent Document 2) ) Has been proposed. These methods are widely used because they are superior in terms of antistatic properties and cost performance, but diglycerin fatty acid esters and phosphonium sulfonates have antistatic properties by migrating to the product surface. Since it is expressed, there is a problem that the antistatic property is lowered by washing or wiping the product.

  In addition, as a technique for developing antistatic performance without being affected by washing and wiping of products, a method of blending polyether ester amide (Patent Document 3) or a method of blending polyether oligomer (Patent Document 4). For example, a method using a polymer-type antistatic agent has been proposed. These methods are excellent in that stable antistatic performance can be obtained, but in order to develop antistatic performance, it is necessary to increase the amount of addition of a polymer type antistatic agent, and as a resin composition There was a problem that the transparency, heat resistance and mechanical properties of the resin were greatly impaired.

  Furthermore, although a method using a polyether ester having a sulfonate group and an ionic surfactant has been proposed (Patent Document 5), in order to develop a stable antistatic performance, an ionic surfactant is added. It is necessary to increase the amount, and there is a problem that transparency as a resin composition is greatly impaired.

Japanese Patent Laid-Open No. 02-196852 JP-A-62-230835 Japanese Patent Laid-Open No. 62-273252 Japanese Patent Laid-Open No. 05-222289 JP 09-249805 A

  An object of the present invention is to provide a polycarbonate resin composition having a heat resistance and a continuous antistatic property while maintaining the transparency and the like inherent to the polycarbonate resin, and a molded product comprising the same.

As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention
8 to 40 parts by weight of a polyether ester (B) composed of a carboxylic acid component and a glycol component, and 0.05 to 1.0 part by weight of an organometallic salt compound (C) with respect to 100 parts by weight of the polycarbonate resin (A) Containing
The carboxylic acid component of the polyether ester (B) is
(I) 2,6-naphthalenedicarboxylic acid compound,
(II) terephthalic acid compound,
(III) a compound having three or more carboxyl groups, and (IV) a carboxylic acid compound containing a sulfonate group represented by the following (formula 1) as a constituent:
The glycol component of the polyether ester (B) is
(V) ethylene glycol,
(VI) diethylene glycol, and (VII) polyalkylene glycol as a constituent,
When the total carboxylic acid component is 100 mol% and the total glycol component is 100 mol%, the copolymerization amount (mol%) of each component (I) to (VII) is represented by the following (formula 2). An antistatic polycarbonate resin composition characterized by satisfying the relationship, and a molded article comprising the same are provided.

（式中、Ｘ^１は炭素数６〜２０の２価の芳香族基又は炭素数１〜８のアルキレン基を示し、Ｍ^＋は金属イオン、テトラアルキルホスホニウムイオン又はテトラアルキルアンモニウムイオンを示す）
（式２）
（I）／（II）／（III）／（IV）＝２０〜４５／３０〜４５／７〜１４／１８〜２５、かつ、
（V）／（VI）／（VII）＝４８〜５８／４０〜５０／１．５〜５ (Formula 1)

(Wherein, X ¹ represents a C 6-20 divalent aromatic group or a C 1-8 alkylene group, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion)
(Formula 2)
(I) / (II) / (III) / (IV) = 20-45 / 30-45 / 7-14 / 18-25, and
(V) / (VI) / (VII) = 48-58 / 40-50 / 1.5-5

  According to the antistatic polycarbonate resin composition of the present invention, heat resistance and continuous antistatic properties can be realized while maintaining the transparency and the like inherent to the polycarbonate resin. In particular, the antistatic polycarbonate resin composition of the present invention is excellent in antistatic properties after washing with water.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples and the like, and is within the scope of the present invention. Any change can be made.

  The antistatic polycarbonate resin composition of the present invention (hereinafter also simply referred to as “polycarbonate resin composition”) contains a polycarbonate resin (A), a specific polyether ester (B), and an organometallic salt compound (C). To do. The polycarbonate resin composition of the present invention may contain other components as necessary.

  The polycarbonate resin (A) is a polymer obtained by a phosgene method in which various dihydroxydiaryl compounds and phosgene are reacted or a transesterification method in which a dihydroxydiaryl compound and a carbonic ester such as diphenyl carbonate are reacted. Among them, a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) can be mentioned.

  As the dihydroxydiaryl compound, in addition to bisphenol A, for example, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy) -3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2- Bis (hydroxyaryl) alkanes such as bis (4-hydroxy-3,5-dichlorophenyl) propane; -Bis (hydroxyaryl) cycloalkanes such as bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane; 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 4,3′-dimethyldiphenyl ether; dihydroxy diaryl sulfides such as 4,4′-dihydroxydiphenyl sulfide; 4,4′-dihydroxydiphenyl sulfoxide, 4,4′-dihydroxy-3,3′-dimethyl Dihydroxy diaryl sulfoxides such as diphenyl sulfoxide; dihydroxy diaryl sulfones such as 4,4′-dihydroxydiphenyl sulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone; It is below. These are used alone or in admixture of two or more. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.

  Furthermore, you may use the said dihydroxy diaryl compound and the trivalent or more phenol compound shown below, for example. Examples of the trivalent or higher valent phenol compound include phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6- Tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis -[4,4- (4,4′-dihydroxydiphenyl) -cyclohexyl] -propane and the like.

  The viscosity average molecular weight of the polycarbonate resin (A) is usually 10,000 to 100,000, preferably 15,000 to 35,000, and more preferably 17,000 to 28,000. When manufacturing this polycarbonate resin (A), a molecular weight regulator, a catalyst, etc. can be used as needed.

  The refractive index of the polycarbonate resin (A) is usually in the range of about 1.584 to 1.586.

The polycarbonate resin composition of the present invention contains a specific polyether ester (B). The polyether ester (B) used in the present invention comprises a carboxylic acid component and a glycol component, and the carboxylic acid component is
(I) 2,6-naphthalenedicarboxylic acid compound,
(II) terephthalic acid compound,
(III) a compound having three or more carboxyl groups, and (IV) a carboxylic acid compound containing a sulfonate group represented by the following (formula 1) as a constituent component, the glycol component:
(V) ethylene glycol,
It has a structure containing (VI) diethylene glycol and (VII) polyalkylene glycol as constituent components. The polyether ester (B) has a branched structure because the (III) component is copolymerized, and the (IV) component having one functional group that forms an ester is copolymerized at the polymer terminal. Polymer.

（式中、Ｘ^１は炭素数６〜２０の２価の芳香族基又は炭素数１〜８のアルキレン基を示し、Ｍ^＋は金属イオン、テトラアルキルホスホニウムイオン又はテトラアルキルアンモニウムイオンを示す） (Formula 1)

(Wherein, X ¹ represents a C 6-20 divalent aromatic group or a C 1-8 alkylene group, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion)

  In the polyether ester (B) used in the present invention, when the total carboxylic acid component is 100 mol% and the total glycol component is 100 mol%, the copolymerization amount (mol) of each component (I) to (VII). %) Satisfies the relationship expressed by the following (formula 2). Thereby, when this polyetherester (B) is knead | mixed with polycarbonate resin (A), the target value of a surface resistance value, a total light transmittance, haze, and heat resistance can be achieved.

(Formula 2)
(I) / (II) / (III) / (IV) = 20-45 / 30-45 / 7-14 / 18-25, and
(V) / (VI) / (VII) = 48-58 / 40-50 / 1.5-5

  Since the polyether ester (B) has a branched structure and a structure in which the ends are blocked, the relationship between the total carboxylic acid component and the total glycol component in the polyether ester (B) may not be an equimolar amount. . The relationship (absolute amount) between the total carboxylic acid component and the total glycol component in the polyether ester (B) is often about 105 to 130 mol% with respect to 100 mol% of the total carboxylic acid component. .

  Examples of the component (I) in the carboxylic acid component of the polyether ester (B) include 2,6-naphthalenedicarboxylic acid and alkyl esters thereof, but 2,6-naphthalenedicarboxylic is preferable because it is easily available. Dimethyl acid is preferred.

  Examples of the component (II) include terephthalic acid and alkyl esters thereof, but terephthalic acid and dimethyl terephthalate are preferable from the viewpoint of easy availability, and terephthalic acid is particularly preferable.

  The component (III) is preferably a compound containing an aromatic ring in order to satisfy the refractive index described below. Specifically, trimellitic acid, trimesic acid, pyromellitic acid, and benzophenone tetracarboxylic acid are preferable components. Trimellitic anhydride is preferable as a raw material compound used when producing the polyether ester (B) by polymerization because it is easily available.

  The component (IV) is preferably a compound containing an aromatic ring in order to satisfy the refractive index described below. Specifically, sodium m-sulfobenzoate, sodium o-sulfobenzoate, and sodium p-sulfobenzoate are preferable components. As a raw material compound used when manufacturing polyetherester (B) by superposition | polymerization, m-sulfobenzoic-acid sodium is preferable from the point that it is easy to acquire. Sodium m-sulfobenzoate is a compound having a structure represented by the following (formula 3).

(Formula 3)

  The carboxylic acid component of the polyether ester (B) is preferably 100 mol% in total of the components (I), (II), (III), and (IV). Other carboxylic acid components may be contained within the range of 5 mol% or less in the total carboxylic acid component, for example, within a range not impaired.

  As the component (VI) in the glycol component of the polyether ester (B), diethylene glycol may be used as a raw material compound, and during polymerization, the ethylene glycol which is the component (V) is condensed and formed as a by-product. Also good.

  As the component (VII), a polyalkylene glycol having a number average molecular weight of 500 to 4000 is preferable. Examples of the polyalkylene glycol include polyethylene glycol, polytrimethylene glycol, polytetramethylene glycol, and copolymers thereof, and among these, polyethylene glycol is preferable. In particular, polyethylene glycol having a number average molecular weight of 500 to 4000 can be preferably used, and polyethylene glycol having a number average molecular weight of 1500 to 2500 can be more preferably used.

  The glycol component of the polyether ester (B) is preferably 100 mol% in total of the component (V), the component (VI), and the component (VII). Other glycol components may be contained in the total glycol component in a range of 5 mol% or less.

  As described above, in the polyether ester (B), when the total carboxylic acid component is 100 mol% and the total glycol component is 100 mol%, the copolymerization amount (mol%) of the respective components (I) to (VII). Satisfies the relationship represented by the following (formula 2), and further preferably satisfies the relationship represented by the following (formula 2 ′).

(Formula 2)
(I) / (II) / (III) / (IV) = 20-45 / 30-45 / 7-14 / 18-25, and
(V) / (VI) / (VII) = 48-58 / 40-50 / 1.5-5
(Formula 2 ')
(I) / (II) / (III) / (IV) = 25-40 / 30-45 / 8-12 / 12 / 22-22, and
(V) / (VI) / (VII) = 50-56 / 42-48 / 1.5-3

  The reduced viscosity of the polyether ester (B) is usually preferably 0.30 dl / g or more, more preferably 0.35 dl / g or more, 0.60 dl / g or less, further 0.55 dl / g or less, In particular, it is preferably 0.50 dl / g or less. When the reduced viscosity is less than 0.30 dl / g, the melt viscosity is low, the difference in melt viscosity from the polycarbonate resin (A) is increased, and there is a concern about the decrease in transparency and bleeding out of the polycarbonate resin composition. Absent. When the reduced viscosity exceeds 0.60 dl / g, when trimellitic anhydride is used as the component (III) during polymerization of the raw material compound when producing the polyether ester (B), the trimellitic anhydride This is not preferable because three-dimensional crosslinking may occur due to the influence of the above. Even if the three-dimensional crosslinking does not occur at the time of polymerization, the polyether ester (B) having a reduced viscosity exceeding 0.60 dl / g may cause the three-dimensional crosslinking due to the thermal history when the polycarbonate resin composition is produced. So it is not preferable. The reduced viscosity of 0.30 dl / g is about 3000 in terms of number average molecular weight.

  The refractive index of the polyether ester (B) is preferably in the range of 1.570 to 1.585, more preferably in the range of 1.573 to 1.579. When the polyether ester (B) whose refractive index is out of the above range is used, the difference in refractive index from the polycarbonate resin (A) is large, so that sufficient transparency may not be imparted to the polycarbonate resin composition.

  Generally, a polyester resin is polymerized under reduced pressure after preparing an oligomer. Examples of the oligomer preparation method for producing the polyether ester (B) used in the present invention include an atmospheric pressure reaction method and a pressure reaction method. When the pressure reaction method is employed, terephthalic acid is preferably used as the component (II), and when the atmospheric pressure reaction method is employed, dimethyl terephthalate is preferably used as the component (II).

  The content of the polyether ester (B) is 8 to 40 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A). When the content of the polyether ester (B) is less than 8 parts by weight, no continuous antistatic property is observed in the polycarbonate resin composition. When content of polyetherester (B) exceeds 40 weight part, transparency and heat resistance of a polycarbonate resin composition will fall. The suitable content of the polyether ester (B) is 12 to 30 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A).

  The polycarbonate resin composition of the present invention contains an organometallic salt compound (C). Examples of the organic metal salt compound (C) used in the present invention include aromatic sulfonic acid metal salts, perfluoroalkanesulfonic acid metal salts, and the like, and preferably p-toluenesulfonic acid metal salts. Salt, potassium salt of 4-methyl-N- (4-methylphenyl) sulfonyl-benzenesulfonamide, potassium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-3'-disulfonate, potassium perfluorobutanesulfonate Etc. can be used. Among these, a metal salt of p-toluenesulfonic acid, such as sodium p-toluenesulfonate, is particularly preferable in that the transparency of the polycarbonate resin composition is improved and the cost performance is excellent.

  Content of organometallic salt compound (C) is 0.05-1.0 weight part with respect to 100 weight part of polycarbonate resin (A). When the content of the organometallic salt compound (C) is less than 0.05 parts by weight, the effect of improving the antistatic property of the polycarbonate resin composition is not recognized. When content of an organometallic salt compound (C) exceeds 1.0 weight part, the haze of a polycarbonate resin composition will become high and transparency will fall. A suitable content of the organometallic salt compound (C) is 0.15 to 0.8 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A).

  In the polycarbonate resin composition of the present invention, a known material other than the polycarbonate resin (A), the polyether ester (B), and the organometallic salt compound (C) may be used as long as the effects of the present invention are not impaired. Various additives, polymers, and the like can be added.

  Examples of various additives and polymers include, for example, light stabilizers; fluorescent brighteners; antioxidants; paraffin wax, n-butyl stearate, synthetic beeswax, natural beeswax, glycerin monoester, montanic acid wax, polyethylene wax Lubricants such as pentaerythritol tetrastearate; colorants such as titanium oxide, carbon black, dyes; calcium carbonate, clay, silica, glass fiber, glass sphere, glass flake, carbon fiber, talc, mica, various whiskers, etc. Fluidity improvers; Flame retardants such as bromine compounds, phosphorus compounds and silicone compounds; Spreaders such as epoxidized soybean oil and liquid paraffin; Other thermoplastic resins; for example, polybutadiene and polyacrylic Metals such as acid esters and ethylene-propylene rubber Acrylic acid esters, styrene, impact modifiers such as rubber-reinforced resin obtained by graft-polymerizing a compound of acrylonitrile.

  Although there is no restriction | limiting in particular about the compounding method of polycarbonate resin (A), polyether ester (B), and organometallic salt compound (C) which are the structural components of the polycarbonate resin composition of this invention, For example, a tumbler, a ribbon blender After batch mixing with a high-speed mixer or the like, the mixture is melt-kneaded using a normal single-screw extruder or twin-screw extruder and pelletized, or each component is weighed separately and from a plurality of supply devices A method of introducing into an extruder and melt-mixing, and further blending a polycarbonate resin (A) with a high concentration of an organometallic salt compound (C), once melt-mixing and pelletizing to obtain a master batch, A method of mixing the master batch and the polyether ester (B) in a desired ratio can be employed. Then, when these components are melt-mixed, arbitrary conditions such as a position to be introduced into the extruder, an extrusion temperature, a screw rotation speed, a supply amount, and the like can be selected and pelletized. The master batch and the polyether ester (B) can be dry-mixed at a desired ratio and then directly fed into a molding machine to form a molded product.

  The polycarbonate resin composition of the present invention is usually molded into an arbitrary shape and used as a molded product (resin composition molded product). There is no restriction | limiting in the shape, dimension, etc. of this molded article, What is necessary is just to set arbitrarily according to the use of the molded article. Examples of molded products include members for IC-related product production lines, panel members that require heat resistance and sustained antistatic properties, and the like.

  There is no restriction | limiting in particular as a method of shape | molding the polycarbonate resin composition of this invention, The shaping | molding method generally employ | adopted about the polycarbonate resin composition can be employ | adopted arbitrarily. For example, a known injection molding method, extrusion molding method, injection / compression molding method, or the like can be employed.

  As described above, the molded article of the present invention thus obtained should be used as a practical molded article having heat resistance and sustained antistatic properties without impairing transparency, which is an excellent property of the polycarbonate resin. Can do.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily changed or modified without departing from the spirit of the present invention. Unless otherwise specified, “%” and “parts” in the examples indicate “% by weight” and “parts by weight” based on the weight standard, respectively.

  Each component used for the Example and the comparative example is as follows.

<Polycarbonate resin (A)> (hereinafter referred to as “PC”)
-Polycarbonate resin synthesized from bisphenol A and phosgene-Caliber 200-13, manufactured by Sumika Stylon Polycarbonate Co., Ltd.
Viscosity average molecular weight: 21500
-Refractive index: 1.584

<Polyetherester (B) 1> (hereinafter referred to as “PEE1”)
・ Polyether ester (carboxylic acid component) with the following copolymer composition
Dimethyl 2,6-naphthalenedicarboxylate / terephthalic acid / trimellitic anhydride / sodium m-sulfobenzoate = 37/33/10/20 (mol%)
(Glycol component)
Ethylene glycol / diethylene glycol / polyethylene glycol (# 2000, number average molecular weight 2000 calculated from hydroxyl value determined by manufacturer) = 52/46/2 (mol%)
-112 mol% of all glycol components with respect to 100 mol% of all carboxylic acid components
-Refractive index: 1.579
Reduced viscosity: 0.43 dl / g

<Synthesis of PEE1>
In a stainless steel autoclave with a stirrer (capacity 2 L), dimethyl 2,6-naphthalenedicarboxylate 178.0 g (0.73 mol), terephthalic acid 86.8 g (0.52 mol), trimellitic anhydride 35.4 g ( 0.18 mol), 90.8 g (0.40 mol) of sodium m-sulfobenzoate, 77.3 g (0.039 mol) of polyethylene glycol and 217.0 g (3.5 mol) of ethylene glycol, and carbon dioxide as a catalyst. 0.18 g of germanium and 1 g of Irganox 1330 (manufactured by BASF, Irganox is a registered trademark) as a stabilizer were charged at 150 ° C. and reacted at 120 ° C. for 120 minutes while raising the temperature to 220 ° C., An oligomer mixture was obtained.

  Thereafter, while raising the temperature to 240 ° C. over 60 minutes, the pressure of the reaction system is gradually reduced to 13.3 Pa (0.1 Torr), and further a polyester polycondensation reaction is performed under the conditions of 240 ° C. and 13.3 Pa. It was. After releasing the pressure, the resin under slightly pressurized pressure is discharged into cold water in a strand form, quenched, then held in cold water for 20 seconds, and then cut to form a cylinder having a cylinder shape with a length of about 3 mm and a diameter of about 2 mm. Ether ester pellets were obtained.

The composition and composition ratio of the obtained polyether ester were determined by ¹ H-NMR measurement (proton nuclear magnetic resonance spectroscopy) at a resonance frequency of 500 MHz using an NMR apparatus (manufactured by VARIAN, 500-MHz). went. In addition, deuterated chloroform / deuterated hexafluoroisopropanol = 85/15 (weight ratio) was used as the solvent. Diethylene glycol was a by-product formed by condensation of ethylene glycol, and this was copolymerized with other components.

  A refractive index is about 0.1 mm thick by a heat press (manufactured by Tester Sangyo Co., Ltd.), and a prism coupler (manufactured by Metricon, Model 2010, wavelength: 632.2 nm (He-Ne)), prism used. : 200-P-4 (Prism N = 2.15988), measurement type: Bulk / substrate). Since the obtained polyether ester is copolymerized with ionic monomer sodium m-sulfobenzoate, it absorbs moisture during the standing time and measurement time after heat pressing. Therefore, after measuring the refractive index, the water content was confirmed with a Karl Fischer moisture meter (temperature: 150 ° C.), and the value obtained by extrapolating the moisture content to 0 was taken as the refractive index.

The reduced viscosity was measured by dissolving 0.05 g of the obtained polyether ester in 25 cm ³ of a mixed solvent (phenol / tetrachloroethane (mass ratio) = 6/4) at 30 ° C. using an Ubbelohde viscosity tube.

<Polyetherester (B) 2> (hereinafter referred to as “PEE2”)
・ Polyether ester (carboxylic acid component) with the following copolymer composition
Dimethyl 2,6-naphthalenedicarboxylate / terephthalic acid / trimellitic anhydride / m-sodium sulfobenzoate = 27/43/10/20 (mol%)
(Glycol component)
Ethylene glycol / diethylene glycol / polyethylene glycol (# 2000, number average molecular weight 2000 calculated from hydroxyl value determined by manufacturer) = 54/44/2 (mol%)
-112 mol% of all glycol components with respect to 100 mol% of all carboxylic acid components
-Refractive index: 1.573
Reduced viscosity: 0.43 dl / g

<Synthesis of PEE2>
In a stainless steel autoclave with a stirrer (capacity 2 L), 137.1 g (0.56 mol) of dimethyl 2,6-naphthalenedicarboxylate, 118.1 g (0.71 mol) of terephthalic acid, 35.9 g of trimellitic anhydride ( 0.19 mol), 92.3 g (0.41 mol) of sodium m-sulfobenzoate, 78.6 g (0.040 mol) of polyethylene glycol and 229.8 g (3.7 mol) of ethylene glycol, and carbon dioxide as a catalyst. 0.18 g of germanium and 1 g of Irganox 1330 (manufactured by BASF, Irganox is a registered trademark) as a stabilizer were charged at 150 ° C. and reacted at 120 ° C. for 120 minutes while raising the temperature to 220 ° C., An oligomer mixture was obtained.

  Thereafter, while raising the temperature to 240 ° C. over 60 minutes, the pressure of the reaction system is gradually reduced to 13.3 Pa (0.1 Torr), and further a polyester polycondensation reaction is performed under the conditions of 240 ° C. and 13.3 Pa. It was. After releasing the pressure, the resin under slightly pressurized pressure is discharged into cold water in a strand form, quenched, then held in cold water for 20 seconds, and then cut to form a cylinder having a cylinder shape with a length of about 3 mm and a diameter of about 2 mm. Ether ester pellets were obtained.

  The composition and composition ratio of the obtained polyether ester were determined in the same manner as in the PEE1. Diethylene glycol was a by-product formed by condensation of ethylene glycol, and this was copolymerized with other components. Further, the refractive index and the reduced viscosity were also determined in the same manner as PEE1.

<Organic metal salt compound (C)> (hereinafter referred to as “metal salt”)
・ Sodium p-toluenesulfonate

<Manufacture of pellets of polycarbonate resin composition> (Examples 1 to 6 and Comparative Examples 1 to 4)
Each of the above components was put into a tumbler at the blending ratio shown in Table 1 below, and after dry mixing for 10 minutes, a twin-screw extruder (manufactured by Nippon Steel Works, TEX30α, shaft diameter: 30 mmφ, L / D) = 41), kneading was performed at a melting temperature of 230 ° C. to obtain pellets of a polycarbonate resin composition.

<Preparation of test piece>
Each of the obtained pellets was dried in advance under the conditions of 110 ° C. × 4 hours (however, Comparative Example 2 adopted the conditions of 80 ° C. × 4 hours), and then injection molding machine (Nippon Steel Co., Ltd.) A flat plate test piece (length 50 mm, width 50 mm, thickness 3 mm) was produced under the conditions of a cylinder set temperature of 260 ° C. using J100E2P). In addition, after producing a dumbbell test piece in accordance with the method specified in JIS K 7139 “Plastic Test Piece” under the condition of a cylinder set temperature of 250 ° C., a test piece for load deflection test (vertical) 80 mm, width 10 mm, thickness 4 mm).

  Hereinafter, each evaluation item and measurement method will be described. The evaluation results are shown in Table 1 below.

1. Antistatic property A flat test piece was washed with tap water for 1 minute, and after conditioning for 24 hours under conditions of 23 ° C. and 50% relative humidity, a high resistivity meter (Hiresta UP, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) The surface resistivity was measured under the conditions of an applied voltage of 1000 V and a sampling time of 10 seconds. The evaluation criteria for antistatic properties are as follows.
(Evaluation criteria)
Good (◯): When the surface specific resistance is less than 1 × 10 ¹³ Ω / □ Defective (×): When the surface specific resistance is 1 × 10 ¹³ Ω / □ or more

2. Transparency <Total light transmittance>
JIS K 7361-1 “Plastic: Test method for total light transmittance of transparent material—Part 1: Single beam by using a flat test piece and using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.) The total light transmittance was measured according to the method prescribed in “Method”. The evaluation criteria for transparency are as follows.
(Evaluation criteria)
Good (O): When the total light transmittance is 75% or more Defective (X): When the total light transmittance is less than 75%

<Haze>
Using a flat test piece, the haze was measured with a haze meter (HM-150, manufactured by Murakami Color Research Laboratory Co., Ltd.) according to the method specified in JIS K 7136 “How to determine haze for plastics and transparent materials”. It was measured. The evaluation criteria for transparency are as follows.
(Evaluation criteria)
Good (O): When haze is less than 16% Poor (x): When haze is 16% or more

3. Heat resistance ISO 75-2 “Plastics-Determination of temperature of deflection under load-Part 2: Plastics” using HDT tester (HDT Tester, Toyo Seiki Seisakusho Co., Ltd.) The deflection temperature under load was measured in accordance with the method specified in “and ebonite”. The evaluation criteria for heat resistance are as follows.
(Evaluation criteria)
Good (O): When the deflection temperature under load is 100 ° C or higher NG (X): When the deflection temperature under load is less than 100 ° C

4). Comprehensive judgment It judged based on evaluation of antistatic property, transparency, and heat resistance. The evaluation criteria are as follows.
(Evaluation criteria)
Good (○): When all are good Defective (×): When even one is defective

  As shown in Table 1, when the configuration of the present invention was satisfied (Examples 1 to 6), it had sufficient performance in all of the continuous antistatic property, transparency and heat resistance.

  On the other hand, when the configuration of the present invention was not satisfied (Comparative Examples 1 to 4), each case had some drawbacks.

  Comparative Example 1 is a case where the content of the polyether ester (B) (PEE1) is less than the specified amount, and although transparency and heat resistance are satisfied, the surface specific resistance is large and the antistatic property is inferior. .

  Comparative Example 2 is a case where the content of the polyether ester (B) (PEE1) is larger than the specified amount, and although the antistatic property is satisfactory, the total light transmittance is low, the haze is high, and the transparency is inferior. In addition, the deflection temperature under load was low and the heat resistance was poor.

  Comparative Example 3 was a case where the content of the organometallic salt compound (C) was less than the specified amount, and although the transparency and heat resistance were satisfactory, the surface specific resistance was large and the antistatic property was inferior.

  Comparative Example 4 was a case where the content of the organometallic salt compound (C) was larger than the specified amount, and although antistatic properties and heat resistance were satisfied, the haze was high and the transparency was poor.

  The antistatic polycarbonate resin composition of the present invention can be used in an environment where it comes into contact with water, repeated use of a product, long-term use, and the like. In addition, the antistatic polycarbonate resin composition of the present invention is required to be a member for production lines of IC-related products that require visibility and dust adhesion is avoided, as well as heat resistance and sustained antistatic properties. It is suitably used for panel members and the like, and its practical utility value is extremely high.

Claims (5)

8 to 40 parts by weight of a polyether ester (B) composed of a carboxylic acid component and a glycol component, and 0.05 to 1.0 part by weight of an organometallic salt compound (C) with respect to 100 parts by weight of the polycarbonate resin (A) Containing
The carboxylic acid component of the polyether ester (B) is
(I) 2,6-naphthalenedicarboxylic acid compound,
(II) terephthalic acid compound,
(III) a compound having three or more carboxyl groups, and (IV) a carboxylic acid compound containing a sulfonate group represented by the following (formula 1) as a constituent:
The glycol component of the polyether ester (B) is
(V) ethylene glycol,
(VI) diethylene glycol, and (VII) polyalkylene glycol as a constituent,
When the total carboxylic acid component is 100 mol% and the total glycol component is 100 mol%, the copolymerization amount (mol%) of each component (I) to (VII) is represented by the following (formula 2). An antistatic polycarbonate resin composition characterized by satisfying the relationship.
(Formula 1)

(Wherein, X ¹ represents a C 6-20 divalent aromatic group or a C 1-8 alkylene group, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion or a tetraalkylammonium ion)
(Formula 2)
(I) / (II) / (III) / (IV) = 20-45 / 30-45 / 7-14 / 18-25, and
(V) / (VI) / (VII) = 48-58 / 40-50 / 1.5-5   The antistatic polycarbonate resin composition of Claim 1 whose content of the said polyetherester (B) is 12-30 weight part with respect to 100 weight part of polycarbonate resin (A).   The antistatic polycarbonate resin composition according to claim 1, wherein the organometallic salt compound (C) is a metal salt of p-toluenesulfonic acid.   The antistatic polycarbonate resin composition according to claim 1, wherein the content of the organometallic salt compound (C) is 0.15 to 0.8 parts by weight with respect to 100 parts by weight of the polycarbonate resin (A). .   A molded article formed by molding the antistatic polycarbonate resin composition according to any one of claims 1 to 4.