JP2014051540A - Antistatic polycarbonate resin composition and molded article formed from the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a molded article of a polycarbonate resin composition that is excellent in transparency, heat resistance and durable antistatic properties and therefore, is suitable for use in a member for a production line of IC related products which is required to have visibility and avoid adhesion of dust, a panel member which is required to have heat resistance, and the like.SOLUTION: An antistatic polycarbonate resin composition comprises 100 pts.wt. of a polycarbonate resin (A), 5-40 pts.wt. of a specific polyether ester (B), not less than 0.05 pt.wt. to less than 0.5 pt.wt. of an organometallic salt compound (C) and 0-160 pts.wt. of a glycol-modified polyester resin (D).

Description

  The present invention relates to a polycarbonate resin composition comprising a polycarbonate resin and a specific polymer and a salt, which are excellent in transparency, heat resistance and sustained antistatic properties, and a molded article comprising the same.

  Polycarbonate resins are excellent in impact resistance, heat resistance, and transparency, and are widely used in various fields such as electric / electronic, optical, building materials, medical, food, and vehicles. However, products using plastics including polycarbonate resins generally have a feature that electrostatic charges are difficult to dissipate due to their 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, transparency as a resin composition, heat resistance and machine There was a problem that physical properties were greatly impaired.

  Furthermore, a method using a polyether ester having a sulfonate group and an ionic surfactant has been proposed (Patent Document 5). In order to develop stable antistatic performance, a large amount of ionic surfactant is used. There was a problem that it was necessary to add, and transparency as a resin composition was 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 continuous antistatic property without impairing transparency and heat resistance, and a molded article comprising the same.

As a result of intensive studies in order to solve the above problems, the present inventors have completed the present invention. That is, the present invention relates to a polyether obtained by polycondensing a component containing 100 parts by weight of a polycarbonate resin (A) and an aromatic dicarboxylic acid substituted with a sulfonate group represented by the following formula (1) as an essential component. Charge comprising 5 to 40 parts by weight of an ester (B), 0.05 part by weight or more and less than 0.5 part by weight of an organometallic salt compound (C) and 0 to 160 parts by weight of a glycol-modified polyester resin (D) The present invention provides a preventive polycarbonate resin composition and a molded product formed by molding the same.
Formula (1)

式（１）中、Ａｒは炭素数６〜１２の３価の芳香族基、Ｒ１およびＲ２はそれぞれ独立に水素原子、炭素数１〜６のアルキル基又は炭素数６〜１２のアリール基を表し、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表す。

In formula (1), Ar represents a trivalent aromatic group having 6 to 12 carbon 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.

  A molded article comprising the antistatic polycarbonate resin composition of the present invention is excellent in transparency, heat resistance and sustained antistatic properties. Therefore, it is suitably used for a member for a production line of an IC-related product that requires visibility and avoids adhesion of dust or a panel member that requires heat resistance, and its practical utility value is extremely high.

  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.

  Examples of the dihydroxydiaryl compound include bisphenol 4-, 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 ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- (4-hydroxyphenyl) cyclopentane, bis (hydroxyaryl) cycloalkanes such as 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3 ' Dihydroxy diaryl sulfoxides such as dimethyldiphenyl sulfoxide, dihydroxy diary such as 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone Sulfone, and the like. These are used individually or in mixture of 2 or more types. In addition to these, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be mixed and used.

  Furthermore, the above dihydroxyaryl compound and a trivalent or higher phenol compound as shown below may be used in combination. Trihydric or higher phenols 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. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst and the like can be used as necessary.

The polyether ester (B) in the present invention is (b1) an aromatic dicarboxylic acid having 6 to 20 carbon atoms, (b2) a poly (alkylene oxide) glycol having a number average molecular weight of 200 to 50000, and (b3) 2 carbon atoms. To 10 glycols can be obtained by polycondensation. Here, the aromatic dicarboxylic acid having 6 to 20 carbon atoms, which is a component constituting the polyether ester, is an aromatic dicarboxylic acid (b1a) 98 to 70 mol% and a sulfonate group represented by the following formula (1). It consists mainly of 2 to 30 mol% of substituted aromatic dicarboxylic acid (b1b).
Formula (1)

  In formula (1), Ar represents a trivalent aromatic group having 6 to 12 carbon 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.

  Here, as the aromatic dicarboxylic acid (b1a), in terms of transparency, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, diphenyl-4,4-dicarboxylic acid, alkyl or halogen substitution thereof. Naphthalenedicarboxylic acid, biphenyldicarboxylic acid and ester-forming derivatives thereof. These can be used alone or in combination of two or more.

  In addition, the aromatic dicarboxylic acid (b1a) is within a range not reducing the glass transition temperature and crystallinity of the polyether ester (B) (for example, 30 mol% or less, preferably 20 mol% or less of the entire (b1a), More preferably, the dicarboxylic acid component having 4 to 20 carbon atoms may be used at 10 mol% or less. Examples of the other dicarboxylic acid components having 4 to 20 carbon atoms include aliphatic dicarboxylic acids such as succinic acid, adipic acid, and sebacic acid, and ester-forming derivatives thereof. Examples of these ester-forming derivatives include aliphatic dicarboxylic acid alkyl esters such as dimethyl succinate, diethyl succinate, dimethyl adipate, diethyl adipate, dimethyl sebacate, and diethyl sebacate.

The aromatic dicarboxylic acid (b1b) substituted with a sulfonate group in the present invention is represented by the following formula (1).
Formula (1)

  In the above formula (1), 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, preferably a hydrogen atom, a methyl group, an ethyl group or the like. It is a C1-C3 alkyl group.

  In the above formula (1), M + represents an ion selected from metal ions, tetraalkylphosphonium ions, and tetraalkylammonium ions. M + includes alkali metal ions such as sodium ion, potassium ion and lithium ion, alkaline earth metal ions such as calcium ion and magnesium ion, zinc ion, tetrabutylphosphonium ion, tetramethylphosphonium ion, tetrabutylammonium ion and tetramethyl. Ammonium ions and the like. Of these ions, alkali metal ions and tetrabutylammonium ions are more preferred. However, in the case of a divalent metal ion, 1 mol of metal ion corresponds to 2 mol of sulfonic acid group.

  Ar in the above formula (1) is a trivalent aromatic group having 6 to 12 carbon atoms such as a benzene ring and a naphthalene ring, and these are also substituents such as an alkyl group, a phenyl group, a halogen, and an alkoxy group. You may have.

  Examples of the aromatic dicarboxylic acid (b1b) include 4-sodium sulfo-isophthalic acid, 5-sodium sulfo-isophthalic acid, 4-potassium sulfo-isophthalic acid, 5-potassium sulfo-isophthalic acid, and 2-sodium sulfo-terephthalic acid. 2-potassium sulfo-terephthalic acid, 4-sulfo-isophthalic acid zinc, 5-sulfo-isophthalic acid zinc, 2-sulfo-terephthalic acid zinc, 4-sulfo-isophthalic acid tetraalkylphosphonium salt, 5-sulfo-isophthalic acid Tetraalkylphosphonium salt, 4-sulfo-isophthalic acid tetraalkylammonium salt, 5-sulfo-isophthalic acid tetraalkylammonium salt, 2-sulfo-terephthalic acid tetraalkylphosphonium salt, 2-sulfo-terephthalic acid tetraalkylammonium salt 4-sodium sulfo-2,6-naphthalenedicarboxylic acid, 4-sodium sulfo-2,7-naphthalenedicarboxylic acid, 4-potassium sulfo-2,6-naphthalenedicarboxylic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid Examples include zinc salts, 4-sulfo-2,6-naphthalenedicarboxylic acid tetraalkylphosphonium salts, 4-sulfo-2,7-naphthalenedicarboxylic acid tetraalkylphosphonium salts, and the like. Examples of these ester-forming derivatives include dimethyl esters and diethyl esters of aromatic dicarboxylic acids specifically listed above.

  Among these, R1 and R2 are both a methyl group and an ethyl group, Ar is a benzene ring, and M + is an alkali metal ion such as sodium or potassium, in terms of polymerizability, mechanical properties, color tone, and the like. And more preferable.

  Specifically, for example, 4-sodium sulfo-isophthalate dimethyl, 5-sodium sulfo-isophthalate dimethyl, 4-potassium sulfo-isophthalate dimethyl, 5-potassium sulfo-isophthalate dimethyl, 2-sodium sulfo-terephthalic acid More preferred are dimethyl, 2-potassium sulfo-dimethyl terephthalate and the like.

  According to the present invention, the aromatic dicarboxylic acid (b1b) substituted with the aromatic dicarboxylic acid (b1a) and the sulfonate group includes 98 to 70 mol% of the total acid content constituting the polyether ester (B), and 2 to 30 mol%. In other words, the aromatic dicarboxylic acid (b1b) substituted with a sulfonate group is copolymerized so as to occupy 2 to 30 mol% of the entire aromatic dicarboxylic acid component. When the ratio of the compound (b1b) is less than 2 mol%, the antistatic effect is not sufficient, or the durability of the antistatic effect against water washing or wiping of the molded product is insufficient. Moreover, when the ratio of this compound exceeds 30 mol%, a polymerization reaction will become difficult and it will become difficult to obtain polyether ester (B) of sufficient polymerization degree. Furthermore, the crystallinity of the polyether ester (B) is lowered, resulting in insufficient drying or poor handling. The aromatic dicarboxylic acid (b1) having 6 to 20 carbon atoms in the present invention is preferably an aromatic dicarboxylic acid (b1b) 3 substituted with 97 to 71 mol% of an aromatic dicarboxylic acid (b1a) and a sulfonate group. 29 mol%, more preferably (b1a) 95 to 73 mol% and (b1b) 5 to 27 mol%, particularly preferably (b1a) 91 to 75 mol% and (b1b) 9 to 25 mol%. Become.

  The poly (alkylene oxide) glycol (b2), which is one of the constituent components of the polyether ester (B) in the present invention, is preferably a polyalkylene glycol mainly composed of polyethylene glycol, in which case polypropylene glycol or the like is used as a copolymerization component. May be included.

  Such poly (alkylene oxide) glycol (b2) has a number average molecular weight of 200 to 50,000. When the molecular weight is less than 200, a sufficient antistatic effect cannot be obtained. From the practical point of view, the upper limit of the molecular weight is about 50,000. The preferred molecular weight of the poly (alkylene oxide) glycol (b2) is 500-30000, more preferably 1000-20000.

Furthermore, within the above molecular weight range, such poly (alkylene oxide) glycol (b2) may have an aromatic ring in the molecule. Examples of the poly (alkylene oxide) glycol (b2) include those having the structures of the following formulas (2) and (3).
Formula (2):
H (O-CH2CH2) pO-Ar1-O (CH2CH2-O) qH
Formula (3):
H (O-CH2CH2) rO-Ph-X-Ph-O (CH2CH2-O) sH

  In the above formulas (2) and (3), Ar1 is a trivalent aromatic group having 6 to 12 carbon atoms such as a benzene ring or a naphthalene ring, and Ph is a benzene ring. These may also have a substituent such as an alkyl group, a phenyl group, a halogen, or an alkoxy group. P, q, r, and s represent an integer of 2 to 60, and -X- represents an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 5 to 10 carbon atoms, -O-, and -S-. , -SO2-. These may be used as poly (alkylene oxide) glycol (b2) itself, which is one of the constituent components of the polyether ester (B), or used as part of other poly (alkylene oxide) glycols. May be.

  The amount of the poly (alkylene oxide) glycol (b2) used is that of the polyether ester (b2) constituting the polyetherester obtained by polycondensation of (b1), (b2) and (b3) ( 10 to 60% by weight with respect to B), in other words, substantially 10 to 60% by weight with respect to the total amount of preparations (b1), (b2), and (b3). If it is less than 10% by weight, the antistatic effect is not sufficient, and if it is more than 80% by weight, the handling property and heat resistance may tend to be poor. A preferable use amount is 15 to 55% by weight, more preferably 20 to 50% by weight, based on the whole polyether ester (B).

  Specifically, the glycol (b3) having 2 to 10 carbon atoms constituting the polyether ester (B) in the present invention is ethylene glycol, 1,4-butanediol, propylene glycol, 1,6-hexanediol, 3- Examples thereof include aliphatic glycols such as methyl-1,5-pentanediol. These may contain an ether bond such as diethylene glycol and a thioether bond such as thiodiethanol. Further, such compounds can be used alone or in combination of two or more. Among the above glycols, 1,6-hexanediol, ethylene glycol, and diethylene glycol are preferable in terms of antistatic effect, crystallinity, and handleability.

  The polyether ester (B) in the present invention can be obtained by heating and melting the components (b1) to (b3) at 150 to 300 ° C. in the presence of a transesterification catalyst.

  Here, the transesterification catalyst is not particularly limited as long as it can be used for a normal transesterification reaction. These transesterification catalysts include antimony compounds such as antimony trioxide, tin compounds such as stannous acetate, dibutyltin oxide and dibutyltin diacetate, titanium compounds such as tetrabutyl titanate, zinc compounds such as zinc acetate, and calcium compounds such as calcium acetate. Examples thereof include alkali metal salts such as compounds, sodium carbonate and potassium carbonate. Of these, tetrabutyl titanate is preferably used.

  Further, the amount of the catalyst used may be the amount used in a normal transesterification reaction, and is generally preferably 0.01 to 0.5 mol%, preferably 0.03 to 0.3 mol, per 1 mol of the dicarboxylic acid used. 3 mol% is more preferable. Further, it is also preferable to use various stabilizers such as an antioxidant in the reaction.

  As the temperature at which the compounds (b1) to (b3) are heated and melted and polycondensed, the initial reaction is an esterification reaction and / or a transesterification reaction at 150 to 250 ° C. for several tens of minutes to a dozen hours. Then, a polymerization reaction for increasing the molecular weight of the reaction product is performed at 180 to 300 ° C. This is because if the temperature is lower than 180 ° C., the reaction does not proceed, and if the temperature is higher than 300 ° C., side reactions such as decomposition tend to occur. The polymerization reaction temperature is more preferably 200 to 80 ° C, further preferably 220 to 260 ° C. The reaction time of this polymerization reaction is usually several tens of minutes to several tens of hours although it depends on the reaction temperature and the amount of catalyst.

  The compounding quantity of the polyether ester (B) in this invention is 5-40 weight part per 100 weight part of polycarbonate resin (A). A blending amount of less than 5 parts by weight is not preferable because continuous antistatic properties are not observed. Moreover, when it exceeds 40 weight part, since transparency and heat resistance as a resin composition will become low, it is unpreferable. A more preferable blending amount is in the range of 10 to 30 parts by weight.

  Examples of the organic metal salt compound (C) used in the present invention include a metal salt of aromatic sulfonic acid and a metal salt of perfluoroalkanesulfonic acid, and preferably 4-methyl-N- (4- Methylphenyl) sulfonyl-benzenesulfonamide potassium salt, potassium diphenylsulfone-3-sulfonate, potassium diphenylsulfone-3-3'-disulfonate, potassium perfluorobutanesulfonate, and the like can be used. In particular, sodium paratoluenesulfonate is excellent in terms of transparency and cost performance.

  The compounding amount of the organometallic salt compound (C) is 0.05 to 0.5 parts by weight per 100 parts by weight of the polycarbonate resin (A). If the blending amount is less than 0.05 parts by weight, the effect of improving the antistatic property is not recognized, which is not preferable. Moreover, when it exceeds 0.5 weight part, since haze becomes high and transparency is inferior, it is not preferable. A more preferred blending amount is in the range of 0.15 to 0.35 parts by weight.

  The glycol-modified polyester resin (D) used in the present invention includes an amorphous polyester resin in which a part of ethylene glycol constituting polyethylene terephthalate is replaced with cyclohexanedimethanol. Those having a substitution rate from ethylene glycol to cyclohexanedimethanol of less than 50 mol% are classified as glycol-modified polyethylene terephthalate, and those having 50 mol% or more are classified as polycyclohexylene dimethylene terephthalate. In particular, polycyclohexylene dimethylene terephthalate is excellent in terms of heat resistance as a composition. The polycyclohexylenedimethylene terephthalate is easily available as a commercial product, and examples thereof include SKYGREEN JN100 manufactured by SK Chemicals.

  The glycol-modified polyester resin (D) is excellent in miscibility with the polycarbonate resin (A). Therefore, by changing the mixing ratio of the polycarbonate resin (A) [refractive index 1.584] and the glycol-modified polyester resin (D) [refractive index 1.562], the refractive index is between 1.562 and 1.584. Can adjust the admixture having a desired refractive index. The transparency of the polycarbonate resin composition can be improved by adjusting the refractive indexes of the polyether ester (B) and the mixture in the present invention to within ± 0.003.

  The blending amount of the glycol-modified polyester resin (D) is 0 to 160 parts by weight per 100 parts by weight of the polycarbonate resin (A). Depending on the refractive index of the polyether ester (B) in the present invention, a glycol-modified polyester resin (D) can be added as desired. However, if the amount exceeds 160 parts by weight, the heat resistance of the composition is lowered, which is not preferable. A more preferable blending amount is in the range of 0 to 120 parts by weight.

  In the antistatic polycarbonate resin composition of the present invention, various known additives, polymers and the like other than those described above can be added as desired within the range not impairing the effects of the present invention. For example, light stabilizer, fluorescent brightener, antioxidant, lubricant [paraffin wax, n-butyl stearate, synthetic beeswax, natural beeswax, glycerin monoester, montanic acid wax, polyethylene wax, pentaerythritol tetrastearate, etc.] , Colorants [e.g., titanium oxide, carbon black, dye], fillers [calcium carbonate, clay, silica, glass fiber, glass sphere, glass flake, carbon fiber, talc, mica, various whiskers, etc.], fluidity improver Flame retardants [bromine, phosphorus, silicone, etc.], spreading agents [epoxidized soybean oil, liquid paraffin, etc.], and other thermoplastic resins and various impact modifiers (polybutadiene, polyacrylate, Add rubber such as ethylene / propylene rubber to methacrylic acid ester, styrene, Rubber-reinforced resin or the like of the compound obtained by graft polymerization such Rironitoriru are exemplified.) Can be added as required.

  Although there is no restriction | limiting in particular about the compounding method of the structural component (A) of this invention, (B), (C), and (D), For example, after mixing collectively with a tumbler, a ribbon blender, a high-speed mixer etc., a mixture is usually A method of melt-kneading and pelletizing by using a single-screw or twin-screw extruder, or a method of measuring each component separately, putting them into a extruder from a plurality of feeders, and melt-mixing them, and (A) (A) and (D) can be blended at a high concentration, and once melt-mixed and pelletized into a master batch, the master batch and (B) can be mixed in a desired ratio. . 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. Further, the master batch and (B) may be dry mixed at a desired ratio, and then directly fed into a molding machine to form a molded product. The method for molding the transparent polycarbonate resin composition having excellent antistatic properties of the present invention is not particularly limited, and known injection molding methods, extrusion molding methods, injection / compression molding methods, and the like can be used. .

  EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” and “parts” in the examples are based on weight standards.

The raw materials used are as follows.
Polycarbonate resin:
Polycarbonate resin synthesized from bisphenol A and phosgene (Caliber 200-13, manufactured by Sumika Stylon Polycarbonate)
Viscosity average molecular weight: 21500, refractive index 1.584, hereinafter abbreviated as “PC”)

Polyetherester:
Synthesized according to the following. (Hereinafter abbreviated as “PEE-1”)
3881 parts dimethyl 2,6-naphthalenedicarboxylate, 642 parts dimethyl 5-sodium sulfoisophthalate, 1233 parts ethylene glycol, 1920 parts 1,6-hexanediol, 2313 parts polyethylene glycol (number average molecular weight 2000) And 3.1 parts of tetrabutyl titanate were placed in a reactor equipped with a rectifying column and a stirrer, and the inside of the vessel was purged with nitrogen, and then heated to 230 ° C. under normal pressure. After reacting for 5 hours while distilling off methanol at 230 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 60 minutes. The temperature was raised to 240 ° C. At that time, the pressure inside the reaction system was gradually reduced to 10 mmHg after 60 minutes, and the pressure inside the system was further reduced to 0.2 mmHg over 15 minutes, and a polymer was obtained 180 minutes after the high vacuum was reached.

According to the following, a polymer for comparison was synthesized. (Hereinafter abbreviated as “PEE-2”)
3881 parts dimethyl 2,6-naphthalenedicarboxylate, 642 parts dimethyl 5-isophthalate, 1233 parts ethylene glycol, 1920 parts 1,6-hexanediol, 2313 parts polyethylene glycol (number average molecular weight 2000) and 3 .1 part of tetrabutyl titanate was placed in a reactor equipped with a rectifying column and a stirrer, the inside of the vessel was purged with nitrogen, and then heated to 230 ° C. under normal pressure. After reacting for 5 hours while distilling off methanol at 230 ° C., the reaction product was put into a reactor having a vacuum distillation system equipped with a stirrer, and the reaction distillate was distilled off under normal pressure for 60 minutes. The temperature was raised to 240 ° C. At that time, the pressure inside the reaction system was gradually reduced to 10 mmHg after 60 minutes, and the pressure inside the system was further reduced to 0.2 mmHg over 15 minutes, and a polymer was obtained 180 minutes after the high vacuum was reached.

Organometallic salt compounds:
P-Toluenesulfonic acid sodium salt (hereinafter abbreviated as metal salt)
Glycol-modified polyester resin:
SKYGREEN JN100 made by SK Chemicals
(Hereafter abbreviated as PCTG)

  Each of the above-mentioned various raw materials was put in a tumbler at the blending ratios shown in Tables 1-2, and after dry mixing for 10 minutes, a twin-screw extruder (TEX30α manufactured by Nippon Steel Works, shaft diameter = 30 mmφ, L / D = 41) was kneaded at a melting temperature of 230 ° C. to obtain pellets of various polycarbonate resin compositions for evaluation.

  Each of the obtained pellets was dried in advance under the conditions of 110 ° C. × 4 hours (however, only Comparative Examples 2, 3 and 6 employed 80 ° C. × 4 hours), and then injection molding machine (Japan) A flat plate test piece (length 50 mm, width 50 mm, thickness 2 mm) was produced under the conditions of a cylinder set temperature of 270 ° C. using J100E2P). Moreover, after producing a dumbbell test piece according to JIS K 7139 under the condition of a cylinder temperature of 270 ° C., a test piece for load deflection test (80 mm in length, 10 mm in width, 4 mm in thickness) was produced by secondary processing.

Hereinafter, various evaluation items and measurement methods in the present invention will be described.
(Surface resistivity)
The molded flat plate test piece was washed with water for 1 minute and conditioned for 24 hours under conditions of 23 ° C. and 50% relative humidity, and then applied with a high resistivity meter (Hiresta UP, manufactured by Mitsubishi Chemical Corporation). The surface resistivity was measured under the conditions of 1000 V and sampling time of 10 seconds. The case where the surface specific resistance was less than 1 × 10 ¹³ (Ω / □) was judged as good (◯), and the case where it was 1 × 10 ¹³ (Ω / □) or more was judged as defective (×).

(Total light transmittance)
Using the flat plate test piece, the total light transmittance was measured according to JIS K 7361 with a haze meter (HM-150, manufactured by Murakami Color Research Laboratory). As a criterion for evaluation, a case where the value of the total light transmittance was 75% or more was judged as good (◯), and a case where it was less than 75% was judged as bad (x).

(Haze)
Haze was measured according to JIS K 7361 with a haze meter (HM-150, manufactured by Murakami Color Research Laboratory) using a flat test piece. As a criterion for evaluation, a case where the haze value was less than 25 was judged as good (◯), and a case where the haze value was 25 or more was judged as poor (x).

(Heat-resistant)
The deflection temperature under load was measured according to JIS K 7191 with an HDT test apparatus (HDT Tester manufactured by Toyo Seiki Co., Ltd.) using a test piece for load deflection test. As a criterion for evaluation, a case where the value of the deflection temperature under load was 100 ° C. or higher was judged as good (◯), and a case where it was less than 100 ° C. was judged as defective (×).

(Comprehensive judgment)
In the evaluation of surface specific resistance, total light transmittance, haze and heat resistance, all good were evaluated as good (◯), and others were determined as poor (x).

  As shown in Table 1 and Table 2, when the configuration of the present invention was satisfied (Examples 1 to 6), all the evaluation items had sufficient performance.

On the other hand, when the configuration of the present invention was not satisfied (Comparative Examples 1 to 6), each case had some drawbacks.
Comparative Example 1 was a case where the blending amount of the polyether ester was less than the specified amount, and although the total light transmittance, haze and heat resistance passed, the surface resistivity was inferior.
Comparative Example 2 was a case where the blending amount of the polyether ester was larger than the specified amount, and the surface resistivity passed, but the total light transmittance, haze and heat resistance were inferior.
Comparative Example 3 was a case where a polyether ester having no sulfo group introduced therein was used. Although the total light transmittance and haze passed, the surface resistivity and heat resistance were inferior.
Comparative Example 4 was a case where the compounding amount of the organometallic salt compound was less than the specified amount, and although the total light transmittance, haze and heat resistance passed, the surface resistivity was inferior.
Comparative Example 5 was a case where the compounding amount of the organometallic salt compound was larger than the specified amount, and the surface specific resistance and heat resistance passed, but the total light transmittance and haze were inferior.
Comparative Example 6 was a case where the blending amount of the glycol-modified polyester resin was larger than the specified amount, and although the surface resistivity passed, the total light transmittance, haze and heat resistance were inferior.

Claims (6)

Polyether ester (B) 5 to 100 parts by weight of a polycarbonate resin (A) obtained by polycondensing a component containing an aromatic dicarboxylic acid substituted with a sulfonate group represented by the following formula (1) as an essential component: Antistatic polycarbonate resin composition comprising 40 parts by weight, organic metal salt compound (C) 0.05 part by weight or more and less than 0.5 part by weight and glycol-modified polyester resin (D) 0 to 160 parts by weight .
Formula (1)

In formula (1), Ar represents a trivalent aromatic group having 6 to 12 carbon 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.
The antistatic polycarbonate resin composition according to claim 1, wherein the amount of the polyether ester (B) is 10 to 30 parts by weight per 100 parts by weight of the polycarbonate resin (A).
2. The antistatic polycarbonate resin composition according to claim 1, wherein the organometallic salt compound (C) is paratoluenesulfonic acid and / or a salt thereof.
2. The antistatic polycarbonate resin according to claim 1, wherein the amount of the organometallic salt compound (C) is 0.15 to 0.35 parts by weight per 100 parts by weight of the polycarbonate resin (A). Composition.
The antistatic polycarbonate resin composition according to claim 1, wherein the glycol-modified polyester resin (D) is polycyclohexylenedimethylene terephthalate.
  A molded product obtained by molding the antistatic polycarbonate resin composition according to claim 1.