JP4685431B2 - Antistatic resin composition - Google Patents

Description

  The present invention relates to an antistatic resin composition having excellent antistatic properties, its sustainability, and thermal stability. More specifically, the present invention relates to an antistatic resin composition that exhibits a superior antistatic property due to a synergistic effect of these compounds by using a polyether ester having a specific ionic compound and a sulfonate group in combination. In particular, the present invention relates to an antistatic polycarbonate resin composition comprising these compounds in a polycarbonate resin. The resin composition has unprecedented good thermal stability, and as a result, it is possible to stably exhibit good mechanical properties.

  Thermoplastic resins such as polycarbonate resins, especially those having a high glass transition temperature, have excellent heat resistance and mechanical strength, and are therefore widely used in electrical, mechanical, automotive and medical applications. Yes. However, the resin material usually has a large surface resistivity, and static electricity induced by contact or friction is hardly lost. Therefore, in the resin molded product, there are cases in which dust adheres to the surface of the molded product, discomfort due to electric shock to the human body, and noise and malfunction in electronic products. That is, the chargeability of the resin molded product may be a problem.

  When imparting antistatic properties to a resin material, it has always been desired that the resulting resin composition impart antistatic properties while maintaining the basic characteristics of the resin. For example, it is required to suppress a decrease in heat resistance and impact resistance of such a resin as much as possible. On the other hand, in recent years, with the rapid development of digital information equipment, resin materials having a higher level of antistatic performance have been demanded in the equipment itself, as well as in the equipment and the production site of the equipment.

  Conventionally, a method of blending an ionic surfactant is known as a method for preventing charging of a resin material. Examples of such ionic surfactants include alkali metal salts of sulfonic acid and phosphonium salts of sulfonic acid. Particularly in polycarbonate resins, the phosphonium salts are widely known as preferred salts. This is because a resin composition having good transparency can be obtained by blending the salt.

  However, the method of blending a low molecular weight ionic surfactant easily loses its effect by touching, wiping or washing the surface portion. Therefore, a technique for maintaining the antistatic performance by using a polymer antistatic agent in which various surfactant components are introduced into the polymer structural unit is known.

  For example, the following techniques are known for polycarbonate resins. (I) A resin composition in which polyether ester amide is blended as a polymer antistatic agent in a resin composition comprising a polycarbonate resin and a styrene polymer (see Patent Document 1). (Ii) A resin composition in which a graft polymer comprising a polyamide polymer as a backbone polymer and a block polymer of a polyalkylene ether and a polyester as a polymer is blended in a thermoplastic resin as a polymer antistatic agent (see Patent Document 2). (Iii) obtained by condensing poly (alkylene oxide) glycol having a number average molecular weight of 200 to 20,000, glycol having 2 to 8 carbon atoms and polyvalent carboxylic acid and / or polyvalent carboxylic acid ester having 4 to 20 carbon atoms A resin composition obtained by mixing 1 to 30 parts by weight of a polyether ester and 99 to 70 parts by weight of a thermoplastic resin (see Patent Document 3).

  However, the actual situation is that sufficient antistatic properties cannot be obtained with the polymer antistatic agent alone. Accordingly, a technique of using such an antistatic agent and an ionic surfactant in combination has also been proposed. For example, the following technique is known. (Iv) A resin composition comprising a polycaprolactone unit-containing polyester elastomer and a sulfonic acid metal salt (see Patent Document 4). (V) A resin composition comprising a polycarbonate resin, a sulfonate group-containing polyether ester, and an ionic surfactant (see Patent Document 5). (Vi) A resin composition in which a polyether ester composed of a naphthalene dicarboxylic acid component, a Na sulfoisophthalic acid component, a 1,6-hexamethylene glycol component, and a polyethylene glycol component and an ionic surfactant are blended with a polycarbonate resin (patent) Reference 6). (Vii) A highly transparent resin composition comprising a polycarbonate resin, a polyether ester having a sulfonate group, and a low molecular weight sulfonate (see Patent Document 7).

  However, it has been difficult to say that any of these techniques has both antistatic performance and characteristics such as heat resistance and impact resistance inherent to the resin. Also in the prior art, such characteristics are exhibited temporarily, but since the thermal stability of the resin composition is inferior, improvement has been demanded in that such characteristics cannot be sufficiently exhibited at a practical level. Examples of such fields that are required include covers for various electronic devices and IC transport trays.

Japanese Patent Laid-Open No. 62-273252 Japanese Patent Laid-Open No. 05-97984 Japanese Patent Laid-Open No. 06-57153 Japanese Patent Laid-Open No. 06-65508 Japanese Patent Laid-Open No. 08-283548 JP 09-249805 A JP 2004-161980 A

  From the above, the object of the present invention is to achieve both the excellent antistatic performance and the characteristics typified by the heat resistance and impact resistance inherent in the resin, as well as the good thermal stability of the characteristics. It is an object of the present invention to provide an antistatic resin composition, particularly an antistatic polycarbonate resin composition, which has been sufficiently exerted.

  As a result of intensive investigations aimed at achieving the above object, the inventors of the present invention met the above object by blending a specific amount of a polyether ester having a sulfonate group and a specific ionic compound in a polycarbonate resin. The present inventors have found that a resin composition to be obtained can be obtained, and further earnestly studied to complete the present invention.

  As described above, there has been knowledge of a resin composition containing a polyether ester having a sulfonate group and an ionic surfactant. However, the present inventors have found an unexpected effect that cannot be obtained with a conventional ionic surfactant by using a specific ionic compound, and have reached the present invention.

According to the present invention, the above problems are (1) 100 parts by weight of a thermoplastic resin (component A) having a glass transition temperature (Tg) of 115 ° C. or higher, an ionic compound (component B) represented by the following general formula ( II ) ) And an antistatic resin composition comprising 0.01 to 20 parts by weight and 0.1 to 50 parts by weight of a polyether ester (component C) having a sulfonate group.

（式（ＩＩ）中、ＹはＢＦ _４ ⁻ または（ＣＦ _３ ＳＯ _２ ） _２ Ｎ ⁻ である一価のアニオンを示す。）

(In formula ( II ), Y represents a monovalent anion which is BF ₄ ⁻ or (CF ₃ SO ₂ ) ₂ N ^— .)

  As described above, the configuration (1) has excellent antistatic performance without greatly deteriorating the properties such as heat resistance and impact resistance, which the thermoplastic resin originally has, and these properties are also good. There is provided a resin composition that is exhibited under thermal stability. In view of the fact that the resin composition containing only the B component does not exhibit a particularly excellent initial antistatic performance as compared with the resin composition containing another ionic surfactant, The synergistic effect is clearly observed in the combined use of C and C component. Although the reason for this is not clear, it is considered that the B component is not uniformly dispersed in the matrix of the A component but is uniformly dispersed in the matrix of the C component. It is expected that the change in the matrix environment stably exists in a state where the effect of the B component is more easily exhibited.

BF ₄ ⁻ achieves a low surface resistivity.

(CF ₃ SO ₂ ) ₂ N ⁻ lowers the melting point of the ionic compound and greatly reduces its viscosity. As a result, the mobility of such ions is increased and a low surface resistivity is achieved.

One of preferred embodiments of the present invention is the above constitution ( 2 ) wherein the C component is a polyether ester having an aromatic dicarboxylic acid component substituted with a sulfonate group represented by the following general formula (III): It is an antistatic resin composition of ( 1 ).

（式中、Ａｒは炭素数６〜２０の３価の芳香族基、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 the formula, Ar represents a trivalent aromatic group having 6 to 20 carbon atoms, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion, or a tetraalkylammonium ion.)

-SO ₃ in the general formula (III) ^- sulfonate salt represented by M ⁺ is a unit constituting the main chain of the polyether ester, be present in any of the units and the molecular chain terminals constituting the side chain Good. Further, for example, when a sulfonate group is directly bonded to a constituent unit of the polymer main chain, it can be bonded to any of an aromatic dicarboxylic acid component, a diol component, and a polyether component. However, it is preferred to bind to the aromatic dicarboxylic acid component. This is because compounds that derive such structural units are widely used, and polyether esters having the structural units can be easily obtained. Furthermore, there is an advantage that the introduction amount of the sulfonate group can be precisely and easily controlled by using the polymerization raw material having the sulfonate group.

Further preferred embodiments are: ( 3 ) the C component is (C1) an aromatic dicarboxylic acid component having no sulfonate group, (C2) an aromatic substituted with a sulfonate group represented by the general formula (III) Of the above constitution (5), which is a polyether ester having an aromatic dicarboxylic acid component, (C3) a glycol component having 2 to 10 carbon atoms, and (C4) a poly (alkylene oxide) glycol component having a number average molecular weight of 200 to 50,000 It is an antistatic resin composition. Such a suitable polyether ester of component C has good thermal stability and, as a result, exhibits a synergistic effect with component B more stably.

One of the preferred embodiments of the present invention is ( 4 ) the antistatic resin composition having the constitutions (1) to ( 3 ), wherein the component A is a polycarbonate resin. Although the thermoplastic resin of the A component is not particularly limited, the combination of the B component and the C component of the present invention has good thermal stability, and therefore is suitable for a resin having a high processing temperature. Therefore, a thermoplastic resin having a glass transition temperature of 130 ° C. or higher is suitable, and among them, a polycarbonate resin is suitable as the component A for the following reason. Polycarbonate resins have good impact resistance not found in other thermoplastic resins, and are excellent in heat resistance. Impact resistance is a characteristic that is easily lowered by blending other components. However, the combination of the combination of the B component and the C component of the present invention causes little reduction in impact resistance and maintains such characteristics even when subjected to a long thermal history.

One of the preferred embodiments of the present invention is ( 5 ) 0.0001 to 1 part by weight of a phosphorus stabilizer (D component) and / or a hindered phenolic antioxidant, based on 100 parts by weight of the A component. It is the antistatic resin composition of said structure (1)-( 4 ) formed by mix | blending an agent (E component).

In a more preferred embodiment, ( 6 ) the antistatic resin composition having the constitution ( 5 ), wherein the phosphorus stabilizer (component D ) is a phosphonite compound or a phosphite compound represented by the following general formula (IV): It is.

（式（ＩＶ）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In formula (IV), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different from each other.)

  Although the resin composition of the present invention has good thermal stability, a better hue can be obtained by blending the stabilizer and the antioxidant, and such characteristics can be maintained for a long time. In particular, when the component A is a polycarbonate resin, the phosphite compound of the above general formula (IV) is preferably blended.

Furthermore, according to another aspect of the present invention, ( 7 ) 100 parts by weight of a polyether ester (component C) having a sulfonate group and an ionic compound (component B) represented by the following general formula ( II ): An antistatic agent comprising a resin composition comprising 1 to 50 parts by weight is provided.

（式（ＩＩ）中、ＹはＢＦ _４ ⁻ または（ＣＦ _３ ＳＯ _２ ） _２ Ｎ ⁻ である一価のアニオンを示す。）

(In formula ( II ), Y represents a monovalent anion which is BF ₄ ⁻ or (CF ₃ SO ₂ ) ₂ N ^— .)

The ionic compound is a liquid at room temperature, and usually has a property that is difficult to handle in melt mixing with other thermoplastic resins. Since such an antistatic agent can be handled in a solid form, its formulation is simple. The antistatic resin composition of the present invention can also be produced by blending such an antistatic agent with a thermoplastic resin. The suitable aspect of C component in the antistatic agent of the said structure ( 7 ) is the same as the case of the said structures (2)-( 3 ).

Details of the present invention will be described below.
<A component: Thermoplastic resin>
The thermoplastic resin of component A of the present invention is a thermoplastic resin having a glass transition temperature (Tg) other than the above component C of 115 ° C. or higher, and is not particularly limited. However, as described above, a thermoplastic resin having a glass transition temperature (Tg) of 130 ° C. or higher is preferable. This is because such a thermoplastic resin requires a high processing temperature, but the combination of the B component and the C component is excellent in thermal stability. On the other hand, the upper limit is preferably 250 ° C, more preferably 230 ° C. Tg is a value obtained by differential scanning calorimetry (DSC) measurement based on JIS K7121.

  Such preferred thermoplastic resins include polycarbonate resin, polyethylene naphthalate resin, polyarylate resin, polyphenylene ether resin, polysulfone resin, polyethersulfone resin, cyclic polyolefin resin, polyetherimide resin, polyamideimide resin, polyimide resin, polyamino Examples thereof include bismaleimide resins and polyether ether ketone resins. Among these, polycarbonate resin, polyethylene naphthalate resin, and polyarylate resin are preferable, and polycarbonate resin is particularly preferable. In addition, said suitable A component should just contain 50 weight% or more of a suitable thermoplastic resin in 100 weight% A component, Preferably it is 60 weight% or more, More preferably, it is 70 weight% or more. That is, a thermoplastic resin other than such a suitable thermoplastic resin may be contained in 50% by weight or less, preferably 40% by weight or less, more preferably 30% by weight or less in 100% by weight of the component A. Two or more suitable thermoplastic resins can be used in combination.

  The polycarbonate resin which is a particularly preferred component A of the present invention will be described. A typical polycarbonate resin (hereinafter, sometimes simply referred to as “polycarbonate”) is obtained by reacting a dihydric phenol and a carbonate precursor. The reaction may be performed by an interfacial polycondensation method, a molten ester, or the like. Examples thereof include an exchange method, a solid phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound.

  Specific examples of the dihydric phenol include hydroquinone, resorcinol, 4,4′-biphenol, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (commonly referred to as “bisphenol”). A ″), 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 2,2-bis (4-hydroxyphenyl) pentane, 4, 4 ′-(p-phenylenediisopropylidene) diphenol, 4,4 ′-(m-phenylenediisopropylidene) Phenol, 1,1-bis (4-hydroxyphenyl) -4-isopropylcyclohexane, bis (4-hydroxyphenyl) oxide, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfoxide, bis (4- Hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis (4-hydroxyphenyl) ester, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, bis (3,5-dibromo- 4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfide, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, etc. Is mentioned. Among these, bis (4-hydroxyphenyl) alkane, especially bisphenol A (hereinafter sometimes abbreviated as “BPA”) is widely used.

  In the present invention, in addition to bisphenol A-based polycarbonate, which is a general-purpose polycarbonate, it is possible to use a special polycarbonate produced using other dihydric phenols as the A component.

  For example, as part or all of the dihydric phenol component, 4,4 ′-(m-phenylenediisopropylidene) diphenol (hereinafter sometimes abbreviated as “BPM”), 1,1-bis (4-hydroxy) Phenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (hereinafter sometimes abbreviated as “Bis-TMC”), 9,9-bis (4-hydroxyphenyl) Polycarbonate (homopolymer or copolymer) using fluorene and 9,9-bis (4-hydroxy-3-methylphenyl) fluorene (hereinafter sometimes abbreviated as “BCF”) has dimensions due to water absorption. It is suitable for applications where the demands for change and shape stability are particularly severe. These dihydric phenols other than BPA are preferably used in an amount of 5 mol% or more, particularly 10 mol% or more of the entire dihydric phenol component constituting the polycarbonate.

In particular, when high rigidity and better hydrolysis resistance are required, the following (1) to (3) copolymer polycarbonates are particularly preferable.
(1) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Of 20 to 80 mol% (more preferably 25 to 60 mol%, more preferably 35 to 55 mol%).
(2) BPA is 10 to 95 mol% (more preferably 50 to 90 mol%, more preferably 60 to 85 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and BCF Is 5 to 90 mol% (more preferably 10 to 50 mol%, more preferably 15 to 40 mol%).
(3) BPM is 20 to 80 mol% (more preferably 40 to 75 mol%, more preferably 45 to 65 mol%) in 100 mol% of the dihydric phenol component constituting the polycarbonate, and Bis -Copolymer polycarbonate in which TMC is 20 to 80 mol% (more preferably 25 to 60 mol%, still more preferably 35 to 55 mol%).

  These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.

  The production methods and characteristics of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. ing.

Of the various polycarbonates described above, those having a water absorption and Tg (glass transition temperature) adjusted within the following ranges by adjusting the copolymer composition and the like have good hydrolysis resistance of the polymer itself, and Since it is remarkably excellent in low warpage after molding, it is particularly suitable in a field where form stability is required.
(I) polycarbonate having a water absorption of 0.05 to 0.15%, preferably 0.06 to 0.13% and Tg of 120 to 180 ° C, or (ii) Tg of 160 to 250 ° C, Polycarbonate which is preferably 170 to 230 ° C. and has a water absorption of 0.10 to 0.30%, preferably 0.13 to 0.30%, more preferably 0.14 to 0.27%.

  Here, the water absorption of the polycarbonate is a value obtained by measuring the moisture content after being immersed in water at 23 ° C. for 24 hours in accordance with ISO 62-1980 using a disc-shaped test piece having a diameter of 45 mm and a thickness of 3.0 mm. is there. Moreover, Tg (glass transition temperature) is a value calculated | required by the differential scanning calorimeter (DSC) measurement based on JISK7121.

  On the other hand, as the carbonate precursor, carbonyl halide, carbonate ester, haloformate or the like is used, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

  In producing a polycarbonate from such a dihydric phenol and a carbonate precursor by an interfacial polymerization method, a catalyst, a terminal terminator, and an antioxidant for preventing the dihydric phenol from being oxidized as necessary. Etc. may be used. The polycarbonate may be a branched polycarbonate copolymerized with a trifunctional or higher polyfunctional aromatic compound. Examples of the trifunctional or higher polyfunctional aromatic compound used here include 1,1,1-tris (4-hydroxyphenyl) ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxy). Phenyl) ethane and the like.

  The structural unit derived from the polyfunctional aromatic compound in the branched polycarbonate is 0.1% in a total of 100 mol% of the structural unit derived from the dihydric phenol and the structural unit derived from the polyfunctional aromatic compound. It is 01 to 1 mol%, preferably 0.05 to 0.9 mol%, particularly preferably 0.05 to 0.8 mol%.

In particular, in the case of the melt transesterification method, a branched structural unit may be generated as a side reaction. However, the amount of the branched structural unit is also 0.1% in a total of 100 mol% with a structural unit derived from a dihydric phenol. Those having a ratio of 001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol% are preferred. The ratio of the branched structure can be calculated by ¹ H-NMR measurement.

  The component A polycarbonate resin is a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, and a copolymer obtained by copolymerizing a bifunctional alcohol (including alicyclic). Polyester carbonate obtained by copolymerizing a polymerized polycarbonate and such a bifunctional carboxylic acid and a bifunctional alcohol together may be used. Moreover, the mixture which blended 2 or more types of the obtained polycarbonate may be used.

  The aliphatic bifunctional carboxylic acid used here is preferably an α, ω-dicarboxylic acid. Examples of the aliphatic difunctional carboxylic acid include, for example, sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid and the like, and saturated aliphatic dicarboxylic acid and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

  Furthermore, in the present invention, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can be used as the component A.

  The component A polycarbonate resin may be a mixture of two or more polycarbonates such as polycarbonates having different dihydric phenols, polycarbonates containing branched components, polyester carbonates, polycarbonate-polyorganosiloxane copolymers, and the like. Good. Furthermore, what mixed 2 or more types of polycarbonates from which a manufacturing method differs, a polycarbonate from which a terminal terminator differs, etc. can also be used.

  In the polymerization reaction of polycarbonate, the reaction by the interfacial polycondensation method is usually a reaction of dihydric phenol and phosgene, and is carried out in the presence of an acid binder and an organic solvent. As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an amine compound such as pyridine is used. As the organic solvent, for example, halogenated hydrocarbons such as methylene chloride and chlorobenzene are used. In order to accelerate the reaction, for example, a catalyst such as a tertiary amine such as triethylamine, tetra-n-butylammonium bromide, or tetra-n-butylphosphonium bromide, a quaternary ammonium compound, or a quaternary phosphonium compound can be used. . At that time, the reaction temperature is usually 0 to 40 ° C., the reaction time is preferably about 10 minutes to 5 hours, and the pH during the reaction is preferably maintained at 9 or more.

  In such a polymerization reaction, a terminal terminator is usually used. Monofunctional phenols can be used as such end terminators. As monofunctional phenols, for example, monofunctional phenols such as phenol, p-tert-butylphenol, and p-cumylphenol are preferably used. Furthermore, as monofunctional phenols, long chain alkyl groups having 10 or more carbon atoms such as decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol are used. A monofunctional phenol substituted with a nucleus can be mentioned, and the phenol is effective in improving fluidity and hydrolysis resistance. Such end terminators may be used alone or in combination of two or more.

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or alcohol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. It is carried out by a method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but in most cases is in the range of 120 to 350 ° C. In the latter stage of the reaction, the reaction system is decompressed to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.

  Examples of the carbonate ester include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Among them, diphenyl carbonate is preferable.

A polymerization catalyst can be used to increase the polymerization rate. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide, sodium salt and potassium salt of dihydric phenol; alkaline earth metal compounds such as calcium hydroxide, barium hydroxide and magnesium hydroxide; Nitrogen-containing basic compounds such as methylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine, and triethylamine can be used. Further, alkali (earth) metal alkoxides, alkali (earth) metal organic acid salts, boron compounds, germanium compounds, antimony compounds, titanium compounds, zirconium compounds, etc., esterification reaction, transesterification The catalyst used for the reaction can be used. These catalysts may be used alone or in combination of two or more. The amount of the catalyst used is preferably selected in the range of 1 × 10 ⁻⁹ to 1 × 10 ⁻⁵ equivalents, more preferably 1 × 10 ^{−8 to} 5 × 10 ⁻⁶ equivalents, relative to 1 mol of dihydric phenol as a raw material. It is.

  In the reaction by the melt transesterification method, for example, 2-chlorophenylphenyl carbonate, 2-methoxycarbonylphenylphenyl carbonate, 2-ethoxycarbonyl is used at the later stage or after completion of the polycondensation reaction for the purpose of reducing the phenolic end groups of the produced polycarbonate. Compounds such as phenylphenyl carbonate can be added.

  Furthermore, in the melt transesterification method, it is preferable to use a deactivator that neutralizes the activity of the catalyst. The amount of the deactivator is preferably 0.5 to 50 mol with respect to 1 mol of the remaining catalyst. Moreover, it is suitable to use in the ratio of 0.01-500 ppm with respect to the polycarbonate after superposition | polymerization, More preferably, it is 0.01-300 ppm, Most preferably, it is a ratio of 0.01-100 ppm. Examples of preferable quenching agents include phosphonium salts such as tetrabutylphosphonium dodecylbenzenesulfonate and ammonium salts such as tetraethylammonium dodecylbenzyl sulfate.

  When the viscosity average molecular weight of the polycarbonate resin of component A is less than 10,000, the strength and the like are lowered, and when it exceeds 50,000, the molding process properties are lowered. Therefore, the range is from 10,000 to 50,000. Is preferable, the range of 12,000 to 30,000 is more preferable, and the range of 15,000 to 28,000 is more preferable.

  The polycarbonate resin may be obtained by mixing those having a viscosity average molecular weight outside the above range. In particular, a polycarbonate resin having a viscosity average molecular weight exceeding the above range (50,000) has high entropy elasticity. As a result, good moldability is exhibited in gas assist molding, extrusion molding, blow molding, injection press molding and foam molding. Such improvement in moldability is even better than that of the branched polycarbonate. In a more preferred embodiment, the polycarbonate resin of component A is a polycarbonate resin having a viscosity average molecular weight of 70,000 to 300,000 (component A-3-1) and a polycarbonate resin having a viscosity average molecular weight of 10,000 to 30,000 ( A polycarbonate resin (A-3 component) having a viscosity average molecular weight of 16,000 to 35,000 (hereinafter sometimes referred to as “high molecular weight component-containing polycarbonate resin”). Can be mentioned.

  In such a high molecular weight component-containing polycarbonate resin (component A-3), the molecular weight of the component A-3-1 is preferably 70,000 to 200,000, more preferably 80,000 to 200,000, still more preferably 100,000. 000 to 200,000, particularly preferably 100,000 to 160,000. The molecular weight of the A-3-2 component is preferably 10,000 to 25,000, more preferably 11,000 to 24,000, still more preferably 12,000 to 24,000, and particularly preferably 12,000 to 23. , 000.

  The high molecular weight component-containing polycarbonate resin (component A-3) can be obtained by mixing the components A-3-1 and A-3-2 in various proportions and adjusting them so as to satisfy a predetermined molecular weight range. . Preferably, in 100% by weight of the A-3 component, the A-3-1 component is 2 to 40% by weight and the A-3-2 component is 60 to 98% by weight, more preferably the A-3-1 component is 3 to 30% by weight and 70 to 97% by weight of the A-3-2 component, more preferably 4 to 20% by weight of the A-3-1 component and 80 to 96% by weight of the A-3-2 component. In particular, the A-3-1 component is preferably 5 to 20% by weight and the A-3-2 component is 80 to 95% by weight. Usually, the molecular weight distribution of the polycarbonate resin is in the range of 2-3. Therefore, it is preferable that the A-3-1 component and the A-3-2 component of the present invention satisfy the molecular weight distribution range. The molecular weight distribution is represented by the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) calculated by GPC (gel permeation chromatography) measurement. And Mw is based on standard polystyrene conversion.

  In addition, as a method for preparing the A-3 component, (1) a method in which the A-3-1 component and the A-3-2 component are independently polymerized and mixed, and (2) JP-A-5-306336. The method of producing a polycarbonate resin having a plurality of polymer peaks in the molecular weight distribution chart by the GPC method, represented by the method shown in the Gazette, in the same system, the polycarbonate resin is a condition of the A-3 component of the present invention And (3) a polycarbonate resin obtained by such a production method (production method (2)), and separately produced A-3-1 component and / or A-3-2 component And the like.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution in which 0.7 g of polycarbonate is dissolved in 100 ml of methylene chloride at 20 ° C., the specific viscosity (η _SP ) calculated by the following formula:
Specific viscosity (η _SP ) = (t−t ₀ ) / t ₀
[T ₀ is methylene chloride falling seconds, t is sample solution falling seconds]
The viscosity average molecular weight M is calculated from the determined specific viscosity (η _SP ) by the following formula.
η _SP /c=[η]+0.45×[η] ² c (where [η] is the intrinsic viscosity)
[Η] = 1.23 × 10 ⁻⁴ M ^0.83
c = 0.7

  In addition, calculation of the viscosity average molecular weight in the polycarbonate resin composition of this invention is performed in the following way. That is, the composition is mixed with 20 to 30 times its weight of methylene chloride to dissolve the soluble component in the composition. Such soluble matter is collected by Celite filtration. Thereafter, the solvent in the obtained solution is removed. The solid after removal of the solvent is sufficiently dried to obtain a solid component that dissolves in methylene chloride. A specific viscosity at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride in the same manner as described above, and the viscosity average molecular weight M is calculated from the specific viscosity in the same manner as described above.

  The polyethylene naphthalate resin which is a preferred A component of the present invention will be described. The polyethylene naphthalate resin of the present invention (hereinafter sometimes referred to as “PEN resin”) is a polyester resin having 2,6-naphthalenedicarboxylic acid as a main acid component and ethylene glycol as a main diol component. That is, the polyethylene naphthalate resin of the present invention may be copolymerized with a small amount of other acid components, diol components, and oxyacid components.

  In the present invention, a more preferable PEN resin is 85 to 97 mol% of 2,6-naphthalenedicarboxylic acid component in 100 mol% of the total dicarboxylic acid component constituting the polyester, and 100 mol% of the total diol component. The ethylene glycol component is 85 to 100 mol%. The combination of the 2,6-naphthalenedicarboxylic acid component and the other acid component moderately suppresses the crystallinity and achieves both molding processability and stretch orientation. In the present invention, the 2,6-naphthalenedicarboxylic acid component means a repeating unit derived from 2,6-naphthalenedicarboxylic acid, and may be introduced into the PEN resin by 2,6-naphthalenedicarboxylic acid and its ester-forming derivative. Is possible. Other acid components can also be introduced into the PEN resin by the acid itself or its ester-forming derivatives. Here, examples of the ester-forming derivative include lower alkyl esters, phenyl esters, and acid anhydrides.

  In the present invention, the notation “aa component” (“aa” indicates the compound name) related to the structural unit in the above-described PEN resin and the polyether ester having a sulfonate group described later is the compound “aa” or The polymer structural unit derived from the ester-forming derivative is shown. For example, the acid component refers to a structural unit derived from an acid compound such as dicarboxylic acid or an ester-forming derivative thereof, and the diol component refers to a structural unit derived from a diol compound or an ester-forming derivative thereof. The ester-forming derivative of dicarboxylic acid is typically an alkyl ester of such acid, and methyl ester is particularly preferably used.

  Further, a PEN resin more preferable in the present invention is selected from 85 to 97 mol% of 2,6-naphthalenedicarboxylic acid component, and isophthalic acid component and terephthalic acid component in 100 mol% of the total dicarboxylic acid component constituting the polyester. And 3-15 mol% of at least one dicarboxylic acid component. By including such a specific amount of isophthalic acid and / or terephthalic acid, it is possible to achieve both reduction in crystallinity and stretch orientation, and to obtain a molded product with sufficient strength and impact resistance that is sufficiently stretched uniformly. It becomes possible. The ratio of isophthalic acid and / or terephthalic acid is more preferably in the range of 5 to 12 mol%. These acids are preferably contained as a copolymerization component in the PEN resin, and terephthalic acid is particularly preferable.

  On the other hand, examples of acid components that can be contained in PEN resins other than isophthalic acid and terephthalic acid include 2,7-naphthalenedicarboxylic acid, tert-butylphthalic acid, diphenoxyethanedicarboxylic acid, diphenyldicarboxylic acid, and diphenoxyethanedicarboxylic acid. Aromatic dicarboxylic acids such as acid, diphenylsulfone dicarboxylic acid, diphenyl ether dicarboxylic acid, phenylmethane dicarboxylic acid, diphenyl ketone dicarboxylic acid, and diphenyl sulfide dicarboxylic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid Alicyclic dicarboxylic acids such as aliphatic dicarboxylic acids, hexahydroterephthalic acid, decalin dicarboxylic acid, and telelarin dicarboxylic acid, etc. (consisting of these acids as described above) Containing ester-forming derivative thereof).

  Examples of diol components other than ethylene glycol that may be contained in the PEN resin include propylene glycol, tetramethylene glycol, 1,3-butanediol, pentamethylene glycol, hexamethylene glycol, neopentyl glycol, and fats such as diethylene glycol. Aromatic glycols such as aliphatic glycols, cycloaliphatic diols such as cyclohexanedimethanol and tricyclodecane dimethylol, dihydric phenols such as bisphenol A, resorcin, hydroquinone, and dihydroxydiphenyl, and alkylene oxide adducts of bisphenol A, polyethylene glycol And polyols such as polytetramethylene glycol, and fluorene such as bishydroxyethoxyphenylfluorene. That.

  Examples of the oxyacid component that may be contained in the PEN resin include oxybenzoic acid and hydroxydiphenylcarboxylic acid.

  Furthermore, the PEN resin of the present invention can contain a trifunctional or higher functional acid component or glycol component as long as the object of the present invention is not impaired. Examples of the trifunctional or higher functional acid component include trimellitic acid, and examples of the trifunctional or higher functional glycol component include glycerin, trimethylpropane, and pentaerythritol. The trifunctional or higher functional component is preferably used in a proportion of 2 mol% or less, more preferably 1 mol% or less, in 100 mol% of each component.

  The PEN resin of the present invention has an intrinsic viscosity measured in an orthochlorophenol solvent at 25 ° C. of preferably 0.55 dl / g or more, more preferably 0.6 dl / g or more, and further preferably 0.65 dl / g. That's it. When the intrinsic viscosity is 0.55 dl / g or more, the crystallization time is increased, and the range of conditions during molding is widened, which is advantageous in many cases. On the other hand, the intrinsic viscosity is preferably 1.3 dl / g or less, more preferably 1.2 dl / g or less. When the intrinsic viscosity is too high, distortion and voids are likely to occur in the molded product, which is not preferable.

  Various conventional polymerization methods can be applied to polymerize the PEN resin of the present invention. As an example, a method in which ethylene glycol, dimethyl ester of 2,6-naphthalenedicarboxylic acid and a copolymer component (such as dimethyl terephthalate) are transesterified while distilling off methyl alcohol, and then polycondensation is performed under reduced pressure. Is exemplified. In the present invention, it is preferable to carry out solid phase polymerization in order to further increase the intrinsic viscosity. Preferred examples of the transesterification catalyst include calcium acetate and magnesium acetate. In addition, examples of the transesterification catalyst include acetates such as magnesium, manganese, calcium, and zinc, monocarboxylates, alcoholates, and oxides. In order to deactivate the transesterification catalyst, it is preferable to add a phosphorus compound such as trimethyl phosphate after the transesterification reaction. As the polymerization reaction catalyst, germanium compounds, titanium compounds, and antimony compounds can be used, such as germanium dioxide, germanium hydroxide, germanium alcoholate, titanium tetrabutoxide, titanium tetraisopropoxide, and titanium oxalate. Illustrated.

  The polyarylate resin which is a preferred A component of the present invention will be described. The polyarylate resin of the present invention is obtained from an aromatic dicarboxylic acid or a derivative thereof and a dihydric phenol or a derivative thereof. The aromatic dicarboxylic acid used for the preparation of the polyarylate may be any one as long as it reacts with a dihydric phenol to give a satisfactory polymer, and one or a mixture of two or more are used.

  Preferred aromatic dicarboxylic acid components include terephthalic acid and isophthalic acid. A mixture thereof may also be used.

  Specific examples of the dihydric phenol component include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, and 2,2-bis (4- Hydroxy-3,5-dichlorophenyl) propane, 4,4'-dihydroxydiphenyl sulfone, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'- Dihydroxydiphenylmethane, 2,2′-bis (4hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4, 4'-dihydroxydiphenyl, hydroquinone, etc. are mentioned. These dihydric phenol components are para-substituted products, but other isomers may be used, and ethylene glycol, propylene glycol, neopentyl glycol and the like may be used in combination with the dihydric phenol component.

  Among these, preferred polyarylate resins include those in which the aromatic dicarboxylic acid component is composed of terephthalic acid and isophthalic acid, and the divalent phenol component is composed of 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). It is done. The ratio of terephthalic acid to isophthalic acid is preferably terephthalic acid / isophthalic acid = 9/1 to 9/1 (molar ratio), particularly preferably 7/3 to 3/7 in terms of melt processability and performance balance.

  Other typical polyarylate resins include those in which the aromatic dicarboxylic acid component is composed of terephthalic acid and the dihydric phenol component is composed of bisphenol A and hydroquinone. The ratio of bisphenol A and hydroquinone is preferably bisphenol A / hydroquinone = 50/50 to 70/30 (molar ratio), more preferably 55/45 to 70/30, and still more preferably 60/40 to 70/30. .

  The viscosity average molecular weight of the polyarylate resin in the present invention is preferably in the range of about 7,000 to 100,000 in view of physical properties and extrusion processability. The polyarylate resin can be selected from any polymerization method of interfacial polycondensation and transesterification.

（式（ＩＩ）中、ＹはＢＦ _４ ⁻ または（ＣＦ _３ ＳＯ _２ ） _２ Ｎ ⁻ である一価のアニオンを示す。） <B component: ionic compound>
The B component of the present invention is an ionic compound represented by the following general formula ( II ).

(In formula ( II ), Y represents a monovalent anion which is BF ₄ ⁻ or (CF ₃ SO ₂ ) ₂ N ^— .)

The characteristics of the two ammonium salts are as follows. Counter ion BF ₄ ^- in which the ammonium salt (B-1 component), mp: 9 ° C., the viscosity is measured at 20 ℃: 1,200mPas, density 1.17 g / ^cm 3, conductivity at 25 ° C.: 1.3 mS / cm, TGA 5% weight loss temperature (measured under a nitrogen stream): A brown liquid having a temperature of about 360 ° C. The ammonium salt (component B-2) whose counter ion is (CF ₃ SO ₂ ) ₂ N ^— has a melting point: −94 ° C., a viscosity measured at 20 ° C .: 120 mPas, a density of 1.42 g / cm ³ , and 25 ° C. Conductivity at: 2.6 mS / cm, TGA 5% weight loss temperature (measured under a nitrogen stream): A colorless transparent liquid having a temperature of about 370 ° C.

<C component: polyether ester having a sulfonate group>
The antistatic resin composition of the present invention exhibits characteristics that are not found in conventional antistatic resin compositions due to its synergistic effect by using a polyether ester having a sulfonate group together with the above ionic compound. . Here, the polyether ester is a polyester having a polyether unit in its repeating unit, and the polyester is a polymer composed of an aromatic dicarboxylic acid component and a glycol component. An alkylene oxide) refers to a polymer having a glycol component in its repeating unit. The repeating unit of the polyether is a unit represented by —O— (R ^X —O) _n — (here, R ^X represents an alkylene group having 1 or more carbon atoms, and n represents 3 or more). The polyether ester can contain a diethylene glycol component.

  The meaning of the notation such as “aromatic dicarboxylic acid component” is as described above. For example, the aromatic dicarboxylic acid component refers to a structural unit derived from an aromatic dicarboxylic acid or an ester-forming derivative thereof.

  Polyether ester of component C can be made into a polymer compound by polymerizing the monomer substituted with sulfonate group, or manufactured by modifying a polymer not substituted with sulfonate group with sulfonate group You can also In the polyether ester of component C, a sulfonate group may be bonded to any position. A preferred C component is a polyether ester in which a sulfonate group is bonded to the aromatic ring of the aromatic dicarboxylic acid component. Further, such a polyether ester may contain an aromatic ring to which one or more sulfonate groups are bonded, but more preferably a polymer containing an aromatic ring to which one sulfonate group is bonded. .

Wherein component C of sulfonate - specific examples of _(-SO ^{3 X +)} are as follows. The metal ions in X ⁺ (hereinafter sometimes referred to simply as counter ions) are, for example, alkali metal ions such as sodium, potassium, lithium, rubidium, and cesium, alkaline earth metal ions such as calcium and magnesium, Includes zinc ions, copper ions, and the like. The organic onium ions in the counter ion include, for example, ammonium ions, phosphonium ions, sulfonium ions, onium ions derived from heteroaromatic rings, and the like. As the organic onium ion, any of primary, secondary, tertiary and quaternary can be used, and quaternary onium ions are preferred. The organic onium ion in the counter ion is more preferably an organic phosphonium ion and an organic ammonium ion, and particularly preferably an organic phosphonium ion. Examples of the phosphonium ion include tetrabutylphosphonium ion and tetramethylphosphonium ion. Examples of the ammonium ion include tetrabutylammonium ion and tetramethylammonium ion.

  The counter ion in component C is more preferably a metal ion, still more preferably an alkali metal ion, an alkaline earth metal ion and a zinc ion, and particularly preferably an alkali metal ion. However, in the case of a divalent metal ion, 1 mol of metal ion corresponds to 2 mol of sulfonic acid group.

The component C contains at least 2 or more sulfonate groups in one molecule of the polymer, preferably 3 or more, and more preferably 4 or more. The number average molecular weight is preferably 1,000 or more, and more preferably 2,000 or more. Furthermore, the concentration of the sulfonate group (—SO ₃ X: X represents a counter ion) contained in the component C is preferably in the range of 5 × 10 ⁻⁷ mol / g to 5 × 10 ⁻² mol / g. More preferably, it is the range of 5 * 10 < ^-6 > -5 * 10 < ^-3 > mol / g.

  As described above, a suitable C component is a polyether ester having an aromatic dicarboxylic acid component substituted with a sulfonate group represented by the following general formula (III).

（式中、Ａｒは炭素数６〜２０の３価の芳香族基、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 the formula, Ar represents a trivalent aromatic group having 6 to 20 carbon atoms, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion, or a tetraalkylammonium ion.)

  More preferable C component is (C1) an aromatic dicarboxylic acid component having no sulfonate group, (C2) an aromatic dicarboxylic acid component substituted with a sulfonate group represented by the general formula (III), (C3 It is a polyether ester comprising a glycol component having 2 to 10 carbon atoms and (C4) a poly (alkylene oxide) glycol component having a number average molecular weight of 200 to 50,000. As used herein, “component” refers to a structural unit derived from an aromatic dicarboxylic acid or an ester-forming derivative thereof, for example, as an “aromatic dicarboxylic acid component”.

  Examples of the aromatic dicarboxylic acid (and its ester-forming derivative) having no sulfonate group for deriving (C1) include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and their ester-forming properties. And derivatives thereof. Among these, a naphthalenedicarboxylic acid component and a biphenyldicarboxylic acid component, particularly a naphthalenedicarboxylic acid component are preferable because they allow a wide range of refractive index adjustment and can adjust the transparency of the resin composition. Specific examples of naphthalenedicarboxylic acid and its ester-forming derivatives include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylic acid, and 2,6-naphthalenedicarboxylic acid. Examples include diethyl, dimethyl 2,7-naphthalenedicarboxylate, and diethyl 2,7-naphthalenedicarboxylate, and the hydrogen atom of the aromatic ring of these compounds may be substituted with an alkyl group, a halogen atom, or the like. The aromatic dicarboxylic acid component (C1) can be contained alone or in combination in a polyether ester.

  (C2) The aromatic dicarboxylic acid component substituted with a sulfonate group is represented by the above formula (III).

  Ar in the above formula (III) is a trivalent aromatic group having 6 to 20 carbon atoms, and specific examples thereof include a trivalent benzene ring and a naphthalene ring, and these rings are an alkyl group and a phenyl group. , Halogen, and an alkoxy group may be substituted.

In the formula (III), M ⁺ represents a metal ion or an organic onium ion, and a specific example thereof can be the same as the above X ⁺ . The counter ion in component C is more preferably a metal ion, still more preferably an alkali metal ion, an alkaline earth metal ion and a zinc ion, and particularly preferably an alkali metal ion. However, in the case of a divalent metal ion, 1 mol of metal ion corresponds to 2 mol of sulfonic acid group.

  Aromatic dicarboxylic acids substituted with a sulfonate group for inducing (C2) and ester-forming derivatives thereof include 4-sodium sulfo-isophthalic acid, 5-sodium sulfo-isophthalic acid, 4-potassium sulfo- Isophthalic acid, 5-potassium sulfo-isophthalic acid, 2-sodium sulfo-terephthalic acid, 2-potassium sulfo-terephthalic acid, 4-sulfo-isophthalic acid zinc salt, 5-sulfo-isophthalic acid zinc salt, 2-sulfo-terephthalic acid Acid zinc salt, 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 tetra Rukyphosphonium 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-potassium sulfo-2,7-naphthalenedicarboxylic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid zinc salt, 4-sulfo-2,7-naphthalenedicarboxylic acid zinc salt, 4-sulfo-2 , 6-Naphthalenedicarboxylic acid tetraalkylammonium salt, 4-sulfo-2,7-naphthalenedicarboxylic acid tetraalkylammonium salt, 4-sulfo-2,6-naphthalenedicarboxylic acid tetraalkylphosphonium salt, 4-sulfo-2,7 -Naphthalenedicarboxylic acid tetraalkylphos Salts or their dimethyl esters, may be mentioned diethyl ester.

Among them, dimethyl ester or diethyl ester of aromatic dicarboxylic acid, in which Ar is a benzene ring and M ⁺ is an alkali metal ion such as sodium or potassium, is polymerizable, antistatic, mechanical properties, and hue. 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 Examples include dimethyl and 2-potassium sulfo-dimethyl terephthalate. The aromatic dicarboxylic acid component (C2) can be contained alone or in combination of two or more in the polyether ester.

  The two acid components (C1) and (C2) constituting the polyether ester of component C are composed of 100 mol% of the total acid component, and (C1) an aromatic dicarboxylic acid component 95 having no sulfonate group. It is preferable that the ratio is ˜50 mol% and (C2) 5 to 50 mol% of the aromatic dicarboxylic acid component substituted with the sulfonate group represented by the above formula (III). When the proportion of the component (C2) is less than 5 mol%, the antistatic effect may not be sufficient. On the other hand, when the component (C2) exceeds 50 mol%, the polymerization reaction becomes difficult, and it may be difficult to obtain a polyether ester having a sufficient degree of polymerization, or the handleability may deteriorate. More preferred proportions of the component (C1) and the component (C2) are (C1) 92 to 65 mol% and (C2) 8 to 35 mol%, and further preferred proportions are (C1) 90 to 70 mol% and ( C2) 10 to 30 mol%.

  The glycol having 2 to 10 carbon atoms for deriving (C3), which is one of the constituent components of the polyether component C of the present invention, specifically includes ethylene glycol and 1,4-butanediol. , Propylene glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, and the like. Such glycol may contain an ether bond such as diethylene glycol and a thioether bond such as thiodiethanol.

  Such glycol may be used independently and may use 2 or more types together. Of these, 1,6-hexanediol is preferably used mainly from the viewpoint of the antistatic effect, and 1,6-hexanediol and ethylene glycol are more preferably used in combination. The preferred ratio of the 1,6-hexanediol component to the ethylene glycol component in the polyether ester of component C is 95 to 50 mol% of 1,6-hexanediol component and 5 to 5 of ethylene glycol component in 100 mol% of glycol component. They are 50 mol%, More preferably, they are 90-70 mol% of 1, 6- hexanediol components and 10-30 mol% of ethylene glycol components.

  As the poly (alkylene oxide) glycol for deriving (C4), which is one of the components of the polyether ester of component C of the present invention, poly (alkylene oxide) glycol mainly composed of poly (ethylene oxide) glycol is suitable. Is exemplified. The poly (alkylene oxide) glycol may include other poly (alkylene oxide) glycols such as poly (propylene oxide) glycol.

  The number average molecular weight of the (C4) poly (alkylene oxide) glycol component is preferably in the range of 200 to 50,000. When the molecular weight is less than 200, the advantage of using the polyether ester that a better antistatic effect can be obtained may not be sufficiently exhibited. In terms of practicality, it is sufficient that the molecular weight is about 50,000. The preferred molecular weight of the poly (alkylene oxide) glycol is 500 to 30,000, more preferably 1,000 to 20,000. The poly (alkylene oxide) glycol component (C4) can be contained alone or in combination of two or more in the polyether ester.

  The poly (alkylene oxide) glycol component of (C4) is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, still more preferably 20 to 40% by weight in 100% by weight of the polyether ester of the C component. Is within the range. If the amount is less than 10% by weight, the antistatic effect which is an advantage of the polyether ester of component C may not be sufficient, and if it exceeds 50% by weight, it becomes disadvantageous in terms of thermal stability. Also, when obtaining a composition having higher transparency, it tends to be disadvantageous in that the refractive index of the polyether ester tends to be low.

  The polyether ester of component C in the present invention has a reduced viscosity (concentration of 1.2 g / dl) measured at 30 ° C. in a mixed solvent of phenol / tetrachloroethane (weight ratio 40/60) of 0.3 or more. preferable. If the reduced viscosity is less than 0.3, heat resistance and mechanical properties may be deteriorated. The upper limit for the reduced viscosity is preferably higher in terms of antistatic effect and mechanical properties since the polymer is a substantially linear polymer, but the practical upper limit of polymerization is about 4.0. It is. The reduced viscosity is more preferably 0.4 or more, and further preferably 0.5 or more.

  The polyether ester of component C in the present invention includes the dicarboxylic acid, glycol, and poly (alkylene oxide) glycol that derive the components (C1), (C2), (C3), and (C4), respectively, and The ester-forming derivative can be obtained by heating and melting at 150 to 300 ° C. in the presence of a transesterification catalyst to cause a polycondensation reaction.

  The transesterification catalyst is not particularly limited as long as it can be used in ordinary transesterification reactions. Such 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, acetic acid Examples include calcium compounds such as calcium, and alkali metal salts such as sodium carbonate and potassium carbonate. Of these, tetrabutyl titanate is preferably used.

  The amount of the catalyst used may be the amount used in a normal transesterification reaction, and is preferably 0.01 to 0.5 mol%, generally 0.03 to 0.3 mol, based on 1 mol of the acid component used. % Is more preferable.

  In addition, it is also preferable to use an antioxidant together during the reaction. Examples of the antioxidant include pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-lauryl thiopropionate), glycerol-3-stearyl thiopropionate, triethylene glycol bis [3 -(3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], Pentaerythritol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1, 3,5-trimethyl-2,4 -Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, N, N-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5 -Di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, and 3,9-bis {1,1-dimethyl- 2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl} -2,4,8,10-tetraoxaspiro (5,5) undecane and the like can be mentioned. The amount of the antioxidant used is preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the polyether ester of component C.

  As the temperature at which the compound for inducing the components (C1) to (C4) is heated and melted and polycondensed, the initial reaction is an esterification reaction and / or transesterification reaction at 150 to 200 ° C. for several tens of minutes to several tens of hours. Is carried out while distilling off the distillate, and then a polymerization reaction for increasing the molecular weight of the reaction product is carried out at 180 to 300 ° C. When the temperature is lower than 180 ° C., the reaction hardly proceeds, and when the temperature is higher than 300 ° C., side reactions such as decomposition tend to occur, and thus the above temperature range is preferable. The polymerization reaction temperature is more preferably from 200 to 280 ° C, particularly preferably from 220 to 260 ° C. Although the reaction time of this polymerization reaction depends on the reaction temperature and the polymerization catalyst, it is usually from several tens of minutes to several tens of hours.

  Furthermore, the suitable polyether ester of component C can be used alone or in combination of two or more.

<About the content of each component>
Next, the contents of the B component and the C component will be described. Content of B component is 0.01-20 weight part with respect to 100 weight part of A component thermoplastic resin, Preferably it is 0.05-10 weight part, More preferably, it is 0.1-5 weight part, More preferably Is in the range of 0.5 to 3 parts by weight. If the content of component B is less than 0.01 part by weight, the antistatic effect of the resin composition tends to be insufficient, and if it exceeds 20 parts by weight, the mechanical properties, heat resistance, and moldability are likely to deteriorate. Content of C component is 0.1-50 weight part with respect to 100 weight part of A component, Preferably it is 5-50 weight part, More preferably, it is the range of 10-40 weight part. When the content of component C is less than 0.1 parts by weight, the antistatic effect tends to be insufficient, and when it exceeds 50 parts by weight, mechanical properties, heat resistance, and molding processability are likely to deteriorate. The synergistic effect of the B component and the C component of the present invention is exhibited even in a small amount with respect to the A component. However, since the characteristics of the antistatic resin composition of the present invention are exhibited in a region where the surface resistivity is lower, the content of the C component is 5 parts by weight or more with respect to 100 parts by weight of the A component. Preferably there is. Furthermore, the ratio of the content of the B component and the C component is preferably 0.1 to 50 parts by weight, more preferably 1 to 25 parts by weight, still more preferably 2 to 2 parts by weight based on 100 parts by weight of the C component. 15 parts by weight.

<D component: phosphorus stabilizer>
Examples of the phosphorus-based stabilizer used for the component D include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.

  Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, dis Allyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A Examples include pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

  Further, as other phosphite compounds, those which react with dihydric phenols and have a cyclic structure can be used. For example, 2,2′-methylenebis (4,6-di-tert-butylphenyl) (2,4-di-tert-butylphenyl) phosphite, 2,2′-methylenebis (4,6-di-tert- Examples include butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite and 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite.

  Examples of the phosphate compound include tributyl phosphate, trimethyl phosphate, tricresyl phosphate, triphenyl phosphate, trichlorophenyl phosphate, triethyl phosphate, diphenyl cresyl phosphate, diphenyl monoorxenyl phosphate, tributoxyethyl phosphate, dibutyl phosphate, dioctyl phosphate, Examples thereof include diisopropyl phosphate, and triphenyl phosphate and trimethyl phosphate are preferable.

  Examples of the phosphonite compound include tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3′-biphenylenedi. Phosphonite, tetrakis (2,4-di-tert-butylphenyl) -3,3′-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite Tetrakis (2,6-di-tert-butylphenyl) -4,3′-biphenylene diphosphonite, tetrakis (2,6-di-tert-butylphenyl) -3,3′-biphenylene diphosphonite, bis (2,4-di-tert-butylphenyl) -4-phenyl-phenylphosphonite, bis (2,4-di tert-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-n-butylphenyl) -3-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl)- 4-phenyl-phenylphosphonite, bis (2,6-di-tert-butylphenyl) -3-phenyl-phenylphosphonite, and the like, and tetrakis (di-tert-butylphenyl) -biphenylenediphosphonite, bis (Di-tert-butylphenyl) -phenyl-phenylphosphonite is preferred, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite, bis (2,4-di-tert-butylphenyl)- More preferred is phenyl-phenylphosphonite. Such a phosphonite compound is preferable because it can be used in combination with a phosphite compound having an aryl group in which two or more alkyl groups are substituted.

  Examples of the phosphonate compound include dimethyl benzenephosphonate, diethyl benzenephosphonate, and dipropyl benzenephosphonate.

  Tertiary phosphine includes triethylphosphine, tripropylphosphine, tributylphosphine, trioctylphosphine, triamylphosphine, dimethylphenylphosphine, dibutylphenylphosphine, diphenylmethylphosphine, diphenyloctylphosphine, triphenylphosphine, tri-p-tolyl. Examples include phosphine, trinaphthylphosphine, and diphenylbenzylphosphine. A particularly preferred tertiary phosphine is triphenylphosphine.

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula (IV) are preferable.

（式（ＩＶ）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In formula (IV), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different from each other.)

  As described above, tetrakis (2,4-di-tert-butylphenyl) -biphenylenediphosphonite is preferable as the phosphonite compound, and the stabilizer containing phosphonite as a main component is Sandostab P-EPQ (trademark, manufactured by Clariant). ) And Irgafos P-EPQ (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and both can be used.

  Among the above formulas (IV), more preferred phosphite compounds are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di). -Tert-butyl-4-methylphenyl) pentaerythritol diphosphite, and bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite.

  Distearyl pentaerythritol diphosphite is commercially available as ADK STAB PEP-8 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and JPP681S (trademark, manufactured by Johoku Chemical Industry Co., Ltd.), and any of them can be used. Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite is ADK STAB PEP-24G (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.), Alkanox P-24 (trademark, manufactured by Great Lakes), Ultranox. P626 (trademark, manufactured by GE Specialty Chemicals), Doverphos S-9432 (trademark, manufactured by Dover Chemical), and Irgafos126 and 126FF (trademark, manufactured by CIBA SPECIALTY CHEMICALS) are also available. Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is commercially available as ADK STAB PEP-36 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be easily used. Further, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite is produced by ADK STAB PEP-45 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and Doverphos S-9228 (trademark). , Manufactured by Dober Chemical Co.) and any of them can be used.

<E component: hindered phenolic antioxidant>
As the hindered phenol compound that is the E component of the present invention, various compounds that are usually blended in a resin can be used. Examples of such hindered phenol compounds include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert -Butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N-dimethylamino) Methyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl) -6-tert-butylphenol), 4,4'-methylenebis (2,6 Di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2,2 ′ -Ethylidene-bis (4,6-di-tert-butylphenol), 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert) -Butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-tert-butyl) Ru-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1, -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3- Methyl-6-tert-butylphenol), 2,2′-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 ′ -Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thiodie Renbis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert- Butylanilino) -1,3,5-triazine, N, N′-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N′-bis [3- (3 , 5-Di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl -2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) iso Cyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert-butyl- 4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3- tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2 {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [Methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy Examples include -5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

  Among the above compounds, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-) is used in the present invention. 4-hydroxyphenyl) propionate, and 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4 , 8,10-Tetraoxaspiro [5,5] undecane is preferably used. In particular, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxa Spiro [5,5] undecane is preferred. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

  The blending amount of the component D is 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight, more preferably 0.01 to 0.3 part by weight based on 100 parts by weight of the thermoplastic resin of the component A. The range is parts by weight. In the said range, the resin composition excellent in thermal stability and hue stability is obtained. Conversely, when the D component exceeds 1 part by weight, hue deterioration and molecular weight reduction are more likely to occur. The compounding quantity of E component is 0.0001-1 weight part with respect to 100 weight part of A component, Preferably it is 0.001-0.5 weight part, More preferably, it is 0.01-0.3 weight part. In the said range, the resin composition which was more excellent in hue stability and long-term dry heat property is obtained. On the contrary, when the E component exceeds 1 part by weight, the hue deteriorates more easily. It is preferable that either component D or component E is blended. The blending is particularly preferred in the polycarbonate resin, polyethylene naphthalate resin, and polyarylate resin, which are particularly preferred components A. A more preferred embodiment is the combined use of the D component and the E component. Also in such a combination, the above-mentioned blending amounts are preferable for both the D component and the E component. More preferably, 0.01 to 0.3 parts by weight of D component and 0.01 to 0.3 parts by weight of E component are blended based on 100 parts by weight of component A.

<About other additives>
The antistatic resin composition of this invention can contain the various additives normally mix | blended with resin other than the said A component-E component.

(I) Blueing agent The antistatic resin composition of the present invention preferably further comprises 0.05 to 3.0 ppm (weight ratio) of a blueing agent in the resin composition. Since the resin composition of the present invention is relatively yellowish, the use of a bluing agent is very effective for imparting a natural transparency to a molded product. Here, the bluing agent refers to a colorant that exhibits a blue or purple color by absorbing light of orange or yellow color, and a dye is particularly preferable. By adding the bluing agent, the antistatic resin composition of the present invention obtains a better hue. If the amount of the bluing agent is less than 0.05 ppm, the effect of improving the hue may be insufficient. On the other hand, if it exceeds 3.0 ppm, the light transmittance decreases, which is not appropriate. A more preferable amount of bluing agent is in the range of 0.2 to 2.0 ppm in the resin composition. Representative examples of bluing agents include Macrolex Violet B and Macrolex Blue RR from Bayer, and Polysynthrene Blue RLS from Clariant.

(Ii) Release Agent It is preferable to add a release agent to the antistatic resin composition of the present invention for the purpose of improving productivity during molding and reducing distortion of the molded product. Known release agents can be used. For example, saturated fatty acid ester, unsaturated fatty acid ester, polyolefin wax (polyethylene wax, 1-alkene polymer, etc., which may be modified with a functional group-containing compound such as acid modification), silicone compound, fluorine compound ( And fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like. The release agent is preferably 0.005 to 2 parts by weight with respect to 100 parts by weight of the thermoplastic resin (component A).

  Among these, fatty acid esters are preferable as a release agent. Such fatty acid esters are esters of aliphatic alcohols and aliphatic carboxylic acids. Such an aliphatic alcohol may be a monohydric alcohol or a dihydric or higher polyhydric alcohol. Moreover, as carbon number of this alcohol, it is the range of 3-32, More preferably, it is the range of 5-30. Examples of such monohydric alcohols include dodecanol, tetradecanol, hexadecanol, octadecanol, eicosanol, tetracosanol, seryl alcohol, and triacontanol. Examples of such polyhydric alcohols include pentaerythritol, dipentaerythritol, tripentaerythritol, polyglycerol (triglycerol to hexaglycerol), ditrimethylolpropane, xylitol, sorbitol, and mannitol. In the fatty acid ester of the present invention, a polyhydric alcohol is more preferable.

  On the other hand, the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, and particularly preferably an aliphatic carboxylic acid having 10 to 22 carbon atoms. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid . Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred.

  Since the above-mentioned aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats (such as beef tallow and pork fat) and vegetable fats (such as palm oil), these aliphatic carboxylic acids. The acid is usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used.

  The fatty acid ester of the present invention may be either a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures. The acid value in the fatty acid ester of the present invention is preferably 20 or less (can substantially take 0) from the viewpoint of thermal stability, more preferably in the range of 4 to 20, and still more preferably in the range of 4 to 12. The hydroxyl value of the fatty acid ester is more preferably in the range of 0.1-30. Further, the iodine value is preferably 10 or less (can take substantially 0). These characteristics can be obtained by a method defined in JIS K 0070.

  The content of the release agent is preferably 0.005 to 2 parts by weight, more preferably 0.01 to 1 part by weight, and still more preferably 0.05 to 0.5 part by weight per 100 parts by weight of the component A. In such a range, the antistatic resin composition has good releasability. In particular, such an amount of fatty acid ester provides an antistatic resin composition having good releasability without impairing good hue and transparency.

(Iii) Ultraviolet absorber The antistatic resin composition of this invention can contain a ultraviolet absorber. Specific examples of the ultraviolet absorber of the present invention include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4 in the benzophenone series. -Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-Benzoyl-4-hydroxy-2- Examples include methoxyphenyl) methane, 2-hydroxy-4-n-dodecyloxybenzophenone, and 2-hydroxy-4-methoxy-2′-carboxybenzophenone.

  Specific examples of the ultraviolet absorber include, for example, 2- (2-hydroxy-5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole in the benzotriazole series. 2- (2-hydroxy-3,5-dicumylphenyl) phenylbenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2,2′- Methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], 2- (2-hydroxy-3,5-di-tert-butylphenyl) ) Benzotriazole, 2- (2-hydroxy-3,5-di-tert-butylphenyl) -5-chlorobenzotriazol 2- (2-hydroxy-3,5-di-tert-amylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-5- tert-butylphenyl) benzotriazole, 2- (2-hydroxy-4-octoxyphenyl) benzotriazole, 2,2'-methylenebis (4-cumyl-6-benzotriazolephenyl), 2,2'-p -Phenylenebis (1,3-benzoxazin-4-one), and 2- [2-hydroxy-3- (3,4,5,6-tetrahydrophthalimidomethyl) -5-methylphenyl] benzotriazole, and 2- (2'-Hydroxy-5-methacryloxyethylphenyl) -2H-benzotriazole and co-polymerized with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

  Specific examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4) in hydroxyphenyltriazine series. , 6-Diphenyl-1,3,5-triazin-2-yl) -5-methyloxyphenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-ethyloxy Phenol, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-propyloxyphenol, and 2- (4,6-diphenyl-1,3,5-triazine-2- Yl) -5-butyloxyphenol and the like. Furthermore, the phenyl group of the above exemplary compounds such as 2- (4,6-bis (2,4-dimethylphenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol is 2,4-dimethyl. Examples of the compound are phenyl groups.

  As the ultraviolet absorber, specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) and the like.

  Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

  Further, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, whereby the ultraviolet-absorbing monomer and / or the light-stable monomer having a hindered amine structure, and an alkyl (meth) acrylate. A polymer type ultraviolet absorber obtained by copolymerization with a monomer such as may be used. Preferred examples of the UV-absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylate. The

  Of these, benzotriazoles and hydroxyphenyltriazines are preferred in terms of ultraviolet absorption, and cyclic iminoesters and cyanoacrylates are preferred in terms of heat resistance and hue (transparency). You may use the said ultraviolet absorber individually or in mixture of 2 or more types.

  Content of a ultraviolet absorber is 0.01-2 weight part with respect to 100 weight part of A component, Preferably it is 0.03-2 weight part, More preferably, it is 0.02-1 weight part, More preferably, it is 0.00. It is 05-0.5 weight part.

(Iv) Dye and Pigment The antistatic resin composition of the present invention can further provide a molded product containing various dyes and pigments and exhibiting various design properties. For example, the inclusion of a fluorescent brightening agent can give a better design effect that makes use of the luminescent color. Further, an antistatic resin composition that is delicately colored with a very small amount of dye or pigment can also be provided.

  Examples of the fluorescent dye (including a fluorescent brightening agent) used in the present invention include a coumarin fluorescent dye, a benzopyran fluorescent dye, a perylene fluorescent dye, an anthraquinone fluorescent dye, a thioindigo fluorescent dye, and a xanthene fluorescent dye. And xanthone fluorescent dyes, thioxanthene fluorescent dyes, thioxanthone fluorescent dyes, thiazine fluorescent dyes, and diaminostilbene fluorescent dyes. Among these, coumarin fluorescent dyes, benzopyran fluorescent dyes, and perylene fluorescent dyes that have good heat resistance and are less likely to deteriorate during molding of a preferable high heat resistant thermoplastic resin are suitable.

  Examples of dyes other than the above bluing agents and fluorescent dyes include perylene dyes, coumarin dyes, thioindigo dyes, anthraquinone dyes, thioxanthone dyes, ferrocyanides such as bitumen, perinone dyes, quinoline dyes, quinacridone And dyes such as dyes, dioxazine dyes, isoindolinone dyes, and phthalocyanine dyes. Furthermore, the resin composition of this invention can mix | blend a metallic pigment, and can also obtain a better metallic color. As the metallic pigment, those having a metal film or a metal oxide film on various plate-like fillers are suitable.

  The content of the dye / pigment is preferably 0.00001 to 1 part by weight and more preferably 0.00005 to 0.5 part by weight per 100 parts by weight of the component A.

(V) Heat stabilizer other than D component and E component The antistatic resin composition of the present invention includes a heat stabilizer other than the phosphorus stabilizer of D component and the hindered phenol antioxidant of E component. An agent can also be blended. Such other heat stabilizer is preferably used in combination with either the D component or the E component, and particularly preferably used in combination with the D component or the E component. Examples of such other heat stabilizers include lactone stabilizers represented by the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene (such stabilizers). Is described in detail in JP-A-7-233160). Such a compound is commercially available as Irganox HP-136 (trademark, manufactured by CIBA SPECIALTY CHEMICALS) and can be used. Furthermore, a stabilizer obtained by mixing the compound with various phosphite compounds and hindered phenol compounds is commercially available. For example, Irganox HP-2921 manufactured by the above company is preferably exemplified. In the present invention, since the D component and the E component are blended in the thermoplastic resin, such a premixed stabilizer can be used. The blending amount of the lactone stabilizer is preferably 0.0005 to 0.05 parts by weight, more preferably 0.001 to 0.03 parts by weight with respect to 100 parts by weight of the component A.

  Other stabilizers include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Illustrated. Such a stabilizer is particularly effective when the resin composition is applied to rotational molding. The amount of the sulfur-containing stabilizer is preferably 0.001 to 0.1 parts by weight, more preferably 0.01 to 0.08 parts by weight, per 100 parts by weight of component A.

(Vi) Compound having heat absorption ability The antistatic resin composition of the present invention may contain a compound having heat absorption ability. Since the antistatic resin composition of the present invention has light transmittance, the compounding of the compound having the heat ray absorbing ability can suppress an increase in indoor temperature. Such a resin composition is particularly suitable for use in vehicle resin window glass and resin window sash glass.

  Such compounds include phthalocyanine-based near-infrared absorbers, metal oxide-based near-infrared absorbers such as ATO, ITO, iridium oxide and ruthenium oxide, and metal boride-based near infrared rays such as lanthanum boride, cerium boride and tungsten boride. Preferred examples include various metal compounds having excellent near-infrared absorption ability such as an absorber, and carbon filler. As such a phthalocyanine-based near infrared absorber, for example, MIR-362 manufactured by Mitsui Chemicals, Inc. is commercially available and easily available. Examples of carbon fillers include carbon black, graphite (including both natural and artificial, and whiskers), carbon fibers (including those produced by vapor phase growth), carbon nanotubes, and fullerenes, preferably carbon. Black and graphite. These can be used alone or in combination of two or more. The content of the phthalocyanine-based near infrared absorber is preferably 0.0005 to 0.2 parts by weight, more preferably 0.0008 to 0.1 parts by weight, with respect to 100 parts by weight of component A, and 0.001 to 0.00. More preferred is 07 parts by weight. The content of the metal oxide near-infrared absorber, the metal boride-based near infrared absorber, and the carbon filler is preferably in the range of 0.1 to 200 ppm (weight ratio) in the resin composition of the present invention. A range of ˜100 ppm is more preferable.

(Vii) Light Diffusing Agent The antistatic resin composition of the present invention can be provided with a light diffusing effect by blending a light diffusing agent. Examples of the light diffusing agent include polymer fine particles, low refractive index inorganic fine particles, and composites thereof. Such polymer fine particles are fine particles already known as light diffusing agents for thermoplastic resins. More preferably, acrylic crosslinked particles having a particle size of several μm, silicone crosslinked particles represented by polyorganosilsesquioxane, and the like are exemplified. Examples of the shape of the light diffusing agent include a spherical shape, a disk shape, a column shape, and an indefinite shape. Such spheres need not be perfect spheres, but include deformed ones, and such columnar shapes include cubes. A preferred light diffusing agent is spherical, and the more uniform the particle size is. The content of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, and still more preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the component A. Two or more light diffusing agents can be used in combination.

(Viii) White pigment for high light reflection The antistatic resin composition of the present invention can be provided with a light reflection effect by blending a white pigment for high light reflection. As such a white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treating agent such as silicone) pigment is particularly preferred. The content of the white pigment for high light reflection is preferably 3 to 30 parts by weight, more preferably 8 to 25 parts by weight with respect to 100 parts by weight of the component A. Two or more kinds of white pigments for high light reflection can be used in combination.

(Ix) Flame retardant In the antistatic resin composition of the present invention, an amount of a flame retardant that does not impair the object of the present invention can be used. Examples of the flame retardant include brominated epoxy resin, brominated polystyrene, brominated polycarbonate, brominated polyacrylate, monophosphate compound, phosphate oligomer compound, phosphonate oligomer compound, phosphonitrile oligomer compound, phosphonic acid amide compound, organic sulfonic acid Examples thereof include metal salts (for example, potassium perfluoroalkane sulfonate and potassium diphenyl sulfone sulfonate), and silicone flame retardants. Each of these flame retardants can be blended in a known amount relative to the thermoplastic resin.

  As the monophosphate compound and the phosphate oligomer compound, one or more phosphorus compounds represented by the following general formula (XIX) are preferably exemplified.

（但し上記式中のＸは、ハイドロキノン、レゾルシノール、ビス（４−ヒドロキシジフェニル）メタン、ビスフェノールＡ、ジヒドロキシジフェニル、ジヒドロキシナフタレン、ビス（４−ヒドロキシフェニル）スルホン、ビス（４−ヒドロキシフェニル）ケトン、ビス（４−ヒドロキシフェニル）サルファイドから誘導されるものが挙げられ、ｊ、ｋ、ｌ、ｍはそれぞれ独立して０または１であり、ｎは０〜５の整数であり、またはｎ数の異なるホスフェートの混合物の場合は０〜５の平均値であり、Ｒ^１、Ｒ^２、Ｒ^３、およびＲ^４はそれぞれ独立してフェノール、クレゾール、キシレノール、イソプロピルフェノール、ブチルフェノール、ｐ−クミルフェノールから誘導されるものである。）

(However, X in the above formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, bis And those derived from (4-hydroxyphenyl) sulfide, wherein j, k, l and m are each independently 0 or 1, n is an integer of 0 to 5, or n different phosphates. And R ¹ , R ² , R ³ , and R ⁴ are each independently derived from phenol, cresol, xylenol, isopropylphenol, butylphenol, p-cumylphenol. .)

Particularly preferably, X is derived from resorcinol, bisphenol A, j, k, l, m are each 1, n is 0 or 1, preferably infinitely close to ¹ , R ¹ , R ² , R ³ , and R ⁴ are each independently derived from phenol or xylenol (particularly 2,6-xylenol).

  In the general formula (XIX), the monophosphate compound includes triphenyl phosphate, and the phosphate oligomer compound includes resorcinol bis (dixylenyl phosphate) as a main component and bisphenol A bis (diphenyl phosphate) as a main component. The flame retardancy is good, the fluidity at the time of molding is good, the hydrolyzability is good, and the long-term decomposition is small.

  Furthermore, the antistatic resin composition of the present invention may contain an anti-dripping agent typified by polytetrafluoroethylene having fibril-forming ability. 0.0001-3 weight part is preferable with respect to 100 weight part of A component, and, as for the quantity of this dripping prevention agent, 0.001-0.1 weight part is more preferable.

(X) Other components other than the above In the antistatic resin composition of the present invention and its molded article, in addition to the A component to the E component and each of the above components, a crosslinked rubber is used as long as the object of the present invention is not impaired. , Inorganic phosphors (for example, phosphors having aluminate as a mother crystal), flow modifiers, crystal nucleating agents, inorganic and organic antibacterial agents, photocatalytic antifouling agents (for example, fine particle titanium oxide, fine particle zinc oxide) , And various known additives for resins such as a photochromic agent may be contained.

<About the manufacturing method of a resin composition>
In producing the antistatic resin composition of the present invention, the production method is not particularly limited. However, since it is important that the antistatic agent is uniformly dispersed in the resin in the molded product, the resin composition of the present invention is obtained by melt-kneading the B component, the C component, and the other components in the A component. It is preferable to manufacture.

  Specific examples of the melt kneading method include a Banbury mixer, a kneading roll, and an extruder. Of these, an extruder is preferable from the viewpoint of kneading efficiency, and a multi-screw extruder such as a twin-screw extruder is more preferable. In such a twin screw extruder, a more preferred embodiment is as follows. As the screw shape, one, two, and three screw screws can be used, and in particular, a two-thread screw having a wide range of application in both the ability to convey the molten resin and the shear kneading ability can be preferably used. The ratio (L / D) of the screw length (L) to the diameter (D) in the twin-screw extruder is preferably 20 to 45, more preferably 28 to 42. When L / D is large, uniform dispersion is likely to be achieved, while when it is too large, decomposition of the resin is likely to occur due to thermal degradation. The screw needs to have one or more kneading zones composed of kneading disk segments (or kneading segments corresponding thereto) for improving kneadability, and preferably 1 to 3 kneading zones.

  Furthermore, as an extruder, what has a vent which can deaerate the water | moisture content in a raw material and the volatile gas which generate | occur | produces from melt-kneading resin can be used preferably. From the vent, a vacuum pump is preferably installed for efficiently discharging generated moisture and volatile gas to the outside of the extruder. It is also possible to remove a foreign substance from the resin composition by installing a screen for removing the foreign substance mixed in the extrusion raw material in the zone in front of the extruder die. Examples of such a screen include a wire mesh, a screen changer, a sintered metal plate (such as a disk filter), and the like.

  Since the ionic compound of the B component of the present invention is usually liquid at room temperature, the following method is preferably exemplified as its supply method. (I) A method of supplying an ionic compound into an extruder accurately using a liquid injection device. In this method, if necessary, the ionic compound can be heated to lower the viscosity and be supplied. (Ii) A method in which the ionic compound and the thermoplastic resin powder are premixed using a mixer such as a Henschel mixer (including a super mixer) and then supplied to the extruder. (Iii) A method in which an ionic compound and a thermoplastic resin of component A or a polyether ester of component C are previously melt-kneaded to form a master pellet.

  One of the methods (ii) is a method in which all necessary raw materials are premixed and supplied to an extruder. Another method is a method in which a master agent containing a high concentration of an ionic compound is prepared, and the master agent is independently or further premixed with the remaining thermoplastic resin or the like and then supplied to an extruder. . The master agent can be selected from either a powder form or a form obtained by compressing and granulating the powder. Other premixing means include, for example, a Nauter mixer, a V-type blender, a Henschel mixer (including a supermixer), a mechanochemical device, and an extrusion mixer, but a high-speed stirring type mixer such as a Henschel mixer. Is preferred. Still another premixing method is, for example, a method in which a thermoplastic resin and an ionic compound are uniformly dispersed in a solvent, and then the solvent is removed, and the ionic compound is frozen and solidified as necessary. In this method, a dispersion aid such as dry ice is also mixed with the thermoplastic resin powder.

  Among the above methods, a method in which an ionic compound and a polyether ester of component C are previously melt-kneaded to obtain an antistatic agent master pellet is suitable for the present invention in terms of excellent versatility. The content ratio of the B component and the C component in the master pellet is preferably 0.1 to 50 parts by weight, more preferably 1 to 25 parts by weight, still more preferably based on 100 parts by weight of the C component. Is 2 to 15 parts by weight.

  The antistatic resin composition extruded from the extruder is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer and pelletized. Since the resin composition of the present invention has antistatic properties, the ratio of dust adhering to the pellet is reduced. However, when it is necessary to further reduce the influence of external dust or the like, it is preferable to clean the atmosphere around the extruder. On the other hand, pellets made of the resin composition of the present invention involve much water used during water cooling during pelletization. Therefore, it is advantageous in the subsequent transportation process and the packaging process that the pelletization is carried out by sufficiently draining using means such as compressed air.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. Such a cylinder includes an elliptic cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.3 mm. In the case of an elliptic cylinder, such a diameter preferably includes both the major axis and the minor axis. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 3.5 mm.

<About a molded product comprising the resin composition of the present invention>
The antistatic resin composition of the present invention obtained as described above can be usually produced by injection molding the pellets produced as described above to produce various products. In such injection molding, not only a normal molding method but also an injection compression molding, an injection press molding, a gas assist injection molding, a foam molding (including those by injection of a supercritical fluid), an insert molding, depending on the purpose as appropriate. A molded product can be obtained using an injection molding method such as in-mold coating molding, heat insulating mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultrahigh-speed injection molding. The advantages of these various molding methods are already widely known. In addition, either a cold runner method or a hot runner method can be selected for molding.

  The antistatic resin composition of the present invention can also be used in the form of various profile extrusion molded articles, sheets, films, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, and the like can also be used. Sheets and films are formed into various shapes by thermoforming methods such as vacuum forming. Furthermore, the resin composition of this invention can also shape | mold a heat-shrinkable tube by applying specific extending | stretching operation. These extrusion molded products can be used as molded products having the antistatic resin composition of the present invention in the surface layer by multilayer extrusion molding. Further, the polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

This provides a molded article of an antistatic resin composition having excellent antistatic properties, its sustainability, and thermal stability. That is, according to the present invention, 0.01 to 20 parts by weight of B component, 0.1 to 50 parts by weight of C component, more preferably 0.0001 to 1 part by weight of D component, and 100 parts by weight of A component, and There is provided a molded article having antistatic properties obtained by melt-molding an antistatic resin composition containing 0.0001 to 1 part by weight of an E component. More specifically, according to a preferred aspect of the present invention, the surface resistance value of a test piece of a smooth flat plate having a surface arithmetic average roughness (Ra) of 0.03 μm is 1 × 10 ¹² or less and 1 × 10 ^7. An antistatic resin composition satisfying the above (preferably 1 × 10 ⁸ or more) is provided. Furthermore, in the polycarbonate resin which is a particularly preferable component A of the present invention, in addition to such antistatic performance, a molded article having excellent impact resistance under good thermal stability is provided. More specifically, it shows ductile fracture in a V-shaped notched Izod impact strength measurement using a 3.2 mm-thick test piece in accordance with ASTM D256, and such ductile fracture is intentionally prolonged in the molding machine cylinder. There is provided a molded article made of a resin composition that is also recognized in a test piece produced by staying. Such ductile fracture satisfies an impact strength of 200 J / m or more, more preferably 300 J / m or more, and particularly preferably 400 J / m or more. The upper limit of impact strength is 1000 J / m or less, preferably 800 J / m or less. Moreover, as a molding machine cylinder temperature in long-term heat retention, the heat history which retains for 10 minutes at 260 degreeC is illustrated.

  The antistatic resin composition of the present invention can be effectively used as a container for transporting electronic parts represented by IC magazine cases, silicon wafer containers, glass substrate storage containers, carrier tapes and the like. The IC magazine case is preferably a profile extrusion molded product. Furthermore, the antistatic resin composition of the present invention can be effectively used for optical disk cartridge cases and information recording medium parts represented by hard disk parts. Further, it can also be used for antistatic or antistatic components in electronic copying equipment and printing equipment such as a charging roll of an electrophotographic photosensitive device.

  In addition, the antistatic resin composition of the present invention is a transparent member for vehicles (a head lamp lens, a blinker lamp lens, a tail lamp lens, a resin window glass) as a molded article consisting of a single substance or as a material constituting the surface layer of the molded article. , Meter covers, etc.), transparent members for gaming machines (decorative parts inside gaming machines (pachinko machines, game machines, etc.), and electronic circuit board covers, bases, etc.), transparent sheet members (including film members, such as resin) Window glass (especially for construction such as double sash resin window glass), solar cell cover, display device lens, outdoor mirror, meter cover, vending machine cover, dummy bottle, blister pack, flat display device cover, and Touch panel, etc.), lighting cover, through lens, sunglasses, gog , And are available, such as in water glasses.

  Furthermore, various surface treatments can be performed on the molded article made of the antistatic resin composition of the present invention. Surface treatment here refers to a new layer on the surface of resin molded products such as vapor deposition (physical vapor deposition, chemical vapor deposition, etc.), plating (electroplating, electroless plating, hot dipping, etc.), painting, coating, printing, etc. A method used for ordinary resin molded products can be applied. Specific examples of the surface treatment include various surface treatments such as hard coat, water / oil repellent coat, ultraviolet absorption coat, infrared absorption coat, and metalizing (evaporation). Hard coat is a particularly preferred and required surface treatment.

  In addition, since the antistatic resin composition of the present invention has improved metal adhesion, application of vapor deposition treatment and plating treatment is also preferred. The molded product thus provided with the metal layer can be used for electromagnetic wave shielding parts, conductive parts, antenna parts, and the like. Such parts are particularly preferably in the form of sheets and films.

  Since the antistatic resin composition of the present invention is excellent in antistatic performance, transparency, hue, and impact resistance, as described above, building, building material, agricultural material, marine material, vehicle, electric / electronic Widely useful in various fields such as equipment, machinery, etc. Therefore, the industrial effect exhibited by the present invention is extremely great.

  The form of the present invention considered to be the best by the present inventors is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

  The following examples further illustrate the present invention. Unless otherwise specified, parts in the examples are parts by weight and% is% by weight. Evaluation was carried out by the following method.

(I) Evaluation of resin composition (i) Antistatic performance: injection molding of a test piece of smooth flat plate having a length of 50 mm × width of 50 mm × thickness of 2.0 mm and a surface arithmetic average roughness (Ra) of 0.03 μm Manufactured by. The test piece was adjusted for one week in an environment of 23 ° C. and 50% humidity immediately after molding. Thereafter, the surface specific resistance value (Ω) of the test piece was measured with a SM-8210 pole super insulation meter manufactured by Toa Denpa Kogyo Co., Ltd. The smaller the value, the better the antistatic performance.

  (Ii) Persistence of antistatic performance: The test piece prepared and measured in (i) above is thoroughly washed with water, then the surface moisture is removed, and stored for one week in an environment at a temperature of 23 ° C. and a relative humidity of 50%. After adjusting the state, the surface resistivity was measured again.

  (Iii) Impact resistance: A test piece having a thickness of 3.2 mm according to ASTM D256 was produced by injection molding. In accordance with ASTM D256, a V-shaped notch was put into the test piece by cutting, and an Izod impact test was conducted to determine its impact strength. The specimen was molded in a 50 second cycle at a cylinder temperature of 260 ° C. and a mold temperature of 60 ° C. PEN was not evaluated because the evaluation of impact strength in an unstretched state was not practical.

  (Iv) Molding heat stability: In the preparation of the test piece of (iii) above, the continuous molding is temporarily interrupted after the completion of the metering step, and the molten resin is retained in the molding machine cylinder for 10 minutes, and then molded again. A heat-settled test piece was prepared. The test piece was subjected to an Izod impact test in the same manner as in (iii) above to determine its impact strength.

(II) Manufacture of resin molded product (in addition, explanation is explained according to the symbols in the following table)
(I) Production of master pellets: 5 parts by weight of B-1 component (ION-B) or B-2 component (ION-T) with respect to 100 parts by weight of C component (TJP-101) shown below. The blended master pellet was manufactured using a vent type twin screw extruder (manufactured by Nippon Steel Works, Ltd .: TEX30XSST (completely meshing, rotating in the same direction, two-thread screw)). The B-1 component or the B-2 component was supplied by the liquid injection device so as to be the predetermined amount, and the supply nozzle of the liquid injection device was disposed in the cylinder block next to the first supply port. The cylinder temperature and die temperature were 180 ° C., and the vent vacuum was 3 kPa, the screw rotation speed was set to 150 rpm, and the discharge amount was set to 18.9 kg. After being once pulled taken through zone was pelletized using a pelletizer.

  (Ii) Manufacture of pellets: Resin composition pellets having the blending ratios shown in the table were prepared as follows. Each component in the table was weighed, and Examples 1-8 and Comparative Examples 1-8 were uniformly mixed using a super mixer, and the other Examples and Comparative Examples were uniformly mixed using a tumbler. The pellets made of the resin composition were prepared. As the extruder, a vent type twin screw extruder (manufactured by Nippon Steel Works: TEX30XSST (completely meshing, rotating in the same direction, two-thread screw)) with a diameter of 30 mmφ was used. Extrusion conditions were a discharge rate of 25 kg / h, a screw rotation speed of 150 rpm, and a vent vacuum of 3 kPa, and the cylinder temperature profile was distributed so as to increase almost evenly in each block. 9 to 12 and Comparative Examples 1 to 5 were screw root temperature 220 ° C. and die temperature 250 ° C. Comparative Examples 6 to 8 were screw root temperature 240 ° C. and die temperature 270 ° C. Example 8 was screw root temperature 270. And a die temperature of 300 ° C. In Example 13, the screw root temperature was 320 ° C. and the die temperature was 350 ° C. . After cooling the extruded strands from a die in a water bath, thoroughly removing the moisture adhering to the strands using compressed air blower, and cut in a subsequent pelletizer pelletized.

  (Iii) Manufacture of smooth flat plate test piece: The obtained pellet was dried at 110 ° C. to 120 ° C. for 5 hours using a hot air circulating dryer. The pellets immediately after drying were subjected to an injection molding machine (manufactured by FANUC: AUTOSHOT T series model 150D) of length 50 mm × width 50 mm × thickness 2.0 mm and surface arithmetic average roughness (Ra) of 0. A test piece of 03 μm smooth flat plate was molded. The molding conditions were as follows.

  In Examples 1 to 7, 9 to 12, and Comparative Examples 1 to 5, the cylinder temperature was 260 ° C. and the mold temperature was 60 ° C. In Comparative Examples 6 to 8, the cylinder temperature was 300 ° C and the mold temperature was 80 ° C. In Example 6, the cylinder temperature was 300 ° C. and the mold temperature was 100 ° C. In Example 13, the cylinder temperature was 330 ° C. and the mold temperature was 100 ° C. The shooting speed was 20 mm / sec and the molding cycle was 50 seconds. The cylinder temperature was set to the same temperature in all zones.

  (Iv) Preparation of sheet-like member: After drying the pellets of Examples 9 to 13 in the same manner, using a single screw extruder with a screw diameter of 40 mm, the same as the cylinder temperature at the time of injection molding of (iii) above An unstretched film having a thickness of 200 μm was produced by extruding from a T-die having a width of 250 mm under conditions of a cylinder temperature and a die temperature 10 ° C. lower than the cylinder temperature. In addition, the temperature control machine was connected to the cooling roll, and it was possible to control the cooling temperature freely, and the temperature of the cooling roll was adjusted to 30 ° C. at which the production was most stable in each film. Although all of these were somewhat inferior to the smooth flat plate test piece, the surface specific resistance value of the same order was obtained.

(Examples 1-13 and Comparative Examples 1-8)
The pellet of the resin composition which consists of each component of a table | surface was manufactured, and the test piece and the sheet-like member were created with the said processing method. The evaluation results are shown in Tables 1-3. The contents of each component in the table are as follows.

(A component)
PC-50WP: Polycarbonate resin powder having a viscosity average molecular weight of 23,500 produced from bisphenol A and phosgene by an interfacial condensation polymerization method (manufactured by Teijin Chemicals Ltd .: Panlite L-1250WP (trade name))
PC-BCF: Aromatic polycarbonate resin powder made of 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene (abbreviated as “BCF”) and bisphenol A (abbreviated as “BPA”) produced by the following method PEN: Polyethylene naphthalate resin (manufactured by Teijin Chemicals Ltd .: Teonex TN8770 (trade name)). (Mole%, IV value is 0.7, glass transition temperature is 115 ° C.)
PAR: Polyarylate resin (manufactured by Unitika Ltd .: U polymer U-100 (trade name))

  [Method for producing PC-BCF]: A reactor equipped with a thermometer and a stirrer was charged with 19580 parts of ion-exchanged water and 3850 parts of a 48.5% by weight aqueous sodium hydroxide solution, to which 1175 parts of BCF, 2835 parts of BPA, and hydrosulfite 9 After dissolving the parts, 13210 parts of methylene chloride was added and 2000 parts of phosgene was blown in at 40 ° C. for about 40 minutes with vigorous stirring. After completion of the phosgene blowing, the temperature was raised to 28 ° C., 94 parts of p-tert-butylphenol and 640 parts of sodium hydroxide were added to emulsify, 6 parts of triethylamine was added, and stirring was continued for 1 hour to complete the reaction. After completion of the reaction, the organic phase was separated, diluted with methylene chloride, washed with water, acidified with hydrochloric acid and washed with water. When the conductivity of the aqueous phase was almost the same as that of ion-exchanged water, the methylene chloride was evaporated in a kneader. 4080 parts of a colorless powder of copolymer having a BCF: BPA molar ratio of 20:80 was obtained. The viscosity average molecular weight of this copolymer polycarbonate (PC-BCF) powder was 20,300. The reaction system was carried out under nitrogen bubbling and nitrogen reflux to block contact with oxygen during the reaction.

(B component)
(B-1 component)
ION-B: ammonium salt whose counter ion is BF ₄ ⁻ in the general formula (II) (Nisshinbo Co., Ltd .: ionic liquid B (trade name))
(B-2 component)
ION-T: An ammonium salt whose counter ion is (CF ₃ SO ₂ ) ₂ N ^— in the general formula (II) (Nisshinbo Co., Ltd .: ionic liquid T (trade name))
(For comparison with B component)
DBS-P: tetrabutylphosphonium salt of dodecylbenzenesulfonic acid (Takemoto Yushi Co., Ltd .: TCS-101 (trade name))
DBS-Na: sodium dodecylbenzenesulfonate (manufactured by Takemoto Yushi Co., Ltd.)

(C component)
TJP-101: polyether ester having a sulfonate group (manufactured by Takemoto Yushi Co., Ltd .; TJP-101 (trade name), such a polyether ester is (C1) an aromatic dicarboxylic acid component having no sulfonate group, ( C2) an aromatic dicarboxylic acid component substituted with a sulfonate group represented by the general formula (III), (C3) a glycol component having 2 to 10 carbon atoms, and (C4) a number average molecular weight of 200 to 50,000. A polyether ester comprising a poly (alkylene oxide) glycol component, wherein the dicarboxylic acid for deriving (C1) is 2,6-naphthalenedicarboxylic acid, and the dicarboxylic acid for deriving (C2) is 5- Sodium sulfoisophthalic acid, the glycol component for deriving (C3), is ethylene glycol and 1,6-hexane. The glycol component for deriving sundiol and (C4) is poly (ethylene oxide) glycol having a number average molecular weight of 2,000. Of the total of 100 mol% of (C1) and (C2), (C1) is 88 In the total 100 mol% of ethylene glycol and 1,6-hexanediol, ethylene glycol is 10 mol% and 1,6-hexanediol is 90 mol%. Further, the poly (ethylene oxide) glycol (C4) is 30% by weight in 100% by weight of the polyether ester, and the concentration of sodium sulfonate base in the polyether ester is 2.9 × 10 ⁻⁴ mol / g. And reduced viscosity measured at 30 ° C. in a mixed solvent of phenol / tetrachloroethane (weight ratio 40/60) Concentration of 1.2g / dl) is 1.35.

(Master pellet of B component and C component)
BCM-B: Master pellet composed of TJP-101 and ION-B prepared by the above production method BCM-T: Master pellet composed of TJP-101 and ION-T prepared by the above production method (D Component and E component)
D-PEP8: (Asahi Denka Kogyo Co., Ltd .: ADK STAB PEP-8 (trade name))
E-AO80: 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane (Asahi Denka Kogyo Co., Ltd .: ADK STAB AO-80 (trade name))

  As is clear from the above table, the antistatic resin composition of the present invention exhibits extremely excellent conductivity by using a polyether ester having a sulfonate group and a specific ionic compound in combination. I understand. Even if a commonly used ionic surfactant is used instead of such an ionic compound, the same characteristics as in the present invention cannot be obtained. From the difference in the effects, the synergistic effect is clearly recognized in the combined use of the B component and the C component of the present invention. Moreover, it turns out that the antistatic resin composition of this invention has favorable heat resistance from the above.

Claims (7)

100 parts by weight of a thermoplastic resin (component A ) having a glass transition temperature (Tg) of 115 ° C. or higher, 0.01 to 20 parts by weight of an ionic compound (component B) represented by the following general formula ( II ), and sulfonic acid An antistatic resin composition comprising 0.1 to 50 parts by weight of a polyether ester (C component) having a base.

(In formula ( II ), Y represents a monovalent anion which is BF ₄ ⁻ or (CF ₃ SO ₂ ) ₂ N ^— .) The above component C, antistatic resin composition according to claim 1, wherein a polyether ester having the following general formula (III) is substituted with a sulfonic acid base represented by aromatic dicarboxylic acid component.

(In the formula, Ar represents a trivalent aromatic group having 6 to 20 carbon atoms, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion, or a tetraalkylammonium ion.) The C component includes (C1) an aromatic dicarboxylic acid component having no sulfonate group, (C2) an aromatic dicarboxylic acid component substituted with a sulfonate group represented by the general formula (III), and (C3) carbon. The antistatic resin composition according to claim 2 , which is a polyether ester having a glycol component of several 2 to 10 and (C4) a poly (alkylene oxide) glycol component having a number average molecular weight of 200 to 50,000. The antistatic resin composition according to any one of claims 1 to 3 , wherein the component A is a polycarbonate resin. Further, 0.0001 to 1 part by weight of a phosphorus stabilizer (D component) and / or a hindered phenol antioxidant (E component) is blended based on 100 parts by weight of the A component. The antistatic resin composition according to claim 4 . 6. The antistatic resin composition according to claim 5 , wherein the phosphorus stabilizer (component D ) is a phosphonite compound or a phosphite compound represented by the following general formula (IV).

(In formula (IV), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different from each other.) Antistatic composition comprising a resin composition comprising 100 parts by weight of a polyether ester (C component) having a sulfonate group and 0.1 to 50 parts by weight of an ionic compound (B component) represented by the following general formula ( II ) Agent.

(In formula ( II ), Y represents a monovalent anion which is BF ₄ ⁻ or (CF ₃ SO ₂ ) ₂ N ^— .)