JP5519092B2 - Antistatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to an antistatic polycarbonate resin composition and a molded product comprising the same, and more particularly to a transparent member for vehicles, a transparent member for gaming machines, and a transparent sheet-like member. More specifically, it has excellent antistatic properties, hue, molding heat resistance, transparency and impact resistance, and in addition, the antistatic performance is sustained during dry heat treatment (hereinafter sometimes simply referred to as “dry heat durability”). The present invention relates to an excellent antistatic polycarbonate resin composition, and a molded article comprising the same, in particular, a vehicle transparent member, a gaming machine transparent member, and a transparent sheet-like member.

  Polycarbonate resins are widely used in electrical, mechanical, automotive, and medical applications because they have excellent transparency, heat resistance, mechanical strength, and the like. However, the polycarbonate resin has a large surface resistivity, and static electricity induced by contact or friction is difficult to disappear. Therefore, a molded product made of polycarbonate resin may cause problems such as adhesion of dust to the surface of the molded product, discomfort due to electric shock to the human body, and generation of noise or malfunction in electronic products. That is, the chargeability of the polycarbonate resin may be a problem.

  Therefore, it has always been desired to impart antistatic properties to the antistatic polycarbonate resin composition while maintaining the basic characteristics of the polycarbonate resin. That is, there has been a demand for a resin composition having good antistatic properties and excellent hue, transparency, and impact resistance.

  Conventionally, a method of blending an ionic surfactant is known as a method for preventing the charging of the polycarbonate resin. Examples of such ionic surfactants include, for example, alkali metal salts of sulfonic acid and phosphonium salts of sulfonic acid. Particularly, the phosphonium salt is widely known as a preferable salt because of its excellent transparency in the resin composition. Yes.

  However, the combination of an ionic surfactant and a polycarbonate resin is inferior in melt stability, so it has a strong tendency to pyrolyze, and not only the hue and appearance of the resulting pellets and products obtained by processing them are reduced. There are problems of corroding the mold and generating odors.

  As a method for improving the hue of a resin composition in which a phosphonium salt of sulfonic acid is blended with a polycarbonate resin, for example, a method of combining the resin composition and (i) a phosphite (see Patent Document 1), ( ii) a method of combining a boric acid derivative (see Patent Document 2), (iii) a method of combining a polystyrene polymer compound (see Patent Document 3), and (iv) a method of combining a sulfur-containing ester compound (Patent Document 4) And (v) a method of combining a phosphite or sulfur-containing ester compound and polycaprolactone (see Patent Document 5), and (vi) a method of combining with phosphorous acid (see Patent Document 6). is there.

  Also known is a method of blending a phosphite with a polycarbonate resin composition obtained by blending a polycarbonate resin obtained by a melting method with a sulfonate compound composed of an organic sulfonate anion and an organic phosphonium cation (see Patent Document 7). .

  In addition, a resin composition in which a phosphonium salt of sulfonic acid is mixed with a polycarbonate resin, and phosphoric acid or an organic acid are combined (see Patent Document 8), or a specific phosphonite compound is combined (see Patent Document 9), Also known are antistatic polycarbonate resin compositions having improved molding heat resistance, transparency and dry heat resistance.

  However, in fields where the hue and transparency of products are more important, an antistatic polycarbonate resin composition having further improved hue and transparency is required. This is because in recent years, products tend to be thinner and larger, and the molding process temperature of the resin composition is higher than before, and the number of cases where the heat history is increased is increasing. Such a requirement is particularly high when the molded product is used through light from a light source. One of the reasons is that it is not preferable that the light passing through the molded product is colored, and the other reason is that it is likely to be subject to coloring restrictions when the molded product is used in a specific color. . In particular, when performing vivid coloring such as a fluorescent color, it is desirable that the original resin is infinitely colorless and transparent. Examples of such a demanded field include a transparent member for a vehicle represented by, for example, a headlamp lens, a cover, and a winker lens, and a transparent component used in a large game machine for a pachinko machine, a slot machine, and a game center. A transparent member for gaming machines is exemplified. Furthermore, various display cases and covers, for printing (when a design is recognized through a transparent part), and vapor deposition (when used like a mirror through a transparent part) are generally used in the shape of a sheet or by thermoforming the sheet. In other fields, it is required to have both high hue and transparency. In addition, resin window sash glass (especially double glazing), garage and arcade covers, outdoor mirrors, meter covers, vending machine covers, flat display device covers, and solar cell covers have similar characteristics. May be required.

Japanese Patent Laid-Open No. 01-014627 Japanese Patent Laid-Open No. 02-284951 Japanese Unexamined Patent Publication No. 03-081362 Japanese Patent Laid-Open No. 05-171024 JP 09-194711 A JP-A-11-080532 JP 2003-105186 A JP 2003-096291 A Japanese Patent Laid-Open No. 2002-020608

  An object of the present invention is to provide an antistatic polycarbonate resin composition excellent in antistatic performance, hue, molding heat resistance, transparency, and impact resistance, more preferably in dry heat resistance, and a molded article comprising the same. In particular, the object is to provide a transparent member for vehicles, a transparent member for gaming machines, and a transparent sheet-like member.

  As a result of intensive investigations aimed at achieving the above object, the present inventors have found that when a specific amount of a low molecular weight sulfonate salt and a phosphate ester is blended with a polycarbonate resin, a polysulfate containing a sulfonate group is more preferably contained. It has been found that a resin composition meeting the above-mentioned purpose can be obtained by blending a polyester containing an ether ester and / or a sulfonate group, and the present invention has been completed through further intensive studies.

According to the present invention, (1) 100 parts by weight of a polycarbonate resin (component A), 0.01 to 4 parts by weight of a low molecular weight dodecylbenzenesulfonate (component B) having a stoichiometric molecular weight of 1000 g / mol or less , An antistatic polycarbonate resin composition comprising 0.001 to 0.3 parts by weight of a phosphoric ester (C component) is provided. According to the configuration (1), the antistatic property having a good hue, molding heat resistance, transparency, impact resistance, and antistatic dry heat sustainability even when the molding processing temperature is higher and the heat history is larger than before. -Soluble polycarbonate resin composition is obtained, and is suitably used for products having a strong tendency to make products thinner and larger.

  Furthermore, according to the present invention, as a more preferable embodiment, (2) the low molecular weight sulfonate is a sulfonate having a molecular weight of 1000 or less, preferably a sulfonic acid phosphonium salt represented by the following general formula (I), The antistatic polycarbonate resin composition (Configuration 2) having the above-described configuration (1), which is preferably dodecylbenzenesulfonic acid phosphonium salt or dodecylbenzenesulfonic acid tetrabutylphosphonium salt, is provided.

（式中、Ａ^１は炭素数１〜４０のアルキル基、炭素数６〜４０のアラルキル基、または炭素数６〜４０のアリール基を示し、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４はそれぞれ独立して、水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアラルキル基または炭素数６〜１５のアリール基を示す。）

(In the formula, A ¹ represents an alkyl group having 1 to 40 carbon atoms, an aralkyl group having 6 to 40 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and R ¹ , R ² , R ^3, and R ⁴ are each represented by Independently, it represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 15 carbon atoms.)

  Furthermore, according to the present invention, as a more preferred embodiment, (3) the phosphate ester comprises an aliphatic monophosphate ester represented by the following general formula (II), preferably trimethyl phosphate, triethyl phosphate, and tributyl phosphate. The antistatic polycarbonate resin composition (Configuration 3) having the above-mentioned configuration (1) or (2), which is at least one phosphate selected from the group, is provided.

（式中、Ｒ^５、Ｒ^６、Ｒ^７はそれぞれ独立して、水素原子または炭素数１〜２０のアルキル基を示す。）

^{(Wherein, R 5, R 6, R} 7 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

According to the configurations (2) and (3), an antistatic polycarbonate resin composition having better hue and transparency is provided.
Furthermore, according to the present invention, as a more preferred embodiment, (4) further comprising 0.01 to 5 parts by weight of a polyether ester having a sulfonate group and / or a polyester having a sulfonate group (component D). The antistatic polycarbonate resin composition (Configuration 4) having the above configurations (1) to (3) is provided.

Here, a sulfonate or a group protons sulfonic acid group _(-SO 3 H) has been substituted with other ^{_{cations, -SO 3 - X + (X}} + is SO ₃ ^- is a counterion ). More specifically, X ⁺ is a cation selected from metal ions and organic onium ions, and metal ions are particularly preferable. The cation may be a divalent or higher ion. Hereinafter, the polyether ester having a D component sulfonate group is simply referred to as “D component polyether ester”, and the D component sulfonate group polyester is simply referred to as “D component polyester”. is there.

  According to the configuration (4) which is a more preferred embodiment, an antistatic polycarbonate resin composition having higher antistatic performance, molding heat resistance and dry heat durability can be provided without impairing transparency and hue. . As a result, such a resin composition has little decrease in transparency and antistatic property even after long-term use. Such an effect is achieved by blending a polymer type sulfonate having a relatively good compatibility with the polycarbonate resin, so that the low molecular weight sulfonate does not aggregate or volatilize over a long period of time, and stably in the resin matrix. It is thought to be due to the existence.

  One preferred embodiment of the present invention is that (5) the polyether ester of component D is represented by (D1) an aromatic dicarboxylic acid component having no sulfonate group, (D2) represented by the following general formula (III) A polyether ester comprising an aromatic dicarboxylic acid component substituted with a sulfonate group, (D3) a glycol component having 2 to 10 carbon atoms, and (D4) a poly (alkylene oxide) glycol component having a number average molecular weight of 200 to 50,000. The antistatic polycarbonate resin composition (Configuration 5) having the above-described configuration (4).

（式中、Ａｒは炭素数６〜２０の３価の芳香族基、Ｍ^＋は金属イオンまたは有機オ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 or an organic onium ion.)

  One preferred embodiment of the present invention is that (6) the polyester of component D is (D5) an aromatic dicarboxylic acid component having no sulfonate group, (D6) a sulfonic acid represented by the above general formula (III) In the antistatic polycarbonate resin composition (Configuration 6) of the above configurations (4) and (5), which is a polyester comprising an aromatic dicarboxylic acid component substituted with a base, and (D7) a glycol component having 2 to 10 carbon atoms. is there.

  According to the constitutions (4) and (5), an antistatic polycarbonate resin composition having a good hue that is remarkably excellent in molding heat resistance is provided. Stabilization of molding heat resistance more than before can significantly improve yellowing and poor appearance during molding, but this effect is achieved by molding using a large molding machine or hot runner mold that tends to retain molten resin. Appears especially at. In addition, such a configuration provides an antistatic polycarbonate resin composition that maintains good transparency and hue even in a long-time dry heat state. The “component” in the polyether ester and polyester refers to a structural unit in these polymers derived from the compound or an ester-forming derivative thereof. For example, an aromatic dicarboxylic acid component refers to a structural unit in a polyether ester or polyester derived from an aromatic dicarboxylic acid or an ester-forming derivative thereof, and a glycol component refers to a glycol compound or an ester-based derivative thereof. The structural unit in the derived polyether ester or polyester is shown.

  One of the preferred embodiments of the present invention is the above constitution (1) to (7) comprising 0.01 to 2 parts by weight of a hindered phenolic antioxidant per 100 parts by weight of the polycarbonate resin (component A). The antistatic polycarbonate resin composition according to (6). (Configuration 7) According to the configuration (7), since it has advantages such as hue at the time of molding, molecular weight stability, hue stability at the time of heat treatment of molded products, etc., it is particularly suitable for products that are easily exposed to high temperatures. New molded articles are provided.

  One of the preferred embodiments of the present invention is the above constitution (1) comprising (8) 0.01-2 parts by weight of a phosphite-based antioxidant per 100 parts by weight of the polycarbonate resin (component A). (7) Antistatic polycarbonate resin composition (Configuration 8). According to this configuration (8), an antistatic polycarbonate resin composition that is more excellent in hue stability is provided.

  One of the preferred embodiments of the present invention is (9) Charging of the above constitutions (1) to (8) comprising 0.01 to 2 parts by weight of an ultraviolet absorber per 100 parts by weight of the polycarbonate resin (component A). It is a preventive polycarbonate resin composition. According to this configuration (9), an antistatic polycarbonate resin composition (configuration 9) which is excellent in antistatic properties, hue, molding heat resistance and transparency and also excellent in weather resistance is provided.

  One of the preferred embodiments of the present invention is (10) a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm or less, and the haze measured by JIS K7105 is 0.1 to 1%. The antistatic polycarbonate resin composition (Configuration 10) having the above-described configurations (1) to (9) that satisfies the requirements. According to this configuration (10), an antistatic polycarbonate resin composition having excellent transparency is provided.

  One of the preferred embodiments of the present invention is that (11) a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm or less is in a state for one week in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The above configuration (1) satisfying that the half-life is 200 seconds or less adjusted and measured with a static Honestometer at a temperature of 23 ° C., a relative humidity of 50%, an applied voltage of 10 kV, and an electrode-sample distance of 20 mm. (10) Antistatic polycarbonate resin composition (Configuration 11). According to this configuration (11), there is provided an excellent antistatic polycarbonate resin composition that does not easily adhere to dust or the like even when stored in the air for a long time and does not impair the transparency and appearance. .

  One of the preferred embodiments of the present invention is (12) a molded article obtained by melt-molding the antistatic polycarbonate resin composition having the constitutions (1) to (11). According to such a configuration (12), a polycarbonate resin molded article having excellent practicality and antistatic performance excellent in hue and transparency is provided.

  One of the preferable aspects of the present invention is the molded product according to (12), wherein (13) the molded product is a vehicle transparent member. The present invention provides a resin composition suitable for a transparent member for vehicles, which is a typical application requiring antistatic properties, hue stability and transparency, and further provides a transparent member for vehicles comprising such a composition. To do.

  One of the preferable aspects of the present invention is the molded article according to (12) above, wherein (14) the molded article is a transparent member for gaming machines. The resin composition of the present invention is characterized by being able to express various designs due to the high degree of freedom of coloring due to a good hue, and maintaining such designs for a long time without being hindered by dust adhesion. Have. Here, the transparent member for gaming machine includes a cover for protecting the electronic circuit board of the gaming machine. By using the same material for the cover and the various members used on the front surface of the gaming machine, it is possible to manufacture the equipment more efficiently and reduce its cost. The cover for protecting the electronic circuit board is particularly required to have antistatic performance in terms of suppressing noise generation and malfunction from the circuit. Therefore, the transparent member for gaming machines and the gaming machine having these advantages are provided by this configuration (14).

  One of the preferable aspects of the present invention is the molded product according to (12), wherein (15) the molded product is a transparent sheet-like member. According to this configuration (15), it is possible to provide a molded product suitable for various sheet-like members particularly requiring antistatic performance.

The details of the present invention will be further described below.
<Component A: Polycarbonate resin>
The component A in the antistatic polycarbonate resin composition of the present invention is a polycarbonate resin that is a main component of the resin composition. 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, it is particularly preferable that the component A constituting the resin composition is a copolymerized polycarbonate of the following (1) to (3). is there.
(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.

When a polyfunctional compound that produces a branched polycarbonate is included, the amount thereof is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to 0.8 mol, based on the total amount of the polycarbonate. Mol%. In particular, in the case of the melt transesterification method, a branched structure may occur as a side reaction. The amount of the branched structure is also 0.001 to 1 mol%, preferably 0.005 to 0.9% in the total amount of the polycarbonate. Those having a 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.

  In addition, the aromatic polycarbonate resin as the component A in the resin composition of the present invention is a polyester carbonate obtained by copolymerizing an aromatic or aliphatic (including alicyclic) bifunctional carboxylic acid, a bifunctional alcohol (fatty acid). It may be a copolymerized polycarbonate copolymerized with a cyclic group) and a polyester carbonate copolymerized with such a bifunctional carboxylic acid and a bifunctional alcohol. 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 aromatic polycarbonate resin as component A is a mixture of two or more of polycarbonates such as polycarbonates having different dihydric phenols, polycarbonates containing branched components, polyester carbonates, and polycarbonate-polyorganosiloxane copolymers. There may be. 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.

  The viscosity average molecular weight of the polycarbonate resin as the component A is not limited. However, when the viscosity average molecular weight is less than 10,000, the strength and the like are lowered, and when it exceeds 50,000, the molding process characteristics are lowered. Therefore, the range of 10,000 to 50,000 is preferable. The range of 15,000 to 30,000 is more preferable, and the range of 15,000 to 28,000 is more preferable. In this case, it is also possible to mix a polycarbonate having a viscosity average molecular weight outside the above range within a range in which moldability and the like are maintained. For example, a high molecular weight polycarbonate component having a viscosity average molecular weight exceeding 50,000 can be blended.

The viscosity average molecular weight referred to in the present invention is first determined by using an Ostwald viscometer from a solution obtained by dissolving 0.7 g of aromatic polycarbonate in 100 ml of methylene chloride at 20 ° C. with a 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

<B component: low molecular weight sulfonate>
The B component of the present invention is a low molecular weight sulfonate. Here, the low molecular weight means a stoichiometric molecular weight, preferably 1,000 g / mol or less, and more preferably 750 g / mol or less.
Examples of the cationic component of the low molecular weight sulfonate include alkali metals such as potassium, sodium, cesium, and rubidium, alkaline earth metals, phosphonium, ammonium, and the like, and examples of the acid component include dodecylbenzenesulfonic acid, perfluoroalkane. Examples thereof include sulfonic acid. Of these, potassium sulfonate, cesium, rubidium, phosphonium, and ammonium salts are preferable, and phosphonium sulfonate is particularly preferable. These can be used alone or in combination of two or more. In the combined use, it is preferable to use a phosphonium sulfonate salt and an alkali (earth) sulfonate metal salt in combination.

（式中、Ａ^１は炭素数１〜４０のアルキル基、炭素数６〜４０のアラルキル基、または炭素数６〜４０のアリール基を示し、Ｒ^１、Ｒ^２、Ｒ^３およびＲ^４はそれぞれ独立して、水素原子、炭素数１〜２０のアルキル基、炭素数６〜２０のアラルキル基または炭素数６〜１５のアリール基を示す。） Although it does not specifically limit as this sulfonic acid phosphonium salt, The sulfonic acid phosphonium salt shown by the following general formula (I) is illustrated suitably.

(In the formula, A ¹ represents an alkyl group having 1 to 40 carbon atoms, an aralkyl group having 6 to 40 carbon atoms, or an aryl group having 6 to 40 carbon atoms, and R ¹ , R ² , R ^3, and R ⁴ are each represented by Independently, it represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms or an aryl group having 6 to 15 carbon atoms.)

  The sulfonic acid phosphonium salt represented by the above general formula (I) has good heat resistance, anti-drying performance, dry heat sustainability, and relatively good compatibility with the polycarbonate resin. An excellent antistatic polycarbonate resin composition is provided.

In the general formula (I), examples of the alkyl group in A ¹ include a dodecyl group, a decyl group, a butyl group, and an ethyl group, and a dodecyl group and a decyl group are particularly preferable. Such an alkyl group includes an aralkyl group in which a part of hydrogen atoms of the alkyl group is substituted with an aryl group. The aralkyl group has 6 to 40 carbon atoms, and examples thereof include a benzyl group and a phenethyl group, and a phenethyl group is particularly preferable. Examples of the aryl group for A ¹ include an unsubstituted or substituted phenyl group, an unsubstituted or substituted naphthyl group, and the like. In these alkyl groups and aryl groups, part of the hydrogen atoms may be substituted with halogen atoms such as fluorine atoms, and the aralkyl groups and aryl groups may contain heteroatoms. Examples include a phenyl group, a naphthyl group, a tolyl group, and a dodecylphenyl group, and a dodecylphenyl group is particularly preferable.

In the general formula (I), R ¹ , R ² , R ³ and R ⁴ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aralkyl group having 6 to 20 carbon atoms, or 6 to 6 carbon atoms. 15 aryl groups are shown. R ¹ , R ² , R ³ and R ⁴ may be the same as or different from each other.

  The alkyl group having 1 to 20 carbon atoms may be a linear or branched alkyl group. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, 2-ethylbutyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group Tetradecyl group, octadecyl group, eicosyl group and the like.

Examples of the aralkyl group having 6 to 20 carbon atoms include benzyl group, 2,6-ditertiarybutyl-4-methylbenzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and 2-phenylisopropyl group.
Examples of the aryl group having 6 to 15 carbon atoms include a phenyl group, a tolyl group, and a naphthyl group.

Among these, R ¹ , R ² , R ³ and R ⁴ are preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 4 to 16 carbon atoms. Further, it is more preferable that R ¹ , R ² , R ³ and R ⁴ are butyl groups or octyl groups, and among them, all are butyl groups, or any one is an octyl group and the rest are butyl groups. Embodiments are preferred. The sulfonic acid phosphonium salt in which R ¹ , R ² , R ³ and R ⁴ are all butyl groups is preferable in terms of easy availability and compatibility with the polycarbonate resin, and any one of them is an octyl group and the rest The sulfonic acid phosphonium salt which is a butyl group is preferable in that the thermal deterioration of the antistatic performance is small. More preferred in practice is a phosphonium sulfonate salt in which R ¹ , R ² , R ³ and R ⁴ are all butyl groups.

  Among them, an aromatic sulfonic acid phosphonium salt is preferably used as the sulfonic acid phosphonium salt. Examples of the aromatic sulfonic acid used in the phosphonium salt of aromatic sulfonic acid include monomeric aromatic sulfonic acid, aromatic carboxylic acid and ester sulfonic acid, aromatic ether sulfonic acid, and aromatic sulfonate. Sulfonic acid, aromatic sulfonic acid, aromatic sulfone sulfonic acid, sulfonic acid of aromatic ketone, heterocyclic sulfonic acid, sulfonic acid of aromatic sulfoxide, and styrene in which hydrogen atom of benzene ring of styrene is substituted with sulfonic acid group There may be mentioned at least one acid selected from the group consisting of: 1 type, or 2 or more types can be used in combination. In addition, in the sulfonic acid phosphonium salt, a part of the hydrogen atoms may be substituted with a halogen atom such as a fluorine atom.

  As a specific example of such a sulfonic acid phosphonium salt, dodecylbenzenesulfonic acid phosphonium salt is more preferable, and particularly preferred is dodecylbenzenesulfonic acid tetrabutylphosphonium salt.

<C component: Phosphate ester>
Examples of the phosphoric acid ester that is the component C of the present invention include one or more phosphoric acid esters represented by the following general formula (IV).

（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、およびビス（４−ヒドロキシフェニル）サルファイドからなる群より選ばれた化合物から誘導される二価の基である。ｎは０〜５の整数であり、またはｎ数の異なるリン酸エステルの混合物の場合は０〜５の平均値であり、Ｒ^８、Ｒ^９、Ｒ^１０、およびＲ^１１はそれぞれ独立して１個以上のハロゲン原子を置換したもしくは置換していない炭素数１〜４０のアルキル基、炭素数６〜４０のアラルキル基、シクロアルキル基、および炭素数６〜４０のアリール基からなる群より選ばれた化合物から誘導される一価の基である。）

(X in the formula is hydroquinone, resorcinol, bis (4-hydroxydiphenyl) methane, bisphenol A, dihydroxydiphenyl, dihydroxynaphthalene, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, and bis ( 4-hydroxyphenyl) divalent group derived from a compound selected from the group consisting of sulfides, n is an integer of 0 to 5, or 0 to 0 in the case of a mixture of different numbers of phosphate esters. R ⁸ , R ⁹ , R ¹⁰ , and R ¹¹ are each independently an alkyl group having 1 to 40 carbon atoms substituted or not substituted with one or more halogen atoms, and 6 carbon atoms. Selected from the group consisting of -40 aralkyl groups, cycloalkyl groups, and aryl groups having 6 to 40 carbon atoms A monovalent group derived from the above compound.)

  The purpose of the present invention is to provide a polycarbonate resin composition that is excellent in hue, heat resistance, and transparency as well as excellent antistatic performance. It is easy to induce thermal decomposition and thermal degradation. As a result, pellets obtained by melt-kneading and molded products obtained by using them exhibit deterioration of appearance such as yellowing and silver generation, and the desired antistatic polycarbonate resin. It is difficult to obtain a composition. However, when only such a sulfonate is put in a glass test tube and heat-treated using a block heater at a temperature similar to the set temperature assumed when processing the antistatic polycarbonate resin composition obtained by the present invention, There is no significant yellowing of the sulfonate in the test tube. On the other hand, when the same test is carried out by replacing the glass test tube with a stainless steel test tube, significant discoloration is observed. Therefore, it is considered that the above-described yellowing and silver generation of the polycarbonate resin composition are highly likely to be affected by the contact between the sulfonate and the kneading machine steel or the molding machine steel during melt kneading or molding. From this, by adding a specific amount of the phosphoric acid ester represented by the above general formula (III) to the polycarbonate resin and the low molecular weight sulfonate, yellowing or silver that suppresses thermal decomposition or thermal degradation of the polycarbonate resin. It is presumed that the desirable antistatic polycarbonate resin composition with less generation is obtained because such a phosphate ester is effective as an inactive agent for active metals contained in equipment steel and suppresses decomposition. . Conventionally known stabilization techniques were mainly based on stabilization of radicals generated by thermal decomposition or thermal degradation or decomposition of peroxides into harmless ones, but the present invention fundamentally suppresses decomposition, It improves the hue and heat resistance of molding. Furthermore, according to the present invention, the phosphate ester not only improves the hue and molding heat resistance, but also promotes stabilization of low molecular weight sulfonates by metal deactivation on the surface of the equipment steel material during dry heat treatment. Thus, it is possible to improve the sustainability of the antistatic performance (sustainability of dry heat) and to provide a resin composition and a molded product having more excellent antistatic properties.

  Therefore, among the phosphoric acid esters represented by the general formula (IV), those that easily migrate to the equipment steel surface in the melt kneader or the molding machine, and that easily develop the metal deactivation effect on the steel surface, that is, Those having excellent affinity and dispersibility to polycarbonate resin and sulfonate, excellent wettability to metal, and stable without being decomposed even at high processing temperatures are preferable. Therefore, an aliphatic monophosphate ester represented by the following general formula (II) is preferably used.

（式中、Ｒ^５、Ｒ^６、Ｒ^７はそれぞれ独立して、水素原子または炭素数１〜２０のアルキル基を示す。）

^{(Wherein, R 5, R 6, R} 7 each independently represent a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

  Aliphatic monophosphates include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (chloropropyl) phosphate, etc., transparency and dispersibility Trimethyl phosphate, triethyl phosphate, and tributyl phosphate are more preferable from the viewpoint of superiority, but trimethyl phosphate is particularly preferable from the viewpoint of transparency.

<D component: Polyester ester having sulfonate group and / or polyester having sulfonate group>
The antistatic polycarbonate resin composition of the present invention exhibits more excellent characteristics by using a polyether ester having a sulfonate group and / or a polyester having a sulfonate group together with the sulfonate. Here, the polyether ester means a polymer having a poly (alkylene oxide) glycol component having a trimer or higher in its repeating unit, and the polyester is a polyester not containing a poly (alkylene oxide) glycol component having a trimer or higher. It is. The polyester may contain a diethylene glycol component. Polyether esters and polyesters of component D can be converted into polymer compounds by polymerizing monomers substituted with sulfonate groups, or polymers not substituted with sulfonate groups can be modified with sulfonate groups. Can also be manufactured.

Here sulfonate contained in component D - 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 ions in such counter ions are more preferably organic phosphonium ions (such as tetrabutylphosphonium ion and tetramethylphosphonium ion), and organic ammonium ions (such as tetrabutylammonium ion and tetramethylammonium ion), Particularly preferred are organic phosphonium ions. Further, the counter ion in the sulfonate group contained in the component D 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 D 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 D 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.

  The polyether ester of component D includes (D1) an aromatic dicarboxylic acid component having no sulfonate group, (D2) an aromatic dicarboxylic acid component substituted with a sulfonate group represented by the following general formula (III), A polyether ester composed of (D3) a glycol component having 2 to 10 carbon atoms and (D4) a poly (alkylene oxide) glycol component having a number average molecular weight of 200 to 50,000 is preferred.

（式中、Ａｒは炭素数６〜２０の３価の芳香族基、Ｍ^＋は金属イオンまたは有機ホスホ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 or an organic phosphonium ion.)

  Examples of the aromatic dicarboxylic acid (and its ester-forming derivative) having no sulfonate group for deriving (D1) include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and their ester-forming properties. And derivatives thereof. Among these, a polyetherester containing a naphthalenedicarboxylic acid component and a biphenyldicarboxylic acid component, particularly a naphthalenedicarboxylic acid component, is a molded article having a higher transparency by bringing the refractive index of the polyether ester closer to that of polycarbonate. It is preferable because it is easy to obtain. 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 (D1) can be contained alone or in combination in a polyether ester.

(D2) 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 specific examples thereof may be the same as those described above for X ⁺ , more preferably a metal ion, still more preferably an alkali. Metal ions, alkaline earth metal ions, and zinc ions are preferred, and alkali metal ions are particularly preferred. However, in the case of a divalent metal ion, 1 mol of metal ion corresponds to 2 mol of sulfonic acid group.

  Examples of the aromatic dicarboxylic acid substituted with a sulfonate group for deriving (D2) 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 (D2) can be contained alone or in combination of two or more in the polyether ester.

  The two types of acid components (D1) and (D2) are composed of 100 mol% of the total acid component, (D1) 95-50 mol% of the aromatic dicarboxylic acid component having no sulfonate group, and (D2) above The proportion is preferably 5 to 50 mol% of the aromatic dicarboxylic acid component substituted with the sulfonate group represented by the formula (III). When the proportion of the component (D2) is less than 5 mol%, the antistatic effect may not be sufficient. On the other hand, when the component (D2) 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 preferable ratios of the component (D1) and the component (D2) are (D1) 92 to 65 mol% and (D2) 8 to 35 mol%, and a more preferable ratio is (D1) 90 to 70 mol% and ( D2) 10 to 30 mol%.

  The glycol having 2 to 10 carbon atoms for deriving (D3), which is one of the constituent components of the polyether ester of component D 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. A preferred ratio of the 1,6-hexanediol component to the ethylene glycol component is 95 to 50 mol% of the 1,6-hexanediol component and 5 to 50 mol% of the ethylene glycol component, more preferably in 100 mol% of the glycol component. Is 90-70 mol% of 1,6-hexanediol component and 10-30 mol% of ethylene glycol component.

  As the poly (alkylene oxide) glycol for deriving (D4), which is one of the constituents of the polyether ester of component D 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 (D4) poly (alkylene oxide) glycol component is preferably in the range of 200 to 50,000. If the molecular weight is less than 200, a better antistatic effect may not be obtained, and the advantage of using a polyether ester 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 (D4) can be contained alone or in combination of two or more in the polyether ester.

  The content of the component (D4) is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, and still more preferably 20 to 40% by weight in 100% by weight of the polyether ester of the D component. . If it is less than 10% by weight, the antistatic effect which is an advantage of the polyether ester of the D component may not be sufficient. If it exceeds 50% by weight, the refractive index of the polyether ester of the D component will be low, It may be difficult to obtain a molded article of a polycarbonate resin composition having high light transmittance and excellent transparency.

  The polyether ester of component D 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 D in the present invention is the above-mentioned component (D1), component (D2), component (D3), and component (D4) that is heated and melted at 150 to 300 ° C. in the presence of a transesterification catalyst, and polycondensed. It can be obtained by reacting.

  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 these antioxidants used is preferably 0.001 to 0.5 parts by weight with respect to 100 parts by weight of the D component polyether ester.

  The temperature at which the above components (D1) to (D4) are heated and melted and polycondensed is distilled as an initial reaction at 150 to 200 ° C. for several tens of minutes to a dozen hours of esterification and / or transesterification. After the distillation of the product, a polymerization reaction for increasing the molecular weight of the reaction product is performed 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.

  The polyester used as the component D includes (D5) an aromatic dicarboxylic acid component having no sulfonate group, (D6) an aromatic dicarboxylic acid component substituted with a sulfonate group represented by the general formula (III), And (D7) a polyester comprising a glycol component having 2 to 10 carbon atoms is preferred.

  Examples of the aromatic dicarboxylic acid having no sulfonate group for inducing (D5) and ester-forming derivatives thereof include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and ester-forming derivatives thereof. Can be mentioned. Among these, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, biphenyldicarboxylic acid, and ester-forming derivatives thereof are preferable. In particular, a polyester containing an isophthalic acid component and a naphthalenedicarboxylic acid component is preferable because the crystallinity of the polyester is lowered, and as a result, a molded product having higher transparency can be easily obtained. The polyester is excellent in compatibility with the polycarbonate resin, and crystallization is inhibited by the influence of the polycarbonate resin. As a result, there is an advantage that the decrease in transparency in the dry heat resistance test is further improved as compared with the case of the polyether ester. Specific examples of naphthalenedicarboxylic acid and ester-forming derivatives thereof include 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, dimethyl 2,6-naphthalenedicarboxylic acid, diethyl 2,6-naphthalenedicarboxylate, , 7-naphthalenedicarboxylate, diethyl 2,7-naphthalenedicarboxylate and the like, and the hydrogen atom of the aromatic ring of these compounds may be substituted with an alkyl group or a halogen atom. The aromatic dicarboxylic acid component (D5) can be contained alone or in combination of two or more in the polyether ester.

  The aromatic dicarboxylic acid component substituted with the sulfonate group of (D6) is represented by the formula (III). Specific examples thereof and more preferable specific examples thereof are the same as those of the component (D2) in the polyether ester of the component D.

  The two acid components (D5) and (D6) constituting the polyester of component D are composed of 100 mol% of the total acid components, and (D5) an aromatic dicarboxylic acid component 99.9 having no sulfonate group. ˜50.0 mol% and (D6) A ratio of 0.1 to 50.0 mol% of the aromatic dicarboxylic acid component substituted with the sulfonate group represented by the formula (III) is preferable. When the proportion of the component (D5) is less than 0.1 mol%, the antistatic effect may not be sufficient. On the other hand, if the component (D6) exceeds 50.0 mol%, problems such as difficulty in polymerization reaction and poor transparency of the formed polycarbonate resin composition arise.

  Specific examples of the glycol having 2 to 10 carbon atoms for deriving (D7) include ethylene glycol, 1,4-butanediol, propylene glycol, 1,6-hexanediol, and 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, ethylene glycol, and neopentyl glycol are preferably used from the viewpoint of securing an antistatic effect and transparency, and it is more preferable to use neopentyl glycol and ethylene glycol in combination. A preferred ratio of the neopentyl glycol component and the ethylene glycol component in the polyester of component D is 90 to 10 mol% of neopentyl glycol component and 10 to 90 mol% of ethylene glycol component, more preferably 100 mol% of glycol component. Is 80-20 mol% neopentyl glycol component and 20-80 mol% ethylene glycol component.

  The polyester of component D in the present invention preferably has a reduced viscosity of 0.2 or more measured at 30 ° C. in a mixed solvent of phenol / tetrahydrofuran (weight ratio 60/40). If the reduced viscosity is less than 0.2, 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 upper limit for practical polymerization is about 3.0. It is. The reduced viscosity is more preferably 0.3 or more, and still more preferably 0.35 or more.

  The polyester of the D component of the present invention can be produced by a transesterification reaction like the polyether ester of the D component, and can further contain the antioxidant during the production.

  Furthermore, the polyether ester and polyester, which are the preferred D components, can be used alone or in admixture of two or more. Although the above polyether ester is excellent in antistatic property, it has a slightly inferior heat resistance and transparency. On the other hand, polyester is excellent in heat resistance and transparency but is easily incompatible with polycarbonate resin and has a slightly inferior antistatic ability. However, each drawback can be compensated by the combined use. Therefore, it is possible to select an appropriate D component as appropriate depending on what characteristics are emphasized from these characteristics. In the present invention, a polyester having a sulfonate group is particularly suitable as the component D because it provides a resin composition particularly suitable for applications in which specific gravity is placed on hue and transparency.

<E component: hindered phenolic antioxidant>
In the antistatic polycarbonate resin composition of the present invention, a hindered phenol antioxidant is further used in order to further stabilize the hue during heat treatment of the molded product.

  Examples of such hindered phenol-based antioxidants include α-tocopherol, butylhydroxytoluene, sinapyl alcohol, vitamin E, n-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-dimethylaminomethyl) 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′-me Renbis (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 -(3-tert-butyl-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-butyl) Enol), 2,2-thiodiethylenebis- [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-butyl Phenyl) 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) isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-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 [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane and the like are exemplified. All of these are readily available. Among them, n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl -4-hydroxybenzyl) benzene, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, tetrakis [3- (3,5-di-tert-butyl-4 -Hydroxyphenyl) propionyloxymethyl] methane is preferred, in particular n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate. The said hindered phenolic antioxidant can be used individually or in combination of 2 or more types.

<F component: Phosphite ester antioxidant>
In the antistatic polycarbonate resin composition of the present invention, a phosphite antioxidant is further used in order to further stabilize the hue and molecular weight during molding and heat treatment.

  Examples of such phosphite antioxidants include 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, 2,2-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, Tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butyl) Enyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, distearyl 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, phenylbisphenol A pentaerythritol diphosphite Examples thereof include phosphite, 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- Butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite, 2,2′-methylenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite 2,2′-ethylidenebis (4-methyl-6-tert-butylphenyl) (2-tert-butyl-4-methylphenyl) phosphite.
Among these, tris (2,4-di-tert-butylphenyl) phosphite is particularly preferable. Phosphite antioxidants may be used alone or in combination of two or more.

<G component: UV absorber>
The antistatic polycarbonate resin composition of the present invention preferably further contains an ultraviolet absorber. The ultraviolet absorbent imparts excellent antistatic performance dry heat sustainability and hue thermal stability to the antistatic polycarbonate resin composition of the present invention.

  Examples of the ultraviolet absorber include 2-hydroxy-4-n-dodecyloxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, and bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane. Benzophenone compounds represented by

  Examples of the ultraviolet absorber include 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-amylphenyl) benzotriazole, 2- (2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenylbenzotriazole, 2,2′methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol], condensate with methyl-3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate-polyethylene glycol The benzotriazole type compound represented by can be mentioned.

  Further, examples of the ultraviolet absorber include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4,6-bis (2,4-dimethyl). And hydroxyphenyltriazine compounds such as phenyl) -1,3,5-triazin-2-yl) -5-hexyloxyphenol.

  Further, examples of the ultraviolet absorber include 2,2′-p-phenylenebis (3,1-benzoxazin-4-one) and 2,2′-m-phenylenebis (3,1-benzoxazin-4-one). And cyclic imino ester compounds such as 2,2′-p, p′-diphenylenebis (3,1-benzoxazin-4-one).

  Also, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, tetrakis (2,2,6,6- Tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetra Carboxylate, poly {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethylpiperidyl ) Imino] hexamethylene [(2,2,6,6-tetramethylpiperidyl) imino]}, polymethylpropyl 3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane. It can also include hindered amine light stabilizers represented by, such light stabilizers in combination with the ultraviolet absorber and various antioxidants, exhibit better performance in terms of weather resistance.

  The ultraviolet absorber and the light stabilizer have a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbing monomer and / or the light stable monomer, an alkyl (meth) acrylate, etc. It may be a polymer-type ultraviolet absorber and / or light stabilizer copolymerized with the above monomer. The UV-absorbing monomer and light-stable monomer contain a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a hindered amine skeleton in the ester substituent of (meth) acrylic acid ester. The compound is preferably exemplified.

<About the amount of each component>
Next, the amount of the B component to the G component will be described. The amount of component B is 0.01 to 4 parts by weight, preferably 0.01 to 3 parts by weight, more preferably 0.1 to 2.8 parts by weight, and still more preferably 100 parts by weight of polycarbonate resin of component A. Is in the range of 0.5 to 2.5 parts by weight. If the amount 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 5 parts by weight, the hue and transparency of the molded product deteriorate, which is not preferable.

The amount of component C is in the range of 0.001 to 0.3 parts by weight with respect to 100 parts by weight of the polycarbonate resin. If the amount of component C is less than 0.001 part by weight, the effect of improving the hue at the time of extrusion and molding and the sustainability of the antistatic performance during dry heat treatment (sustainability to dry heat) tends to be insufficient, and 1 part by weight On the other hand, it is not preferable because the hue deterioration and the molecular weight decrease are more likely to occur.

  The amount of component D is 0.01 to 5 parts by weight, preferably 0.1 to 4 parts by weight, and more preferably 0.2 to 3 parts by weight with respect to 100 parts by weight of the polycarbonate resin of component A. If the amount of component D is less than 0.01 parts by weight, sufficient molding heat resistance and antistatic effect cannot be obtained, and if it exceeds 5 parts by weight, the transparency and hue of the molded product are deteriorated.

  Here, as described above, the counter ion of the sulfonate group of component D may be either a metal ion or an organic onium ion such as an organic phosphonium ion. However, in view of transparency, hue, antistatic performance, etc., the total sulfonate group including the B component and the D component is preferably composed of both a phosphonium sulfonate group and a metal sulfonate group. Further, in the ratio of both, the sulfonic acid metal base is preferably 0.02 to 2 mol, more preferably 0.03 to 1 mol, and still more preferably 0.04 to 0.00 mol. 5 moles. Therefore, it is preferable to adjust the ratio of the B component and the D component and the ratio of the phosphonium sulfonate group and the sulfonate metal base in the B component and the D component so as to satisfy such conditions. It is preferable to blend a polyether ester having a base and / or a polyester having a sulfonic acid metal base into the polycarbonate resin so as to satisfy the above ratio.

  The amount of component E is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, still more preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the polycarbonate resin of component A. It is. If the amount is less than 0.01 part by weight, the hue of the resin composition or a melt-molded product obtained from the resin composition and the hue during heat treatment of the molded product are likely to be insufficiently stabilized. Is not preferable because the hue and transparency of the molded product deteriorate.

  The amount of component F is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, still more preferably 0.05 to 0.5 parts by weight, based on 100 parts by weight of the polycarbonate resin of component A. It is. If it is less than 0.01 part by weight, the hue and molecular weight during molding and heat treatment are likely to be insufficiently stabilized, and if it exceeds 2 parts by weight, the resin composition will have an excessive amount of heat and the heat resistance of the resin composition will be reduced. It is not preferable because transparency is also deteriorated. The weight ratio (E / F) between the E component and the F component is preferably 1/9 to 9/1, more preferably 2/8 to 8/2, and still more preferably 7/3 to 3/7.

  The amount of component G is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 1 part by weight, still more preferably 0.05 to 0.6 parts by weight, based on 100 parts by weight of the polycarbonate resin of component A. Part.

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

(I) Phosphorus stabilizer The antistatic polycarbonate resin composition of the present invention is further blended with various phosphorus stabilizers other than the phosphoric acid ester in order to improve the thermal stability during the molding process. Is preferred. Examples of such phosphorus stabilizers include phosphoric acid, phosphorous acid, and tertiary phosphine, and such phosphorus stabilizers can be used alone or in combination of two or more. The phosphorus stabilizer is preferably 0.01 to 0.3 parts by weight based on 100 parts by weight of the component A.

(Ii) Antioxidant In the polycarbonate resin composition of the present invention, an antioxidant other than the hindered phenol antioxidant may be used in order to further stabilize the hue at the time of heat treatment of the molded product. it can.
Such other antioxidants include sulfur-containing stabilizers such as pentaerythritol tetrakis (3-mercaptopropionate), pentaerythritol tetrakis (3-laurylthiopropionate), and glycerol-3-stearylthiopropionate. Agents are exemplified. 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, based on 100 parts by weight of component A.

(Iii) Blueing agent The polycarbonate 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. 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 polycarbonate resin composition of the present invention can obtain 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.

(Iv) Release agent It is preferable to add a release agent to the polycarbonate resin composition of the present invention for the purpose of improving productivity at the time of 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 based on 100 parts by weight of 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.

  The above 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 lard and vegetable oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are 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, more preferably 4 to 20 and even more preferably 4 to 12 from the viewpoint of thermal stability. The acid value can be substantially zero. 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. The iodine value can be substantially zero. 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, still more preferably 0.05 to 0.5 parts by weight based on 100 parts by weight of the component A. It is. In such a range, the polycarbonate resin composition has good release properties and release properties. In particular, such an amount of fatty acid ester provides a polycarbonate resin composition having good mold release and roll release properties without impairing good hue and transparency.

(V) Dye / pigment The polycarbonate resin composition of the present invention can further contain various dyes / pigments and can provide a molded product exhibiting various design properties. Since the polycarbonate resin composition of the present invention is excellent in transparency, it is extremely suitable for use in transmitting light. Therefore, for example, by adding a fluorescent brightening agent, the polycarbonate resin composition of the present invention is given a higher light transmittance and natural transparency, and a fluorescent brightening agent or other fluorescent dye that emits light is added. By blending, it is possible to impart a better design effect utilizing the luminescent color. Further, a polycarbonate resin composition which is finely colored with a very small amount of dye and pigment and has high transparency 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 are preferable because they have good heat resistance and little deterioration during molding of the polycarbonate resin.

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, more preferably 0.00005 to 0.5 part by weight, based on 100 parts by weight of the component A.

(Vi) Other Heat Stabilizers The polycarbonate resin composition of the present invention may contain other heat stabilizers other than the phosphorus stabilizers and hindered phenol antioxidants. Such other heat stabilizers are preferably used in combination with any of these stabilizers and antioxidants, and particularly preferably used in combination with both. 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, such a premixed stabilizer can also 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, based on 100 parts by weight of the component A.

(Vii) Compound having heat ray absorption ability The polycarbonate resin composition of the present invention may contain a compound having heat ray absorption ability. A polycarbonate resin composition in which such a compound is blended can suppress an increase in temperature in the room. Such a polycarbonate resin composition is particularly suitable for use in resin window glass for vehicles 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, based on 100 parts by weight of component A, 0.001 to 0 0.07 part by weight is more preferable. 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.

(Viii) Light diffusing agent Since the polycarbonate resin composition of the present invention is excellent in transparency and hue, a resin composition having a good hue and light diffusibility is provided by further blending a light diffusing agent. Can do. Examples of such a light diffusing agent include polymer fine particles (preferably acrylic crosslinked particles and silicone crosslinked particles having a particle diameter of several μm), low refractive index inorganic fine particles, and composites thereof. Examples of the shape include a spherical shape (including a deformed shape that does not need to be a perfect sphere), a disc shape, a columnar shape (including a cube), and an indefinite shape. The light diffusing agent is preferred because it is generally spherical and easily available, and the more uniform the particle size is. The amount of the light diffusing agent is preferably 0.005 to 20 parts by weight, more preferably 0.01 to 10 parts by weight, still more preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the polycarbonate resin of component A. is there. Two or more light diffusing agents can be used in combination.

(Ix) White pigment for high light reflection Since the polycarbonate resin composition of the present invention is excellent in transparency and hue, a resin having a good hue and light reflection can be obtained by further blending a white pigment for high light reflection. A composition can be provided. As the white pigment, a titanium dioxide (particularly titanium dioxide treated with an organic surface treatment agent such as silicone) pigment is particularly preferable. The amount of the white pigment for high light reflection is preferably 1 to 25 parts by weight, more preferably 2 to 20% by weight based on 100 parts by weight of the polycarbonate resin of component A. Two or more kinds of white pigments for high light reflection can be used in combination.

(X) Flame Retardant The polycarbonate resin composition of the present invention may contain various compounds known as flame retardants for polycarbonate resins.
Examples of such flame retardants include (i) organometallic salt flame retardants other than the above component B (for example, alkali (earth) organic sulfonate metal salts, borate metal salt flame retardants, metal stannate flame retardants, etc.) ), (Ii) silicone flame retardants comprising silicone compounds, and (iii) halogen flame retardants (eg brominated epoxy resins, brominated polystyrenes, brominated polycarbonates (including oligomers), brominated polyacrylates, and chlorines) And the like).

(Xi) Organic metal salt-based flame retardant An organic metal salt-based flame retardant is advantageous in that heat resistance is substantially maintained and antistatic properties can be imparted. The organometallic salt flame retardant most advantageously used in the present invention is a fluorine-containing organometallic salt compound. The fluorine-containing organometallic salt compound of the present invention refers to a metal salt compound comprising an anion component composed of an organic acid having a fluorine-substituted hydrocarbon group and a cation component composed of a metal ion. More preferred specific examples include metal salts of fluorine-substituted organic sulfonic acids, metal salts of fluorine-substituted organic sulfates, and metal salts of fluorine-substituted organic phosphates. Fluorine-containing organometallic salt compounds can be used alone or in combination of two or more. Among them, a metal salt of a fluorine-substituted organic sulfonic acid is preferable, and a metal salt of a sulfonic acid having a perfluoroalkyl group is particularly preferable. Here, the carbon number of the perfluoroalkyl group is preferably in the range of 1-18, more preferably in the range of 1-10, and still more preferably in the range of 1-8.

  The metal constituting the metal ion of the organometallic salt flame retardant is an alkali metal or an alkaline earth metal. Examples of the alkali metal include lithium, sodium, potassium, rubidium and cesium. Examples of the alkaline earth metal include beryllium. , Magnesium, calcium, strontium and barium. More preferred is an alkali metal. Accordingly, a preferred organometallic salt flame retardant is an alkali metal perfluoroalkyl sulfonate. Among such alkali metals, rubidium and cesium are suitable when transparency requirements are higher, but these are not general-purpose and difficult to purify, resulting in disadvantages in terms of cost. is there. On the other hand, although lithium and sodium are advantageous in terms of cost and flame retardancy, they may be disadvantageous in terms of transparency. In consideration of these, the alkali metal in the perfluoroalkylsulfonic acid alkali metal salt can be properly used, but perfluoroalkylsulfonic acid potassium salt having an excellent balance of properties is most suitable in any respect. Such potassium salts and alkali metal salts of perfluoroalkylsulfonic acid composed of other alkali metals can be used in combination.

  Such alkali metal perfluoroalkylsulfonates include potassium trifluoromethanesulfonate, potassium perfluorobutanesulfonate, potassium perfluorohexanesulfonate, potassium perfluorooctanesulfonate, sodium pentafluoroethanesulfonate, perfluorobutanesulfone. Acid sodium, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, cesium perfluorobutane sulfonate, cesium perfluorooctane sulfonate, Cesium perfluorohexane sulfonate, rubidium perfluorobutane sulfonate, and perful B hexane sulfonate rubidium, and these may be used in combination of at least one or two. Of these, potassium perfluorobutanesulfonate is particularly preferred.

  The fluorine-containing organometallic salt preferably has a fluoride ion content as measured by ion chromatography of 50 ppm or less, more preferably 20 ppm or less, and even more preferably 10 ppm or less. The lower the fluoride ion content, the better the flame retardancy and light resistance. The lower limit of the fluoride ion content can be substantially zero, but is practically preferably about 0.2 ppm in view of the balance between the refining man-hour and the effect. Such alkali metal salt of perfluoroalkylsulfonic acid having a fluoride ion content is purified, for example, as follows. The perfluoroalkylsulfonic acid alkali metal salt is dissolved in 2 to 10 times by weight of the metal salt in ion-exchanged water in the range of 40 to 90 ° C. (more preferably 60 to 85 ° C.). The alkali metal salt of perfluoroalkylsulfonic acid is a method of neutralizing perfluoroalkylsulfonic acid with an alkali metal carbonate or hydroxide, or perfluoroalkylsulfonyl fluoride with an alkali metal carbonate or hydroxide. It is produced by a neutralizing method (more preferably by the latter method). The ion-exchanged water is particularly preferably water having an electric resistance value of 18 MΩ · cm or more. The solution in which the metal salt is dissolved is stirred at the above temperature for 0.1 to 3 hours, more preferably 0.5 to 2.5 hours. Thereafter, the liquid is cooled to 0 to 40 ° C, more preferably in the range of 10 to 35 ° C. Crystals precipitate upon cooling. The precipitated crystals are removed by filtration. This produces a suitable purified perfluoroalkylsulfonic acid alkali metal salt.

  The compounding amount of the fluorine-containing organometallic salt compound is preferably 0.005 to 0.6 parts by weight, more preferably 0.005 to 0.2 parts by weight, still more preferably 0.00 based on 100 parts by weight of the component A. 008 to 0.13 parts by weight. The more preferable range is, the effects (for example, flame retardancy and antistatic properties) expected by the blending of the fluorine-containing organic metal salt are exhibited, and the adverse effect on the light resistance of the polycarbonate resin composition is reduced.

(X-ii) Silicone Flame Retardant The silicone compound used as the silicone flame retardant of the present invention improves flame retardancy by a chemical reaction during combustion. As the compound, various compounds conventionally proposed as flame retardants for aromatic polycarbonate resins can be used. The silicone compound binds itself during combustion or binds to a component derived from the resin to form a structure, or gives a flame retardant effect to the polycarbonate resin by a reduction reaction during the structure formation. It is considered. Therefore, it is preferable that a group having high activity in such a reaction is contained, and more specifically, a predetermined amount of at least one group selected from an alkoxy group and a hydrogen (ie, Si—H group) is contained. preferable. As a content rate of this group (alkoxy group, Si-H group), the range of 0.1-1.2 mol / 100g is preferable, the range of 0.12-1 mol / 100g is more preferable, 0.15-0. The range of 6 mol / 100 g is more preferable. Such a ratio can be determined by measuring the amount of hydrogen or alcohol generated per unit weight of the silicone compound by the alkali decomposition method. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a methoxy group.

Generally, the structure of a silicone compound is constituted by arbitrarily combining the following four types of siloxane units. That is,
M units: (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH) SiO _1/2 Monofunctional siloxane units such as (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 , (CH ₃ ) (C ₆ H ₅ ) (CH ₂ ═CH) SiO _1/2 ,
D unit: (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ ═CH) SiO, (C ₆ H ₅ ) ₂ SiO Bifunctional siloxane units such as
T unit: (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ ═CH) SiO _3/2 , (C ₆ H ₅ ) SiO _3/2 etc. A trifunctional siloxane unit of
Q unit: a tetrafunctional siloxane unit represented by SiO ₂ .

Specifically, the structure of the silicone compound used in the silicone-based flame retardant is represented by the following formulas: D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _{p , M m D n Q q,} M m T p Q q, M m D n T p Q q, D n T p, D n Q q, include _{D n} T p _{Q q.} Among these, preferable structures of the silicone compound are M _m D _n , M _m T _p , M _m D _n T _p , and M _m D _n Q _q , and more preferable structures are M _m D _n or M _m D _n. T _p .

Here, the coefficients m, n, p, and q in the above formulas are integers of 1 or more representing the degree of polymerization of each siloxane unit, and the sum of the coefficients in each formula is the average degree of polymerization of the silicone compound. . This average degree of polymerization is preferably in the range of 3 to 150, more preferably in the range of 3 to 80, still more preferably in the range of 3 to 60, and particularly preferably in the range of 4 to 40. The better the range, the better the flame retardancy. Further, as described later, a silicone compound containing a predetermined amount of an aromatic group is excellent in transparency and hue.
When any of m, n, p, and q is a numerical value of 2 or more, the siloxane unit with the coefficient can be two or more types of siloxane units having different hydrogen atoms or organic residues to be bonded. .

  The silicone compound may be linear or have a branched structure. The organic residue bonded to the silicon atom is preferably an organic residue having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms. Specific examples of such an organic residue include alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, and a decyl group, a cycloalkyl group such as a cyclohexyl group, an aryl group such as a phenyl group, And aralkyl groups such as tolyl groups. More preferably, they are a C1-C8 alkyl group, an alkenyl group, or an aryl group. As the alkyl group, an alkyl group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable.

  Further, the silicone compound used as the silicone flame retardant preferably contains an aryl group. More preferably, the ratio (aromatic group amount) of the aromatic group represented by the following general formula (V) is 10 to 70% by weight (more preferably 15 to 60% by weight).

（式（Ｖ）中、Ｘはそれぞれ独立にＯＨ基、炭素数１〜２０の一価の有機残基を示す。ｎは０〜５の整数を表わす。さらに式（Ｖ）中においてｎが２以上の場合はそれぞれ互いに異なる種類のＸを取ることができる。）

(In formula (V), each X independently represents an OH group or a monovalent organic residue having 1 to 20 carbon atoms. N represents an integer of 0 to 5. Further, in formula (V), n is 2). In these cases, different types of X can be taken.)

The silicone compound used as the silicone-based flame retardant may contain a reactive group in addition to the Si-H group and the alkoxy group. Examples of the reactive group include an amino group, a carboxyl group, an epoxy group, and a vinyl group. Examples thereof include a group, a mercapto group, and a methacryloxy group.
Preferred examples of the silicone compound having a Si—H group include silicone compounds containing at least one of structural units represented by the following general formulas (VI) and (VII).

（式（ＶＩ）および式（ＶＩＩ）中、Ｚ^１〜Ｚ^３はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基、または下記一般式（ＶＩＩＩ）で示される化合物を示す。α^１〜α^３はそれぞれ独立に０または１を表わす。ｍ１は０もしくは１以上の整数を表わす。さらに式（ＶＩ）中においてｍ１が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (VI) and formula (VII), Z ^{1 to} Z ³ each independently represent a hydrogen atom, a monovalent organic residue having 1 to 20 carbon atoms, or a compound represented by the following general formula (VIII). Α ^{1 to} α ³ each independently represents 0 or 1. m1 represents 0 or an integer of 1 or more, and the repeating unit in the case where m1 is 2 or more in formula (VI) is a plurality of repeating units different from each other. Can take units.)

（式（ＶＩＩＩ）中、Ｚ^４〜Ｚ^８はそれぞれ独立に水素原子、炭素数１〜２０の一価の有機残基を示す。α^４〜α^８はそれぞれ独立に０または１を表わす。ｍ２は０もしくは１以上の整数を表わす。さらに式（ＶＩＩＩ）中においてｍ２が２以上の場合の繰返し単位はそれぞれ互いに異なる複数の繰返し単位を取ることができる。）

(In formula (VIII), Z ^{4 to} Z ⁸ each independently represents a hydrogen atom or a monovalent organic residue having 1 to 20 carbon atoms. Α ^{4 to} α ⁸ each independently represents 0 or 1. m 2 Represents 0 or an integer greater than or equal to 1. Furthermore, in the formula (VIII), when m2 is 2 or more, the repeating unit can take a plurality of different repeating units.

  Examples of the silicone compound having an alkoxy group in the silicone compound used for the silicone-based flame retardant include at least one compound selected from compounds represented by the general formula (IX) and the general formula (X).

（式（ＩＸ）中、β^１はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^１、γ^２、γ^３、γ^４、γ^５、およびγ^６は炭素数１〜６のアルキル基およびシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキル基である。δ^１、δ^２、およびδ^３は炭素数１〜４のアルコキシ基を示す。）

(In Formula (IX), β ¹ represents a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group or aralkyl group having 6 to 12 carbon atoms. Γ ¹ , γ ² , γ ³ , γ ⁴ , γ ⁵ , and γ ⁶ represent an alkyl group and a cycloalkyl group having 1 to ⁶ carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms, and at least one group is aryl. And δ ¹ , δ ² , and δ ³ are each an alkoxy group having 1 to 4 carbon atoms.)

（式（Ｘ）中、β^２およびβ^３はビニル基、炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示す。γ^７、γ^８、γ^９、γ^１０、γ^１１、γ^１２、γ^１３およびγ^１４は炭素数１〜６のアルキル基、炭素数３〜６のシクロアルキル基、並びに炭素数６〜１２のアリール基およびアラルキル基を示し、少なくとも１つの基がアリール基またはアラルキルである。δ^４、δ^５、δ^６、およびδ^７は炭素数１〜４のアルコキシ基を示す。）

(In formula (X), β ² and β ³ represent a vinyl group, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and an aryl group and an aralkyl group having 6 to 12 carbon atoms. γ ⁷ , γ ⁸ , γ ⁹ , γ ¹⁰ , γ ¹¹ , γ ¹² , γ ^13, and γ ¹⁴ are each an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, and 6 to 12 carbon atoms. An aryl group and an aralkyl group, and at least one group is an aryl group or an aralkyl group, and δ ⁴ , δ ⁵ , δ ⁶ , and δ ⁷ represent an alkoxy group having 1 to 4 carbon atoms.

(X-iii) Halogen Flame Retardant As the halogen flame retardant of the present invention, brominated polycarbonate (including oligomer) is particularly suitable. Brominated polycarbonate has excellent heat resistance and can greatly improve flame retardancy. In the brominated polycarbonate used in the present invention, the structural unit represented by the following general formula (XI) is at least 60 mol%, preferably at least 80 mol%, particularly preferably substantially the following general formula. A brominated polycarbonate compound composed of a structural unit represented by (XI).

（式（ＸＩ）中、Ｘは臭素原子、Ｒは炭素数１〜４のアルキレン基、炭素数１〜４のアルキリデン基または−ＳＯ_２−である。）
また、かかる式（ＸＩ）において、好適にはＲはメチレン基、エチレン基、イソプロピリデン基、−ＳＯ_２−、特に好ましくはイソプロピリデン基を示す。

(In Formula (XI), X is a bromine atom, R is an alkylene group having 1 to 4 carbon atoms, an alkylidene group having 1 to 4 carbon atoms, or —SO ₂ —).
In the formula (XI), R preferably represents a methylene group, an ethylene group, an isopropylidene group, —SO ₂ —, and particularly preferably an isopropylidene group.

  The brominated polycarbonate has a small number of remaining chloroformate groups and preferably has a terminal chlorine content of 0.3 ppm or less, more preferably 0.2 ppm or less. The amount of terminal chlorine is determined by dissolving a sample in methylene chloride, adding 4- (p-nitrobenzyl) pyridine and allowing it to react with terminal chlorine (terminal chloroformate). -3200). When the amount of terminal chlorine is 0.3 ppm or less, the thermal stability of the polycarbonate resin composition becomes better, and molding at a higher temperature becomes possible. As a result, a polycarbonate resin composition that is superior in molding processability is provided.

The brominated polycarbonate preferably has a small number of remaining hydroxyl terminals. More specifically, the amount of terminal hydroxyl groups is preferably 0.0005 mol or less, more preferably 0.0003 mol or less with respect to 1 mol of the structural unit of brominated polycarbonate. The amount of terminal hydroxyl groups can be determined by dissolving a sample in deuterated chloroform and measuring it by ¹ H-NMR method. Such a terminal hydroxyl group amount is preferable because the thermal stability of the polycarbonate resin composition is further improved.

  The specific viscosity of the brominated polycarbonate is preferably in the range of 0.015 to 0.1, more preferably in the range of 0.015 to 0.08. The specific viscosity of the brominated polycarbonate is calculated according to the above-described specific viscosity calculation formula used for calculating the viscosity average molecular weight of the polycarbonate resin which is the component A of the present invention.

(Xi) Anti-dripping agent The polycarbonate resin composition of the present invention may contain an anti-dripping agent. By using such an anti-dripping agent in combination with the above flame retardant, better flame retardancy can be obtained. Examples of the anti-dripping agent include a fluorinated polymer having a fibril-forming ability. Examples of such a polymer include polytetrafluoroethylene, tetrafluoroethylene copolymers (for example, tetrafluoroethylene / hexafluoropropylene copolymers). , Etc.), partially fluorinated polymers as shown in U.S. Pat. No. 4,379,910, polycarbonate resins produced from fluorinated diphenols, etc., preferably polytetrafluoroethylene (hereinafter referred to as PTFE). Is).

Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability has a very high molecular weight, and exhibits a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in this publication in the range of 10 ⁷ to 10 ¹³ poise, preferably in the range of 10 ⁸ to 10 ¹² poise.

  Such PTFE can be used in solid form or in the form of an aqueous dispersion. In addition, PTFE having such fibril-forming ability can improve the dispersibility in the resin, and it is also possible to use a PTFE mixture in a mixed form with other resins in order to obtain better flame retardancy and mechanical properties. is there. Further, as disclosed in JP-A-6-145520, those having a structure having such a fibrillated PTFE as a core and a low molecular weight polytetrafluoroethylene as a shell are also preferably used.

  Examples of commercially available fibrillated PTFE include Teflon (registered trademark) 6J from Mitsui DuPont Fluorochemical Co., Ltd., Polyflon MPA FA500, F-201L from Daikin Chemical Industries, Ltd., and the like. Commercially available aqueous dispersions of fibrillated PTFE include: Fluon AD-1, AD-936 manufactured by Asahi IC Fluoropolymers, Fluon D-1, D-2 manufactured by Daikin Industries, Ltd., Mitsui A representative example is Teflon (registered trademark) 30J manufactured by DuPont Fluorochemical Co., Ltd.

  As a mixed form of fibrillated PTFE, (1) a method in which an aqueous dispersion of fibrillated PTFE and an aqueous dispersion or solution of an organic polymer are mixed and co-precipitated to obtain a co-agglomerated mixture (JP-A-60-258263). (2) A method of mixing an aqueous dispersion of fibrillated PTFE and dried organic polymer particles (Japanese Patent Laid-Open No. 4-272957). Described method), (3) A method in which an aqueous dispersion of fibrillated PTFE and an organic polymer particle solution are uniformly mixed, and the respective media are simultaneously removed from the mixture (Japanese Patent Laid-Open Nos. 06-220210, (Method described in Japanese Patent Application Laid-Open No. 08-188653), (4) A method of polymerizing monomers forming an organic polymer in an aqueous dispersion of fibrillated PTFE (Method described in JP-A-9-95583), and (5) an aqueous dispersion of PTFE and an organic polymer dispersion are uniformly mixed, and then a vinyl monomer is further polymerized in the mixed dispersion. Thereafter, those obtained by a method for obtaining a mixture (a method described in JP-A No. 11-29679) can be used. Examples of commercially available fibrillated PTFE in a mixed form include “Metablene A3800” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. and “BLENDEX B449” (trade name) manufactured by GE Specialty Chemicals.

  In order to effectively utilize the good hue and transparency of the polycarbonate resin composition of the present invention, the fibrillated PTFE is preferably finely dispersed as much as possible. As a means of achieving such fine dispersion, the above mixed form of fibrillated PTFE is advantageous. A method of directly supplying an aqueous dispersion in a melt kneader is also advantageous for fine dispersion. However, in the case of the aqueous dispersion form, consideration is required in that the hue is slightly deteriorated. The proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, in 100% by weight of the mixture. When the ratio of fibrillated PTFE is in such a range, good dispersibility of fibrillated PTFE can be achieved.

  The content of the fibrillated PTFE in the polycarbonate resin composition is preferably 0.001 to 1 part by weight, more preferably 0.1 to 0.7 part by weight based on 100 parts by weight of the component A.

(Xii) Acidity adjusting agent The polycarbonate resin composition of the present invention can be blended with an acidity adjusting agent comprising a low-molecular or polymeric carboxylic acid compound or carboxylic anhydride compound. The B component and the D component, particularly the B component, are decomposed not a little by a thermal decomposition reaction or an oxidation reaction in a temperature region where the polycarbonate resin is usually melt processed. Furthermore, among the by-products generated by the decomposition reaction, there are colored substances and substances that cause a side reaction with the polycarbonate resin. Therefore, when the molded product is heated and melted or a thermal history occurs in the molded product, discoloration of the molded product occurs. Deterioration of hue or molecular weight may occur due to. Hue deterioration and molecular weight reduction are more likely to occur at higher temperatures. However, it is considered that decomposition of these antistatic agents easily occurs because a nucleophilic reaction to a sulfonic acid group is likely to occur particularly in a basic atmosphere. In order to suppress such decomposition, a method of adjusting the acidity of the resin by adding an acidity adjusting agent to the resin composition as described above is preferable. The acidity adjusting agent is a compound having pk (logarithm of the reciprocal of the acid dissociation constant) in a weakly acidic region, and a preferable range of pk is 4 to 7, particularly preferably 4.5 to 5.5. Low molecular acidity modifiers include aliphatic monocarboxylic acids such as acetic acid, propionic acid, palmitic acid, stearic acid, and arachidic acid, aliphatic dicarboxylic acids such as oxalic acid, malonic acid, and succinic acid, acetic anhydride And an acid anhydride of an aliphatic carboxylic acid such as succinic anhydride, an aromatic monocarboxylic acid such as benzoic acid, and an aromatic dicarboxylic acid such as isophthalic acid. Examples of the polymeric acidity adjusting agent include a styrene-acrylic acid copolymer and a styrene-maleic anhydride copolymer. Such carboxylic acid compounds and carboxylic acid anhydride compounds not only act to suppress the nucleophilic decomposition reaction, but also form and stabilize an ester-like structure with a benzenesulfonic acid derivative that is considered to be a decomposition byproduct of the antistatic agent. It is considered that there is an effect of suppressing the decomposition of the polycarbonate resin and the antistatic agent by further side reaction. The amount of the acidity adjusting agent is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.5 part by weight, per 100 parts by weight of component A. By blending the acidity adjusting agent, the antistatic polycarbonate resin composition of the present invention can exhibit the desired good characteristics even under higher temperature molding conditions.

(Xiii) Reinforcing filler Various known fillers can be blended in the polycarbonate resin composition of the present invention as a reinforcing filler. Since the polycarbonate resin composition of the present invention has a good hue and transparency, a polycarbonate resin composition having a good hue can be obtained by blending an appropriate reinforcing filler. As such a reinforcing filler, a silicate mineral filler or glass filler with high whiteness is preferable. Examples of such silicate mineral fillers include talc, mascobite mica, synthetic fluorine mica, smectite, and wollastonite. Examples of the glass filler include glass fiber, glass flake, and glass milled fiber. As the silicate mineral filler and the glass filler, fillers whose surfaces are coated with metal oxides such as titanium oxide, zinc oxide, cerium oxide, and silicon oxide can also be used.

The reinforcing filler may be surface-treated with various surface treatment agents in advance. Such surface treatment agents include silane coupling agents (including alkylalkoxysilanes and polyorganohydrogensiloxanes), higher fatty acid esters, acid compounds (for example, phosphorous acid, phosphoric acid, carboxylic acid, and carboxylic acid anhydrides). Etc.) and various surface treatment agents such as wax. Furthermore, it may be granulated with a sizing agent such as various resins, higher fatty acid esters, and waxes.
The reinforcing filler can be blended up to 100 parts by weight based on 100 parts by weight of component A. The upper limit is preferably 25 parts by weight, more preferably 20 parts by weight.

(Xiv) Other components other than the above In addition to the B component to the G component and each of the above components, the polycarbonate resin composition of the present invention and the molded product thereof may have other thermoplastic properties as long as the object of the present invention is not impaired. Resin, inorganic phosphor (for example, phosphor having aluminate as mother crystal), flow modifier, crystal nucleating agent, inorganic and organic antibacterial agent, photocatalytic antifouling agent (for example, fine titanium oxide, fine zinc oxide) ), And various known resin additives such as a photochromic agent may be contained.

  Examples of other thermoplastic resins include polyester resins such as polyethylene terephthalate and polybutylene terephthalate (excluding component D), polyamide resins, polyimide resins, polyetherimide resins, polyurethane resins, silicone resins, polyphenylene ether resins, polyphenylene sulfide resins. , Polyolefin resin such as polysulfone resin, polyethylene, polypropylene, polystyrene resin, acrylonitrile / styrene copolymer (AS resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), polymethacrylate resin, phenol resin, epoxy resin, etc. Resin. Examples of the elastomer include isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and MBS (methyl methacrylate / styrene / butadiene, which is a core-shell type elastomer. ) Rubber and MAS (methyl methacrylate / acrylonitrile / styrene) rubber.

<About the manufacturing method of a resin composition>
In producing the polycarbonate 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 polycarbonate resin in the molded product, the resin composition of the present invention is obtained by melt-kneading the components A to G and other components. Preferably it is manufactured.

  Specific examples of the melt kneading method include a Banbury mixer, a kneading roll, and an extruder. Among them, 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, whereas 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.

  Furthermore, the method of supplying the antistatic agent to the extruder is not particularly limited, but the antistatic agent used in the present invention may be a relatively viscous liquid. In such a case, the following method is used. Is also preferable. (I) A method in which the antistatic agent is heated to reduce the viscosity, and is accurately fed into the extruder using a liquid injection device. (Ii) A method in which the antistatic agent and the polycarbonate 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 of pre-melting and kneading an antistatic agent and a polycarbonate resin into a master pellet.

  One of the methods (ii) is a method in which all necessary raw materials are premixed and supplied to an extruder. In another method, a master agent containing a high concentration of an antistatic agent is prepared, and the master agent is independently or further premixed with the remaining polycarbonate 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. Is preferred. Still another premixing method is, for example, a method in which a polycarbonate resin and an antistatic agent are uniformly dispersed in a solvent and then the solvent is removed.

  The resin extruded from the twin-screw extruder is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be 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.

  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. 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. 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 polycarbonate 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 polycarbonate resin composition of the present invention can also be used in the form of various shaped extrusions, 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. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. 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 the antistatic polycarbonate resin composition that retains the transparency, heat resistance, and mechanical strength of the polycarbonate resin. That is, according to the present invention, 0.01 to 4 parts by weight of the B component, 0.001 to 1 part by weight of the C component, more preferably 0.01 to 5 parts by weight of the D component, and 100 parts by weight of the A component. More preferably, an antistatic polycarbonate resin composition comprising 0.01 to 2 parts by weight of the E component, 0.01 to 2 parts by weight of the F component, and 0.01 to 2 parts by weight of the G component is melt-molded. Goods are provided. According to the present invention, 0.01 to 4 parts by weight of B component, 0.001 to 1 part by weight of C component, 0.01 to 5 parts by weight of D component, and 0.01 to 2 part of E component with respect to 100 parts by weight of A component. Part by weight, 0.01 to 2 parts by weight of F component, 0.01 to 2 parts by weight of G component, and 0.05 to 3.0 ppm (weight ratio) of the antistatic polycarbonate resin composition are blended. A molded product remarkably excellent in hue obtained by melt molding the antistatic polycarbonate resin composition is provided.

  As described above, the antistatic polycarbonate resin composition of the present invention is excellent in hue and transparency, and as a result, it is possible to obtain a molded article having extremely good hue and transparency. More specifically, in a 2 mm-thick smooth flat plate having an arithmetic average roughness (Ra) of 0.03 μm or less, the haze measured by JIS K7105 is 0.1 to 1% (more preferably, 0.1%). 1 to 0.5%) is provided. In addition, a smooth flat plate having a thickness of 2 mm having an arithmetic average roughness (Ra) of 0.03 μm or less was conditioned for 1 week in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and a temperature of 23 ° C. was measured using a static onemeter. The half-life measured under the conditions of a relative humidity of 50%, an applied voltage of 10 kV, and an electrode-sample distance of 20 mm is 200 seconds or less (preferably 180 seconds or less, more preferably 150 or less). 11. An antistatic polycarbonate resin composition according to any one of 11 is provided. More preferably, a YI value calculated by measuring a molded plate having a thickness of 2 mm molded from the resin composition at a cylinder temperature of 310 ° C. and a mold temperature of 80 ° C. based on ASTM E1925 is 0-2. An antistatic polycarbonate resin composition that further satisfies the requirement is provided.

  A polycarbonate resin composition capable of providing a molded product having such haze value, withstand voltage half-life and YI value has very good transparency, antistatic property and hue, and is particularly transparent for headlamp lenses and other automobiles. Suitable for members. Therefore, the molded product according to the present invention has not only excellent mechanical properties such as impact resistance, but also excellent quality in terms of its texture.

  As the molded article of the present invention, various transparent members for vehicles (head lamp lens, blinker lamp lens, tail lamp lens, resin window glass, meter cover, etc.), transparent members for gaming machines (game machines (pachinko machines, game machines, etc.)) Internal decorative parts, electronic circuit board covers and bases thereof, transparent sheet-like members (including film members, for example, resin window glass (especially for double sash resin window glass), solar cell covers, display devices Lenses, outdoor mirrors, meter covers, vending machine covers, flat display device covers, touch panels, etc.), and illumination lamp covers.

  Furthermore, various surface treatments can be performed on the molded article made of the antistatic polycarbonate 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 aromatic polycarbonate resins 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.

  The antistatic polycarbonate resin composition of the present invention is excellent in antistatic performance, dry heat durability, hue, molding heat resistance, transparency, and impact resistance, so that it is a building, building material, agricultural material, marine material. It is widely useful in various fields such as vehicles, electrical / electronic equipment, machinery, and the like. Among them, transparent members for vehicles such as automobile headlamp lenses, transparent members for electronic circuit board covers such as decoration members and board covers for gaming machines (pachinko machines, game machines, etc.), transparent sheets such as building materials, In addition, the present invention provides an extremely useful molded product for the transparent film member, and the industrial effect of 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 (II) Antistatic property: smooth flat test piece 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 Was stored in an environment at a temperature of 23 ° C. and a relative humidity of 50% for one week, and the state was adjusted. Then, the charged half-life of the test piece was measured with a static Honest Meter (H-0110 manufactured by Shido Electric Static Co., Ltd.). S ₁ (second) was obtained. This measurement was performed under the conditions of a temperature of 23 ° C., a relative humidity of 50%, an applied voltage of 10 kV, and an electrode-sample distance of 20 mm. The smaller the value of the charged voltage half-life, the better the antistatic performance.
(I-II) Hue (YI value): A smooth flat test piece 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 was obtained from Nippon Denshoku Corporation ) Calculated by using the following formula based on ASTM-E1925 from X, Y and Z values measured for transmitted light using a color difference meter Z-1001DP type. It shows that the yellowness of a shaping | molding board is so strong that YI value is large.
YI = [100 (1.28X−1.06Z)] / Y
(I-III) Molding heat resistance (ΔYI value): difference between the hue of the test piece obtained by continuous molding and the hue of the test piece obtained by molding after 5 minutes of resin stay in the molding machine cylinder (ΔYI) Value). A smaller ΔYI value indicates better molding heat resistance. The hue of the test piece obtained by stay molding was evaluated using the same method as in (I-II) above.
ΔYI = YI (Still Molded Product) -YI (Continuous Molded Product)
(I-IV) Transparency (haze): length of 50 mm × width of 50 mm × thickness of 2.0 mm, and surface average arithmetic roughness (Ra) of 0.03 μm or less. The color was measured with NDH-300A manufactured by Color Co., Ltd. The larger the haze value, the greater the light diffusion and the lower the transparency.
(IV) Impact resistance (Izod impact strength with notch): A test was performed using a 3.2 mm-thick specimen prepared according to ASTM standard D-256 and according to the standard.
(I-VI) Dry heat durability (charged voltage half-life after dry heat treatment): The test piece after the measurement of (I-I) above is stored in a gear oven at a temperature setting of 120 ° C. for 200 hours, and taken out after storage. The test piece was stored for one week in an environment of a temperature of 23 ° C. and a relative humidity of 50%, and the state was adjusted. Then, the charged half-life was measured in the same manner as in the above (II), and S ₂ (second )

(II) Production of resin molded product (II-I) Preparation of polyetherester (D-1 component) 150.8 parts 2,6-naphthalenedicarboxylic acid dimethyl ester (D1 component), 24.9 parts 5- Sodium dimethyl sulfosulfophthalate (D2 component), 47.9 parts ethylene glycol (D3-1 component), 74.6 parts 1,6-hexanediol (D3-2 component), 89.8 parts polyethylene glycol ( Number average molecular weight 2000; D4 component), and 0.14 parts of tetrabutyl titanate were placed in a reactor equipped with a rectification column and a stirrer, and the inside of the vessel was purged with nitrogen. Warm up. While distilling off the methanol produced by the reaction, the temperature was gradually raised from 200 ° C. to 230 ° C. in 6 hours to complete the reaction. Thereafter, the reaction product was transferred to a reactor having a vacuum distillation system equipped with a stirrer, and while stirring at a temperature of 230 ° C., 6.7 × 10 ² Pa after 60 minutes and 1.3 × 10 after 100 minutes. ^{After 2} Pa and 120 minutes, the inside of the system was gradually reduced in pressure to 0.67 × 10 ² Pa, and a polyether ester copolymer was obtained by carrying out a polymerization reaction while distilling off the reaction distillate. The reduced viscosity of the obtained polyetherester copolymer was 1.35 (in a mixed solvent of phenol / tetrachloroethane (weight ratio 40/60), the concentration was 1.2 (g / dl) at 30 ° C. Measured value). Moreover, the ratio of D1 component and D2 component is 85:15 (molar ratio), and the ratio of D3-1 component and D3-2 component is 19:81 (mol) in the obtained polyetherester copolymer. The content of the D4 component was 26% by weight.

(II-II) Manufacture of pellets Low molecular weight sulfonate, phosphate ester, polyether ester, polyester, and other additives are added to 100 parts of polycarbonate resin powder produced by interfacial condensation polymerization from bisphenol A and phosgene. In addition, 0.0001 part of a blueing agent (manufactured by Bayer: Macrolex Violet B) is blended in the blending amounts shown in Tables 1 to 3, and mixed in a blender, and then melt-kneaded using a vent type twin screw extruder. And pellets were obtained. An antistatic agent that is a viscous liquid at room temperature was prepared by using a supermixer with a premix of polycarbonate resin powder having a proportion of 10% by weight. Further, other stabilizers were preliminarily prepared with a polycarbonate resin powder in advance with a concentration of 10 to 100 times as much as the blending amount, and then the whole was mixed by a blender. The vent type twin-screw extruder used was TEX30XSST (completely meshed, rotating in the same direction, double thread screw) manufactured by Nippon Steel Works. The kneading zone was of one type before the vent opening. The extrusion conditions were a discharge rate of 25 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 260 ° C. from the first supply port to the die part.

(II-III) Preparation of test piece After the obtained pellets were dried at 120 ° C for 7 hours in a hot air circulating dryer, using an injection molding machine, the cylinder temperature was 310 ° C and the mold temperature was 80 ° C, and A smooth flat test piece having a length of 50 mm, a width of 50 mm, a thickness of 2.0 mm, and a surface arithmetic average roughness (Ra) of 0.03 μm was molded under the condition of a shooting speed of 20 mm / sec. SG260M-HP manufactured by Sumitomo Heavy Industries, Ltd. was used as the injection molding machine.

(II-IV) Preparation of injection molded member After the obtained pellets were dried by the same method, the through-type headlamp lens shown in FIGS. 1 and 2 under conditions of a cylinder temperature of 310 ° C. and a mold temperature of 80 ° C. The molded product and the electronic circuit cover molded product (height 20 mm, thickness 1.5 mm) shown in FIG. 3 were injection molded to produce an injection molded member. SG260M-HP manufactured by Sumitomo Heavy Industries, Ltd. was used as the injection molding machine. The molded member was evaluated visually based on the criteria of transparency, opaqueness, and yellowing. That is, it was determined that “transparent” was observed as colorless and transparent, “opaque” was observed when transparency was insufficient, and “yellow” was observed when yellowing was observed.

(II-V) Preparation of sheet-like member After the obtained pellets were dried by the same method, a 250 mm width was obtained under the conditions of a cylinder temperature of 280 ° C. and a die temperature of 280 ° C. using a single screw extruder with a screw diameter of 40 mm. An unstretched film having a thickness of 200 μm was produced by extrusion from a T die. 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. Evaluation of such a sheet-like member was carried out visually by the judgment criteria of transparent, opaque, and yellowing as in the case of the injection molded member.

(Examples 1-20 and Comparative Examples 1-15)
The pellet of the resin composition which consists of each component of Table 1-Table 3 was manufactured, and the test piece and the transparent member were created with the said processing method. The evaluation results are shown in Tables 1 to 3.
(A component)
A-1: Polycarbonate resin powder having a viscosity average molecular weight of 22,200 produced by an interfacial condensation polymerization method from bisphenol A and phosgene (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WP)
A-2: Polycarbonate resin powder having a viscosity average molecular weight of 23,900 produced from bisphenol A and phosgene by an interfacial condensation polymerization method (manufactured by Teijin Chemicals Ltd .: Panlite L-1250WP)

(B component)
B-1: Tetrabutylphosphonium salt of dodecylbenzenesulfonic acid (Takemoto Yushi Co., Ltd .: TCS-101)
B-2: Potassium dodecylbenzenesulfonate (manufactured by Takemoto Yushi Co., Ltd.)
B-3: Cesium salt of dodecylbenzenesulfonic acid (manufactured by Takemoto Yushi Co., Ltd.)
B-4: Dodecylbenzenesulfonic acid didodecylmethylammonium salt (manufactured by Sanyo Chemical Co., Ltd .: Chemistat 3112C-6)

(C component)
C-1: Trimethyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd .: TMP)
C-2: Triphenyl phosphate (manufactured by Daihachi Chemical Industry Co., Ltd .: TPP)
C-3: Phosphate ester mainly composed of bisphenol A bis (diphenyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd .: CR-741)
C-4: Resorcinol bis (dixylenyl phosphate) (Asahi Denka Kogyo Co., Ltd .: ADK STAB FP-500)

(D component)
D-1: Polyether ester copolymer prepared by the above method (reduced viscosity 1.35 dl / g, sodium sulfonate base is about 1.5 × 10 ⁻⁴ mol / g)
D-2: Sodium sulfonate-modified polyester (Toyobo Co., Ltd .: Byron 280) (polyethylene terephthalate / isophthalate copolymer containing 5-sodium sulfoisophthalic acid unit as a repeating unit, reduced viscosity 0.54 dl / g, (The sodium sulfonate base is about 5.9 × 10 ⁻⁴ mol / g)
D-3: Sodium sulfonate modified polyester (Toyobo Co., Ltd .: Byron 240) (polyethylene terephthalate / isophthalate copolymer containing 5-sodium sulfoisophthalic acid unit as a repeating unit, reduced viscosity 0.45 dl / g, (Sodium sulfonate base is about 2.9 × 10 ⁻⁴ mol / g)

(E component)
E-1: 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)
(F component)
F-1: Triphenyl phosphite (Asahi Denka Kogyo Co., Ltd .: ADK STAB TPP)
F-2: Bis (2,4-di-t-butylphenyl) pentaerythritol diphosphite (Asahi Denka Kogyo Co., Ltd .: ADK STAB PEP-24G)

(Other)
AO-1: Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (Ciba Specialty Chemicals KK: Irganox 1076)
UVA: Benzotriazole-based ultraviolet absorber (Kemipro Kasei Co., Ltd .: Chemisorb 79)

  As is apparent from the above table, the resin composition of the present invention has good antistatic properties, hue, molding heat resistance, transparency, impact resistance, and antistatic performance with good durability during dry heat treatment. It can be seen that a molded article having Furthermore, it turns out that it is suitable for the transparent member for vehicles in which transparency and antistatic performance are requested | required, the member for electronic circuit board covers, and a transparent sheet-like member.

The front view (the figure projected on the platen surface at the time of shaping | molding. Therefore, such an area becomes the maximum projection area) of the molded article of the through-head type | mold headlamp lens simulated type | mold of the motor vehicle shape | molded in the Example is shown. As shown, the lens has a dome shape. The AA sectional view taken on the line of the molded article of the through-head type headlamp lens simulation type | mold of the motor vehicle shape | molded in the Example is shown. It is a front view of a cover molded product.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Lens dome part 2 Lens outer peripheral part 3 Molded product gate (width 30mm, gate part thickness 4mm)
4 Sprue (gate diameter 7mmφ)
5 Diameter of the outer periphery of the lens (220mm)
6 Diameter of lens dome (200mm)
7 Lens dome height (20mm)
8 Lens molded product thickness (4mm)
9 Cover molded product gate (4 points, 0.65 mm diameter pin gate, symmetrical with respect to the symmetry axis (12) and symmetry axis (13), respectively)
10 Length of cover molding (die size 200mm)
11 Width of cover molded product (100mm mold size)
12 Axis of symmetry in width direction of cover molded product 13 Axis of symmetry in length direction of cover molded product 14 Position of gate of cover molded product (length from symmetry axis (12), 35 mm in mold size)
15 Position of the gate of the cover molded product (the length from the axis of symmetry (13), which is 60 mm in the mold dimensions)

Claims (16)

  Polycarbonate resin (component A) 100 parts by weight, low molecular weight dodecylbenzenesulfonate (component B) 0.01-4 parts by weight and stoichiometric molecular weight of 1000 g / mol or less, and phosphate ester (component C) 0 An antistatic polycarbonate resin composition comprising 0.001 to 0.3 parts by weight. Low molecular weight dodecylbenzene sulfonate dodecylbenzenesulfonic acid phosphonium salts or claim 1 antistatic polycarbonate resin composition according dodecylbenzenesulfonic acid tetrabutylphosphonium salt. The antistatic polycarbonate resin composition according to claim 1 or 2 , wherein the phosphate ester is an aliphatic monophosphate ester represented by the following general formula (II).

(Wherein R ⁵ , R ⁶ and R ⁷ each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms) The antistatic polycarbonate resin composition according to claim 3, wherein the aliphatic monophosphate is at least one phosphate selected from the group consisting of trimethyl phosphate, triethyl phosphate, and tributyl phosphate. Polyether esters and / or polycarbonate resin (A component) of the polyester (D component) having a sulfonate group per 100 parts by weight having a sulfonic acid base, comprising 0.01 to 5 parts by weight claims claim 1-4 The antistatic polycarbonate resin composition according to any one of the above. (D1) an aromatic dicarboxylic acid component having no sulfonate group, (D2) an aromatic dicarboxylic acid component substituted with a sulfonate group represented by the following general formula (III), The antistatic polycarbonate resin composition according to claim 5 , which is a polyether ester comprising D3) a glycol component having 2 to 10 carbon atoms and (D4) a poly (alkylene oxide) glycol component having a number average molecular weight of 200 to 50,000. object.

(In the formula, Ar represents a trivalent aromatic group having 6 to 20 carbon atoms, and M ⁺ represents a metal ion or an organic onium ion.) (D5) an aromatic dicarboxylic acid component having no sulfonate group, (D6) an aromatic dicarboxylic acid component substituted with a sulfonate group represented by the general formula (III), and (D7) The antistatic polycarbonate resin composition according to claim 5 or 6 , which is a polyester comprising a glycol component having 2 to 10 carbon atoms. The antistatic property according to any one of claims 1 to 7 , comprising 0.01 to 2 parts by weight of a hindered phenol-based antioxidant (component E) per 100 parts by weight of the polycarbonate resin (component A). Polycarbonate resin composition. The antistatic agent according to any one of claims 1 to 8 , which comprises 0.01 to 2 parts by weight of a phosphite antioxidant (F component) per 100 parts by weight of a polycarbonate resin (A component). Polycarbonate resin composition. The antistatic polycarbonate resin composition according to any one of claims 1 to 9 , comprising 0.01 to 2 parts by weight of an ultraviolet absorber (G component) per 100 parts by weight of the polycarbonate resin (A component). . 0.03μm following arithmetic average roughness in smooth flat plate thickness 2mm with (Ra), any one of the claims 1-10 haze measured by JIS K7105 satisfies that the 0.1% to 1% Item 6. An antistatic polycarbonate resin composition according to Item. The charging according to any one of claims 1 to 11 , which satisfies a withstand voltage half-life of 200 seconds or less as measured with a smooth flat plate having a thickness of 2 mm and having an arithmetic average roughness (Ra) of 0.03 µm or less. Preventive polycarbonate resin composition. A molded product obtained by melt-molding the antistatic polycarbonate resin composition according to any one of claims 1 to 12 . The molded article according to claim 13 , wherein the molded article is a vehicle transparent member. The molded article according to claim 13 , wherein the molded article is a transparent member for game machines. The molded article according to claim 13 , wherein the molded article is a transparent sheet-like member.

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