JP4606762B2 - Antistatic polycarbonate resin composition - Google Patents

Description

  The present invention relates to an antistatic polycarbonate resin composition excellent in hue, transparency, and impact resistance, and a molded article comprising the composition, 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.

  It has always been desired to impart antistatic properties to an 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 impact resistance, transparency, and hue.

  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.

  A resin composition in which a phosphonium salt of sulfonic acid is blended with a polycarbonate resin, and two tert-butyl groups represented by octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate are substituted by a nucleus. The resin composition which combined the hindered phenol compound which was made is publicly known (refer to patent documents 6 and 7).

  Polycarbonate resin, polyether ester having sulfonic acid metal base, sodium diisopropylnaphthalenesulfonate, and 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] Transparent antistatic property comprising a specific ratio of -1,1, -dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane and containing the polyether ester in a relatively high concentration A resin composition and a film made of the resin composition are known (see Patent Document 8).

  A transparent chargeable resin composition comprising a specific ratio of a polycarbonate resin, a polyether ester having a sulfonic acid metal base, an ionic surfactant, and a hindered phenol compound, and containing the polyether ester at a relatively high concentration It is known that the hindered phenol compound is preferably a compound in which a methyl group and a tert-butyl group are substituted with a nucleus (see Patent Document 9).

  Moreover, the resin composition which mix | blended the phosphonium salt of the sulfonic acid with the polycarbonate resin, and the phosphoric acid and the organic acid were combined (refer patent documents 10 and 11), or the specific phosphonite compound was combined (refer patent document 12). Also known are antistatic polycarbonate resin compositions having improved transparency, hue, molding heat resistance and dry heat resistance.

  However, in fields where transparency and hue of products are more important, an antistatic polycarbonate resin composition having further improved transparency and hue has been demanded. 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. There is also a need for both high transparency and hue. 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 2002-080707 A Japanese Patent Laid-Open No. 10-219095 JP 11-343401 A JP 2002-064249 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, transparency, hue and impact resistance, and more preferably excellent in dry heat resistance, and a molded article comprising the composition, particularly a vehicle. An object of the present invention is to provide a transparent member for a game, a transparent member for a gaming machine, and a transparent sheet-like member.

  As a result of intensive investigations to achieve the above object, the present inventors have more suitably added a specific amount of a specific sulfonic acid phosphonium salt and a hindered phenol compound having a specific functional group to a polycarbonate resin. Has further found that a resin composition meeting the above-mentioned purpose can be obtained by blending a polyether ester containing a sulfonate group and / or a polyester containing a sulfonate group. Completed the invention.

  As described above, in the antistatic polycarbonate resin composition containing a polyether ester containing a sulfonate group at a relatively high concentration, there has been a finding that the above-mentioned specific hindered phenol compound is useful. However, sufficient transparency has not been achieved with the resin composition. Moreover, when there was no knowledge about combining a specific sulfonic acid phosphonium salt with such a hindered phenol compound, the present inventors found the above-mentioned unexpected effect and led to the present invention.

  As described above, 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 sulfonic acid phosphonium salt (component B) represented by the following general formula (I), and An antistatic polycarbonate resin composition comprising 0.001 to 3 parts by weight of a hindered phenol compound (component C) having a functional group represented by the formula (II) is provided.

（式中、Ａ^１は炭素数１〜４０のアルキル基（炭素数６〜４０のアラルキル基を含む）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５〜１５のアリール基を示す。）

(In the formula, A ¹ represents an alkyl group having 1 to 40 carbon atoms (including 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 Each independently 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 5 to 15 carbon atoms.)

  Furthermore, according to the present invention, as a more preferred embodiment, (2) 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) is further contained. An antistatic polycarbonate resin composition having the above constitution (1) is provided.

Here, a sulfonate or a group protons sulfonic acid group _(-SO 3 H) has been substituted with other _cations, ^-SO 3 ^- in counter-ions ^{- X +} (X + is -SO ₃ A group represented by: 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 (1), the object of the present invention is achieved. Hereinafter, the hindered phenol compound having the specific functional group may be referred to as “semi-hindered phenol” for the sake of simplicity. The hindered phenol compound is more commonly a compound in which a tert-butyl group is bonded to both carbon atoms adjacent to the carbon atom to which the OH group is bonded. The reason why the semi-hindered phenols of the present invention give a better hue is not clear. However, the present inventors inferred that one of the reasons is that there is a slightly less hindrance of the alkyl group to the OH group, which may increase the reactivity of the OH group and consequently stabilize the dissociation of the phosphonium salt. is doing. On the other hand, one of the reasons is that the radical trapping ability is further increased. In any case, it is considered that the compound is effective in suppressing the decomposition of the salt in that a more remarkable effect is recognized under the formulation of the phosphonium salt.

  According to the configuration (2) which is a more preferred embodiment, an antistatic polycarbonate resin composition having higher antistatic performance and excellent dry heat resistance is 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. The effect is that the phosphonium salt is stably present in the resin matrix without agglomeration or volatilization over a long period of time by blending a polymer type sulfonate having a relatively good compatibility with the polycarbonate resin. It is thought to be due to.

  One of the preferred embodiments of the present invention is that (3) 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 having the above-mentioned constitution (2).

（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 of the preferred embodiments of the present invention is that (4) D component polyester is (D5) an aromatic dicarboxylic acid component having no sulfonate group, (D6) sulfonic acid represented by the following general formula (III) An antistatic polycarbonate resin composition having the above constitutions (2) to (3), 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.

（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.)

  According to the configurations (3) and (4), an antistatic polycarbonate resin composition having a good hue and remarkably excellent thermal stability is provided. Although the thermal stability is further stabilized as compared with the prior art, yellowing and poor appearance during molding are remarkably improved, but this effect is particularly apparent in molding with a large molding machine in which molten resin tends to stay. 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 its ester-forming derivative. 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 (4), further comprising (5) 0.005 to 2 parts by weight of a phosphorus stabilizer per 100 parts by weight of the polycarbonate resin (component A). The antistatic polycarbonate resin composition. According to this configuration (5), an antistatic polycarbonate resin composition that is more excellent in hue stability is provided.

  One of the preferred embodiments of the present invention is (6) a smooth flat plate having a thickness of 2 mm made of the resin composition and having an arithmetic average roughness (Ra) of 0.03 μm, and the haze measured by JIS K7105 is 0.00. It is an antistatic polycarbonate resin composition of the said structure (1)-(5) satisfying that it is 1-1%. According to this configuration (6), an antistatic polycarbonate resin composition having excellent transparency is provided.

  In addition, one of the preferred embodiments of the present invention is that (7) a 2 mm-thick molded plate molded from the resin composition at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. is measured based on ASTM E1925. The antistatic polycarbonate resin composition of the above constitution (6) satisfying that the YI value calculated by the formula is in the range of 0.3 to 0.9. A preferred form of such a resin composition is a pellet. According to this configuration (7), there is provided a polycarbonate resin composition capable of providing a molded product having excellent hue and transparency that satisfies the YI value, particularly a pellet thereof.

  One of the preferred embodiments of the present invention is that (8) the sulfonate group contained in the B component and the D component is substantially composed of a phosphonium base and a metal sulfonate group in the total amount, and the ratio of both Is an antistatic polycarbonate resin composition having the above constitutions (1) to (7) in the range of 0.02 to 2 mol of the sulfonic acid metal base with respect to 1 mol of the phosphonium sulfonate base. By satisfying such a specific ratio, an antistatic polycarbonate resin composition having better transparency and antistatic properties is provided.

  One of the preferred embodiments of the present invention is (9) a molded product obtained by melt-molding the antistatic polycarbonate resin composition having the constitution (1) to (8). According to this configuration (9), a polycarbonate resin molded product having excellent antistatic performance and excellent transparency and hue is provided.

  One of the preferable aspects of the present invention is (10) the molded product according to (9), wherein the molded product is a transparent member for a vehicle. The resin composition of the present invention provides a resin composition suitable for a transparent member for vehicles, which is a typical application requiring antistatic performance, transparency, and hue stability, and a vehicle comprising such a composition. A transparent member is provided.

  One of the preferable aspects of the present invention is (11) the molded product according to (9), wherein the molded product 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 machines having these advantages are provided by the configuration (11).

  One of the preferable aspects of the present invention is (12) the molded product according to (9), wherein the molded product is a transparent sheet-like member. According to this configuration (12), 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 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, particularly bisphenol A (hereinafter sometimes abbreviated as “BPA”) is widely used.

  In the present invention, in addition to the 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 of 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 specifically, phosgene, diphenyl carbonate, dihaloformate of dihydric phenol or the like can be mentioned.

  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 bifunctional carboxylic acid include, for example, sebacic acid (decanedioic acid), dodecanedioic acid, tetradecanedioic acid, octadecanedioic acid, icosanedioic acid, etc., linear 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 between a dihydric phenol and phosgene, and is reacted 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 the 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 dodecyl benzyl 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

（式中、Ａ^１は炭素数１〜４０のアルキル基（炭素数６〜４０のアラルキル基を含む）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５〜１５のアリール基を示す。） <B component: phosphonium salt of sulfonic acid>
The B component of the present invention is a sulfonic acid phosphonium salt represented by the following general formula (I).

(In the formula, A ¹ represents an alkyl group having 1 to 40 carbon atoms (including 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 Each independently 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 5 to 15 carbon atoms.)

  Since the sulfonic acid phosphonium salt represented by the general formula (I) has relatively good compatibility with the polycarbonate resin, an antistatic polycarbonate resin composition excellent in transparency can be obtained.

In the above formula (I), examples of the alkyl group in A ¹ include a dodecyl group, a decyl group, a butyl group, and an ethyl group. 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. 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.

In said general formula (I), R < ¹ >, R < ² >, R < ³ > and R < ⁴ > are respectively independently a hydrogen atom, a C1-C20 alkyl group, a C6-C20 aralkyl group, or C5-C5. 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, and eicosyl group.

  Examples of the aralkyl group having 6 to 20 carbon atoms include benzyl group, 2,6-di-tert-butyl-4-methylbenzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and 2-phenylisopropyl group. It is done. Examples of the aryl group having 5 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 a butyl group or an octyl group. Among them, all are butyl groups, or any one is an octyl group and the rest are butyl groups. Is 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 good compatibility with the polycarbonate resin, and any one of them remains as an octyl group. A sulfonic acid phosphonium salt in which is a butyl group is preferable in that it has little thermal deterioration of antistatic performance. More preferred in practice is a phosphonium sulfonate salt in which R ¹ , R ² , R ³ and R ⁴ are all butyl groups.

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

<C component: Semi-hindered phenols>
Component C is a hindered phenol compound having a functional group represented by the following formula (II) in the molecule.

  The purpose of the present invention is to provide a polycarbonate resin composition having excellent antistatic performance as well as transparency and hue, but only with the above-mentioned phosphonium salt of sulfonic acid, it is easy to induce thermal decomposition and thermal deterioration of the polycarbonate resin, As a result, pellets obtained by melt-kneading and molded products obtained using the same exhibit deterioration in appearance such as yellowing and silver generation, and it is difficult to obtain a desired antistatic polycarbonate resin composition.

  When a phosphonium salt of sulfonic acid is blended with a polycarbonate resin and melted and kneaded at a high temperature, the resin composition yellows due to the thermal decomposition of the sulfonate itself due to a high processing temperature, and the polycarbonate resin is thermally decomposed due to the decomposition product. Yellowing occurs. In order to suppress the decomposition of the polycarbonate resin, it is important to stabilize the dissociation of sulfonic acid phosphonium salt, which is an ionic compound, and to trap radicals generated in the initial stage of thermal decomposition. . In this respect, the semi-hindered phenols of the present invention are effective.

  As described above, since the steric hindrance around the OH group is somewhat low, the semi-hindered phenols of the present invention are presumed to be highly effective in stabilizing dissociation and initial radical trapping. On the other hand, when the nucleus-substituted methyl group in the formula (II) is a substituent having higher steric hindrance than represented by the tert-butyl group, the resulting peroxide radical is excellent in stabilizing effect. It is considered that the dissociation stability and radical trapping ability of the phosphonium salt is inferior because of its high value. Furthermore, when there is no nucleus-substituted methyl group in the above formula (II) and only the tert-butyl group is a nucleus-substituted group, it is presumed that the radical stabilizing effect is inferior and a sufficient effect is not exhibited.

  The molecular weight of the semi-hindered phenol compound used in the present invention is preferably 400 to 2,000, more preferably 500 to 1,500, still more preferably 550 to 1,200. Such semi-hindered phenols having a suitable molecular weight range have excellent volatility resistance and heat resistance, and are excellent in compatibility with polycarbonate resins, so that a resin composition having both better hue and transparency can be achieved. Is done.

  By blending a hindered phenol compound having a functional group represented by the above formula (II) in the molecule, an antistatic polycarbonate resin composition having better hue and transparency than the conventional one can be obtained. Such compounds include triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- (3-tert-butyl- 4-hydroxy-5-methylphenyl) acetate, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl]- 2,4,8,10-tetraoxaspiro [5,5] undecane, 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1 , 1-Dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, tetrakis [methylene-3- (3-tert-butyl-4-hydro Roxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) benzene, and tris (3-tert -Butyl-4-hydroxy-5-methylbenzyl) isocyanurate and the like.

  Among them, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate and 3,9-bis [2- {3- (3-tert-butyl-4- Hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane is preferred, especially 3,9-bis [2- {3 -(3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane is preferred. . The compound particularly suitable as the component C is commercially available, for example, from Asahi Denka Kogyo Co., Ltd. as ADK STAB AO-80 (trade name) and from Sumitomo Chemical Co., Ltd. as Sumilizer GA-80 (trade name). Can also be used.

<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 together with the sulfonic acid phosphonium salt, a polyether ester having a sulfonate group and / or a polyester having a sulfonate group. 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.

Where D component of the sulfonate group - specific examples of _(-SO ^{3 X +)} are as follows. The metal ions in X ⁺ (hereinafter sometimes referred to simply as counter ions) are, for example, alkali metal ions such as sodium, potassium, lithium, rubidium, and cesium, alkaline earth metal ions such as calcium and magnesium, Includes zinc ions, copper ions, and the like. The organic onium ions in the counter ion include, for example, ammonium ions, phosphonium ions, sulfonium ions, onium ions derived from heteroaromatic rings, and the like. As the organic onium ion, any of primary, secondary, tertiary and quaternary can be used, and quaternary onium ions are preferred. The organic onium 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. Furthermore, the counter ion in 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、テトラアルキルホスホニウムイオン又はテトラアルキルアンモニウムイオンを表す。）

(In the formula, Ar represents a trivalent aromatic group having 6 to 20 carbon atoms, and M ⁺ represents a metal ion, a tetraalkylphosphonium ion, or a tetraalkylammonium ion.)

  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 a specific example thereof can be the same as the above X ⁺ . The counter ion 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.

  Examples of the aromatic dicarboxylic acid substituted with a sulfonate group and an ester-forming derivative thereof for deriving (D2) 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 acid components (D1) and (D2) constituting the polyether ester of component D are composed of 100 mol% of the total acid components, and (D1) an aromatic dicarboxylic acid component 95 having no sulfonate group. It is preferable that the ratio is ˜50 mol% and (D2) 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 preferred proportions of the component (D1) and the component (D2) are (D1) 92 to 65 mol% and (D2) 8 to 35 mol%, and a more preferred proportion 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. Preferred proportions of 1,6-hexanediol component and ethylene glycol component in the polyether ester of component D are 95 to 50 mol% of 1,6-hexanediol component and ethylene glycol component 5 to 100 mol% of glycol component. They are 50 mol%, More preferably, they are 90-70 mol% of 1, 6- hexanediol components and 10-30 mol% of ethylene glycol components.

  As the poly (alkylene oxide) glycol for deriving (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. When the molecular weight is less than 200, the advantage of using the polyether ester that a better antistatic effect can be obtained may not be sufficiently exhibited. In terms of practicality, it is sufficient that the molecular weight is about 50,000. The preferred molecular weight of the poly (alkylene oxide) glycol is 500 to 30,000, more preferably 1,000 to 20,000. The poly (alkylene oxide) glycol component (D4) can be contained alone or in combination of two or more in the polyether ester.

  The poly (alkylene oxide) glycol component of (D4) is preferably 10 to 50% by weight, more preferably 15 to 45% by weight, still more preferably 20 to 40% by weight in 100% by weight of the polyether ester of the D component. Is within the range. 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 its ester-forming derivatives 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, when 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 an average molecular weight of 5,000 or more. If the average molecular weight is less than 5,000, heat resistance and mechanical properties may be deteriorated. The upper limit for the average molecular weight is preferably higher in terms of mechanical properties since the polymer is a substantially linear polymer, but the practical upper limit for the average molecular weight is about 100,000.

  The polyester of the D component of the present invention can be produced by a transesterification reaction similarly to the polyether ester of the D component, and can further contain the above 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.

<About the amount of each component>
Next, the amount of the B component to the D 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 parts by weight, the antistatic effect of the resin composition tends to be insufficient, and if it exceeds 5 parts by weight, the transparency and hue of the molded product are deteriorated. The amount of component C is in the range of 0.001 to 3 parts by weight, preferably 0.005 to 2 parts by weight, and more preferably 0.01 to 1.5 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, it is not preferable because the hue deteriorates easily during extrusion and molding. On the other hand, if it exceeds 3 parts by weight, the hue deteriorates and the molecular weight decreases more easily. Absent. 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, a sufficient antistatic effect cannot be obtained, and if it exceeds 5 parts by weight, the transparency and hue of the molded product are deteriorated.

  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. It is preferable that the ratio of the B component and the D component, and the ratio of the phosphonium sulfonate base and the metal sulfonate base in the D component are adjusted so as to satisfy such conditions, and in particular, a polyether having a sulfonate metal base as the D component. It is preferable to blend the polyester having an ester and / or a sulfonic acid metal base into the polycarbonate resin so as to satisfy the above ratio.

<About other additives>
The polycarbonate resin composition of the present invention can contain various additives that are usually blended in the polycarbonate resin, in addition to the above components A to D.

(I) Phosphorus stabilizer It is preferable that various phosphorous stabilizers are further blended mainly for the purpose of improving the thermal stability during molding of the resin composition of the present invention. Examples of such phosphorus stabilizers include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.

  Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, 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-butylpheny) ) 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 Phyto, bis (nonylphenyl) pentaerythritol diphosphite, dicyclohexyl pentaerythritol diphosphite, and the like.

  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.

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

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

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

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

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphite compounds or phosphonite compounds are preferable. In particular, tris (2,4-di-tert-butylphenyl) phosphite, tetrakis (2,4-di-tert-butylphenyl) -4,4′-biphenylenediphosphonite and bis (2,4-di-) tert-Butylphenyl) -phenyl-phenylphosphonite is preferred. A combination of these and a phosphate compound is also a preferred embodiment. The amount of the (i) phosphorus stabilizer is 0.0001 to 1 part by weight, preferably 0.001 to 0.1 part by weight, and more preferably 0.005 to 100 parts by weight of the polycarbonate resin (component A). -0.1 parts by weight. When the amount of the stabilizer is too much less than the above range, it is difficult to obtain a good stabilizing effect. When the amount exceeds the above range, the physical properties of the composition may be lowered.

(Ii) 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. Since the resin composition of the present invention is relatively yellowish, the use of a bluing agent is very effective for imparting a natural transparency to a molded product. Here, the bluing agent refers to a colorant that exhibits a blue or purple color by absorbing light of orange or yellow color, and a dye is particularly preferable. By adding the bluing agent, the 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.

(Iii) Other hindered phenol compounds The polycarbonate resin composition of the present invention may contain a hindered phenol compound other than the component C. As described above, it is speculated that the component C of the present invention has a specific functional group, thereby suppressing the decomposition of the antistatic agent and providing a suitable action for radical trapping. On the other hand, even if a hindered phenol compound having other characteristics is contained, the effect of the present invention is exhibited. By using a hindered phenol compound having higher radical stabilization, a polycarbonate resin composition having higher hue and transparency can be provided. The hindered phenol compound other than the component C is preferably 0.001 to 0.2 parts by weight, more preferably 0.005 to 0.05 parts by weight, still more preferably 0.01 to 0. 03 parts by weight. In particular, the amount is preferably 1 to 100 parts by weight, more preferably 5 to 60 parts by weight, and still more preferably 10 to 50 parts by weight with respect to 100 parts by weight of component C.

  Examples of hindered phenol compounds other than component C include n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylfel) propionate, 2-tert-butyl-6- (3 ′). -Tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenyl acrylate, 2,2'-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis ( 3-methyl-6-tert-butylphenol), 1,6-hexanediol bis [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, and tetrakis [methyle 3- (3 ', 5'-di -tert- butyl-4-hydroxyphenyl) such as propionate] methane are exemplified. A particularly preferred hindered phenol compound other than component C is n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-tert-butylfel) propionate.

(Iv) Release agent It is preferable to mix | blend a release agent with the polycarbonate resin composition of this invention for the purpose of the productivity improvement at the time of the shaping | molding, and the reduction of the distortion of a molded article. 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 (E.g., fluorine oil represented by polyfluoroalkyl ether), paraffin wax, beeswax and the like. The release agent is preferably 0.005 to 2 parts by weight with respect to 100 parts by weight of the polycarbonate resin (component A).

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

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

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

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

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

(V) Ultraviolet Absorber The polycarbonate resin composition of the present invention is extremely suitable for use in transmitting light because of its excellent transparency. In order to suppress discoloration of the molded product due to such light (light from the light source or natural light when used outdoors), an ultraviolet absorber can be appropriately blended.

  Specific examples of the ultraviolet absorber of the present invention include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2-hydroxy-4 in the benzophenone series. -Benzyloxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxytrihydridolate benzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2, 2 ′, 4,4′-tetrahydroxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxy-5-sodiumsulfoxybenzophenone, bis (5-benzoyl-4-hydro Shi-2-methoxyphenyl) methane, 2-hydroxy -4-n-dodecyloxy benzoin phenone, and 2-hydroxy-4-methoxy-2'-carboxy benzophenone may be exemplified.

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

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

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

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

  Furthermore, the ultraviolet absorber has a structure of a monomer compound capable of radical polymerization, so that the ultraviolet absorbent monomer and / or the light stable monomer and a single amount of alkyl (meth) acrylate or the like can be obtained. It may be a polymer type ultraviolet absorber copolymerized with a body. Preferred examples of the ultraviolet absorbing monomer include compounds containing a benzotriazole skeleton, a benzophenone skeleton, a triazine skeleton, a cyclic imino ester skeleton, and a cyanoacrylate skeleton in the ester substituent of (meth) acrylic acid ester. The

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

  The amount of the ultraviolet absorber is 0.01 to 2 parts by weight, preferably 0.03 to 2 parts by weight, more preferably 0.02 to 1 part by weight, and still more preferably 100 parts by weight of the polycarbonate resin (component A). Is 0.05 to 0.5 parts by weight.

(Vi) Dye / pigment Since the polycarbonate resin composition of the present invention has good transparency, it can further provide a molded product containing various dyes / pigments and exhibiting various design properties. For example, by including a fluorescent whitening agent, it gives a higher light transmission and natural transparency, and by including a fluorescent whitening agent or other fluorescent dye that emits light, the luminescent color is utilized. A design effect can be imparted. 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 fluorescent dyes (including fluorescent brighteners) used in the present invention include coumarin fluorescent dyes, benzopyran fluorescent dyes, perylene fluorescent dyes, anthraquinone fluorescent dyes, thioindigo fluorescent dyes, and xanthene fluorescent dyes. And xanthone-based fluorescent dyes, thioxanthene-based fluorescent dyes, thioxanthone-based fluorescent dyes, thiazine-based fluorescent dyes, and diaminostilbene-based 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 amount of the dye / pigment is preferably 0.00001 to 1 part by weight, more preferably 0.00005 to 0.5 part by weight, per 100 parts by weight of the polycarbonate resin of component A.

(Vii) Compound having heat ray absorbing ability Since the polycarbonate resin composition of the present invention is excellent in transparency, a compound having heat ray absorbing ability is further blended to suppress the high temperature in the room blocked by the resin composition. be able to. In particular, such a composition is 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 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, and 0.001 to 0 parts per 100 parts by weight of the polycarbonate resin (component A). 0.07 part by weight is more preferable. The metal oxide near-infrared absorber, metal boride-based near infrared absorber and carbon filler are preferably in the range of 0.1 to 200 ppm (weight ratio) in the resin composition of the present invention, and in the range of 0.5 to 100 ppm. Is more preferable.

(Viii) Light Diffusing Agent Since the polycarbonate resin composition of the present invention is excellent in transparency and hue, it is possible to provide a resin composition having a good hue and light diffusing property by further blending a light diffusing agent. it can. 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 The polycarbonate resin composition of the present invention is excellent in transparency and hue, and therefore, by adding a white pigment for high light reflection, a resin composition having a good hue and light reflection. Things 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 In the polycarbonate resin composition of the present invention, an amount of a flame retardant that does not impair the object of the present invention can be used. Examples of flame retardants include brominated epoxy resins, brominated polystyrene, brominated polycarbonate, brominated polyacrylates, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, phosphonic acid amide compounds, and components D Organic acid metal salts (for example, potassium perfluoroalkanesulfonate and potassium diphenylsulfonesulfonate), silicone flame retardants and the like. Each of these flame retardants can be blended in a known amount relative to the polycarbonate resin.

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

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

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

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

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

  Furthermore, the polycarbonate resin composition of the present invention may contain a dripping inhibitor represented by polytetrafluoroethylene having fibril-forming ability. The amount of the anti-dripping agent is preferably 0.0001 to 3 parts by weight, more preferably 0.001 to 0.1 parts by weight with respect to 100 parts by weight of the polycarbonate resin of component A.

(Xi) Acidity adjuster The polycarbonate resin composition of the present invention may contain an acidity adjuster composed of 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.

(Xii) Other components other than the above In addition to the B component to the D 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, and polyphenylene sulfide resins. Polysulfone resin, polyolefin resin such as polyethylene and 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, for example, isobutylene / isoprene rubber, styrene / butadiene rubber, ethylene / propylene rubber, acrylic elastomer, polyester elastomer, polyamide elastomer, and core shell type MBS (methyl methacrylate / styrene / butadiene). ) 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 melt-kneads the A component, the B component, the C component, and the other components. It is preferable to manufacture by doing.

  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 the 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 and 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 common shapes, such as a cylinder, a prism, and a sphere, it is a cylinder more suitably. 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 and the like by extrusion. For forming sheets and films, an inflation method, a calendar method, a casting method, and the like can also be used. Furthermore, it can be formed as 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 an antistatic polycarbonate resin composition that retains the transparency, hue, and impact resistance 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 3 parts 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, a molded product obtained by melt-molding an antistatic polycarbonate resin composition containing 0.005 to 2 parts by weight of a phosphorus stabilizer is provided. According to the present invention, 0.01 to 4 parts by weight of B component, 0.001 to 3 parts by weight of C component, 0.01 to 5 parts by weight of D component, and antistatic polycarbonate resin composition with respect to 100 parts by weight of A component There is provided a molded product obtained by melt-molding an antistatic polycarbonate resin composition containing 0.05 to 3.0 ppm (weight ratio) of a bluing agent. Furthermore, according to the present invention, component B is 0.01 to 4 parts by weight, component C is 0.001 to 3 parts by weight, component D is 0.01 to 5 parts by weight, and acid value is 4 to 100 parts by weight of component A. A molded article obtained by melt-molding an antistatic polycarbonate resin composition comprising 0.01 to 1 part by weight of 20 fatty acid esters is provided.

  As described above, the antistatic polycarbonate resin composition of the present invention is excellent in transparency and hue, and as a result, it is possible to obtain a molded article having extremely good transparency and hue. More specifically, in a 2 mm thick flat plate made of the polycarbonate resin composition of the present invention and having an arithmetic average roughness (Ra) of 0.03 μm, the haze measured by JIS K7105 is 0.1 to 1%. There is provided an antistatic polycarbonate resin composition satisfying certain conditions (more preferably 0.1 to 0.5%). More preferably, the YI value calculated by measuring, based on ASTM E1925, a 2 mm thick molded plate molded from the resin composition at a cylinder temperature of 280 ° C. and a mold temperature of 80 ° C. is 0.3 to An antistatic polycarbonate resin composition that further satisfies the range of 0.9 is provided.

  A polycarbonate resin composition capable of providing a molded product having such a haze value or YI value has extremely good transparency and hue, and is particularly suitable for a headlamp lens and other transparent members for automobiles. 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.

  The molded article of the present invention includes various transparent members for vehicles (head lamp lens, winker lamp lens, tail lamp lens, resin window glass, meter cover, etc.), and 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, etc.), 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 means 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). A hard coat is a particularly preferred and required surface treatment.

  Since the antistatic polycarbonate resin composition of the present invention is excellent in antistatic performance, transparency, hue, and impact resistance, it can be used in buildings, building materials, agricultural materials, marine materials, vehicles, electric / electronic devices, machines. It is widely useful in various other fields. 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 performance: 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. The smaller the value of the charged voltage half-life, the better the antistatic performance.
(I-II) Transparency (haze): length of 50 mm × width of 50 mm × thickness of 2.0 mm, haze of a smooth flat test piece having a surface arithmetic average roughness (Ra) of 0.03 μm. It measured by NDH-300A by Corporation | KK. The larger the haze value, the greater the light diffusion and the lower the transparency.
(I-III) 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-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.

(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 100 parts of polycarbonate resin powder produced from bisphenol A and phosgene by interfacial polycondensation method, phosphonium salt of sulfonic acid, polyether ester, polyester, hindered phenolic antioxidant having specific functional group After blending 0.00008 parts of the blueing agent (manufactured by Bayer: Macrolex Violet B) with the blending amount of the agent and other additives in the table, and mixing with a blender, the vent type twin screw extruder Used to melt and knead to obtain pellets. 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 5 hours in a hot air circulation dryer, the cylinder temperature was 280 ° C and the mold temperature was 80 ° C using an injection molding machine, 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. As the injection molding machine, FANUC (manufactured by: AUTOSHOT T series model 150D) was used.

(II-IV) Preparation of injection-molded member After the obtained pellets were dried by the same method, the through-head type headlamp lens molded product shown in FIG. 1 and the cylinder temperature of 280 ° C. and the mold temperature of 80 ° C. An electronic circuit cover molded product (height 20 mm, thickness 1.5 mm) shown in FIG. 2 was 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, “transparent” observed as colorless and transparent, “opaque” observed as insufficient transparency, and “yellowed” observed yellowing.

(II-V) Preparation of sheet-like member After the obtained pellets were dried by the same method, using a single screw extruder with a screw diameter of 40 mm, the cylinder temperature was 270 ° C and the die temperature was 270 ° C. 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 1-10 and Comparative Examples 1-8)
The pellet of the resin composition which consists of each component of a table | surface was manufactured, and the test piece and the transparent member were created with the said processing method. The evaluation results are shown in Tables 1-3. The contents of each component indicated by symbols in the table are as follows. Moreover, from the compounding ratio in a table | surface, the number-of-moles of the sulfonate metal base with respect to 1 mol of sulfonic acid phosphonium bases was described in the table | surface.

(A component)
PC: Polycarbonate resin powder having a viscosity average molecular weight of 22,200 produced by interfacial condensation polymerization from bisphenol A and phosgene (manufactured by Teijin Chemicals Ltd .: Panlite L-1225WP)
(B component)
DBS-P: tetrabutylphosphonium salt of dodecylbenzenesulfonate (manufactured by Takemoto Yushi Co., Ltd .: TCS-101)
(C component)
AO-80: 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane (Asahi Denka Kogyo Co., Ltd .: ADK STAB AO-80 (trade name))
(Similar to C component)
AO-40 (for comparison with component C): 4,4′-butylidenebis (3-methyl-6-tert-butylphenol) (Asahi Denka Kogyo Co., Ltd .: ADK STAB AO-40 (trade name))
IRG1010 (for comparison with component C): tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4-hydroxyphenyl) propionate] methane (Ciba Specialty Chemicals KK: Irganox 1010 (commercial product) Name))
(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)
(Other additives)
DBS-K (combination with component B): potassium dodecylbenzenesulfonate (manufactured by Takemoto Yushi Co., Ltd.)
DBS-C (combination with B component): Cecium salt of dodecylbenzenesulfonic acid (manufactured by Takemoto Yushi Co., Ltd.)
P-EPQ: Phosphonite heat stabilizer (manufactured by Clariant: Sandstub P-EPQ)
IRG1076 (in combination with component C): Phenol antioxidant (Ciba Specialty Chemicals KK: Irganox 1076)
EW: Saturated fatty acid ester-based mold release agent (Riken Vitamin Co., Ltd .: Riquester EW-400)
UVA: Benzotriazole-based ultraviolet absorber (Kemipro Kasei Co., Ltd .: Chemisorb 79)

  As is apparent from the above table, it can be seen that the resin composition of the present invention can provide a molded product having good antistatic performance, transparency, hue, and impact resistance. 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 molded article of the through-head type headlamp lens simulation type | mold of the motor vehicle shape | molded in the Example is shown. As shown, the lens has a dome shape. [1-A] is a front view (a figure projected onto a platen surface during molding. Therefore, such an area is the maximum projected area), and [1-B] is a cross-sectional view taken along line AA. It is a front view which shows a cover molded product.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Headlamp lens main body 2 Domed part of lens 3 Outer peripheral part of lens 4 Gate of molded product (width 30 mm, gate part thickness 4 mm)
5 Sprue (diameter 7mmφ of gate part)
6 Diameter of the outer periphery of the lens (220mm)
7 Lens dome diameter (200mm)
8 Height of lens dome (20mm)
9 Lens molded product thickness (4mm)
11 Cover molded product 12 Cover molded product gate (4 points, diameter 0.65 mmφ pin gate, symmetrical with respect to the symmetry axis (15) and the symmetry axis (16), respectively)
13 Length of cover molding (die size 200mm)
14 Cover molded product width (die size 100mm)
15 Symmetric axis 16 in the width direction of the cover molded product 16 Symmetric axis 17 in the length direction of the cover molded product 17 Position of the gate of the cover molded product (length from the symmetrical axis (15) and 35 mm in the mold dimensions)
18 Gate position of box-shaped molded product (length from axis of symmetry (16), 60 mm in mold dimensions)

Claims (7)

A polycarbonate resin (A component) 100 parts by weight, 0.01 to 4 parts by weight of a phosphonium sulfonate component (B) represented by the following formula (I), a functional group represented from below following formula (II) Replaced by 0.001 to 3 parts by weight of a hindered phenol compound (C component) , and (D5) an aromatic dicarboxylic acid component having no sulfonate group, (D6) a sulfonate group represented by the following general formula (III) An antistatic polycarbonate resin composition comprising 0.01 to 5 parts by weight of a polyester (D component) composed of an aromatic dicarboxylic acid component and (D7) a glycol component having 2 to 10 carbon atoms .

(In the formula, A ¹ represents an alkyl group having 1 to 40 carbon atoms (including 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 Each independently 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 5 to 15 carbon atoms.)

(In the formula, Ar represents a trivalent aromatic group having 6 to 20 carbon atoms, and M ⁺ represents a metal ion.) The antistatic polycarbonate resin composition according to claim 1, further comprising 0.005 to 2 parts by weight of a phosphorus stabilizer per 100 parts by weight of the polycarbonate resin (component A). In smooth flat plate thickness 2mm having an arithmetic mean roughness of 0.03μm consists of the resin composition (Ra), or claim 1 haze measured in JIS K7105 satisfies that the 0.1% to 1% The antistatic polycarbonate resin composition according to claim 2 . The molded article formed by melt-molding the antistatic polycarbonate resin composition of any one of Claims 1-3 . The molded article according to claim 4 , wherein the molded article is a transparent member for a vehicle. The molded article according to claim 4 , wherein the molded article is a transparent member for a game machine. The molded article according to claim 4 , wherein the molded article is a transparent sheet-like member.

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