JP2015117307A - Polycarbonate resin composition and molded article of the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition having improved scratch resistance, flowability, and impact properties, and a molded article of the same.SOLUTION: There is provided an aromatic polycarbonate resin composition comprising, (A) 100 pts.wt of an aromatic polycarbonate resin (A component), and with respect to the resin, (B) 5 to 100 pts.wt of a modified methyl methacrylate polymer (B component), (C) 1 to 10 pts.wt of a silicone-based core-shell copolymer (C component), and (D) 0.1 to 6 pts.wt of a slidability improver (D component). The modified methyl methacrylate polymer is either a modified methyl methacrylate homopolymer or a modified methyl methacrylate copolymer, and is obtained by a reaction with at least one chain transfer agent selected from the group consisting of mercapto esters, cycloalkyl thiols, substituted cycloalkyl thiols, hydroxyl thiols, aryl thiols, substituted aryl thiols, and aminoalkyl thiols.

Description

  The present invention, by blending a specific modified methyl methacrylate polymer in an aromatic polycarbonate resin composition containing an aromatic polycarbonate resin, an impact modifier, and a sliding property improver, scratch resistance, fluidity, The present invention relates to an aromatic polycarbonate resin composition and a molded article having improved impact characteristics.

  Polycarbonate resins have excellent transparency, heat resistance, mechanical strength, and the like, and thus are widely used in electrical, mechanical, automotive, and medical applications. However, since polycarbonate resin has a lower surface hardness than metal and glass products, it has poor scratch resistance, and has the disadvantage that the surface is easily damaged when wiped with cloth or handled roughly. doing.

  On the other hand, a method for forming a coating film having a high surface hardness on the surface of a product using an aromatic polycarbonate resin has been proposed, and as a film material, for example, a coating agent of silicon resin or acrylic resin is known. . However, since these coating agents have a problem in the adhesion of the coating film, they are difficult to coat for products with complicated shapes, are expensive in price, and are limited in industrial use. In addition, a method for painting the product surface is also known, but this method is difficult to obtain a uniform coating film depending on the product shape as well as the coating, and because of the use of an organic solvent, the solvent deterioration of the polycarbonate resin In addition, the effect of improving the surface hardness is low unless the coating film thickness is large. Furthermore, there is also a disadvantage that the appearance is impaired due to peeling of the coating surface or coating surface.

  In order to obtain a polycarbonate resin having excellent surface hardness, a method of blending a copolymer of methyl methacrylate and aromatic (meth) acrylate with an aromatic polycarbonate resin has been proposed. (Refer to Patent Document 1 and Patent Document 2) However, when this method is wiped with a cloth or reciprocated with a metal ball, it is easily scratched, and furthermore, the high impact characteristics characteristic of polycarbonate resin are impaired. There are drawbacks.

  Further, as a method for improving the sliding properties of polycarbonate resin, a method of blending polytetrafluoroethylene resin, silicone oil and polyolefin wax has been proposed. (Refer to Patent Document 3 and Patent Document 4) These compositions can improve sliding characteristics and reduce the coefficient of friction, but have a drawback of being easily scratched on hard objects.

  Thus, what is known as a polycarbonate resin excellent in scratch resistance is a composition with improved surface hardness or slidability, but these still do not have sufficient scratch resistance properties, It is difficult to say that the resin composition is excellent in both impact resistance and fluidity.

JP 2010-13607 A JP 2012-25790 A Japanese Patent Laid-Open No. 9-12856 JP 2000-309698 A

  An object of the present invention is to provide a polycarbonate resin composition excellent in scratch resistance, fluidity, and impact properties and a molded product thereof, particularly an automobile interior and exterior member.

  As a result of intensive investigations, the inventors have found that the aromatic polycarbonate resin composition containing an impact modifier and a slidability improver is blended with a specific modified methyl methacrylate polymer to thereby provide scratch resistance. The inventors have found that an aromatic polycarbonate resin composition and a molded article excellent in fluidity and impact characteristics can be obtained, and have completed the present invention. That is, the present invention is as follows.

(1) (A) 5 to 100 parts by weight of (B) modified methyl methacrylate polymer (B component) per 100 parts by weight of aromatic polycarbonate resin (A component), (C) silicone-based core-shell copolymer 1 to 10 parts by weight of (C component), (D) 0.1 to 6 parts by weight of slidability improver (D component), and the modified methyl methacrylate polymer is a modified methyl methacrylate homopolymer or modified methyl By reaction with at least one chain transfer agent selected from the group consisting of a methacrylate copolymer and selected from the group consisting of mercaptoester, cycloalkylthiol, substituted cycloalkylthiol, hydroxylthiol, arylthiol, substituted arylthiol and aminoalkylthiol Aromatic polycarbonate resin composition characterized by being obtained .
(2) The aromatic polycarbonate resin composition as described in 1 above, which contains 10 to 100 parts by weight of (E) polyester resin (E component) with respect to 100 parts by weight of component A.
(3) The aromatic polycarbonate resin composition as described in 1 or 2 above, wherein the component D is at least one selected from the group consisting of fatty acid esters, polyolefin waxes, and silicone oils.
(4) The aromatic polycarbonate resin composition as described in any one of 1 to 3 above, wherein the component D is a polyolefin wax having a molecular weight of 1,000 to 10,000.
(5) A molded product obtained from the aromatic polycarbonate resin composition according to any one of 1 to 4 above.
(6) The molded product according to 5 above obtained by injection molding.
(7) The molded product according to 5 or 6 above, which is a member for automobiles.

  The aromatic polycarbonate resin composition and molded article of the present invention are prepared by blending a specific modified methyl methacrylate polymer into an aromatic polycarbonate resin composition containing an aromatic polycarbonate resin, an impact modifier, and a slidability improving agent. This makes it possible to have excellent scratch resistance, fluidity, and impact characteristics. Therefore, the industrial effect that it produces is exceptional.

Hereinafter, the present invention will be described in detail.
<About component A>
The aromatic polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol and a carbonate precursor, and the reaction method includes an interfacial polycondensation method, a melt transesterification method, a solid phase of a carbonate prepolymer. Examples include a transesterification method and a ring-opening polymerization method of a cyclic carbonate compound.

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

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

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

These special polycarbonates may be used alone or in combination of two or more. Moreover, these can also be mixed and used for the bisphenol A type polycarbonate generally used.
The production method 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, etc. 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, carbonyl halide, carbonate ester, haloformate, or the like is used as the carbonate precursor, and specific examples include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol, and the like.

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

When the polyfunctional compound that produces a branched polycarbonate is included, the amount thereof is preferably 0.001 to 1 mol%, more preferably 0.005 to 0.9 mol%, particularly preferably 0.01 to the total amount of the polycarbonate. 0.8 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 and the like, and saturated aliphatic dicarboxylic acid and cyclohexanedicarboxylic acid. Preferred are alicyclic dicarboxylic acids such as As the bifunctional alcohol, an alicyclic diol is more preferable, and examples thereof include cyclohexanedimethanol, cyclohexanediol, and tricyclodecane dimethanol.

Furthermore, in the present invention, a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units can be used as the component A.
The aromatic polycarbonate resin as component A is a mixture of two or more of polycarbonates such as polycarbonates having different dihydric phenols, polycarbonates containing branched components, polyester carbonates, and polycarbonate-polyorganosiloxane copolymers. There may be. Furthermore, what mixed 2 or more types of polycarbonates from which a manufacturing method differs, a polycarbonate from which a terminal terminator differs, etc. can also be used.

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

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

The reaction by the melt transesterification method is usually a transesterification reaction between a dihydric phenol and a carbonate ester, and the alcohol or alcohol produced by mixing the dihydric phenol and the carbonate ester with heating in the presence of an inert gas. It is carried out by a method of distilling phenol. The reaction temperature varies depending on the boiling point of the alcohol or phenol produced, but in most cases is in the range of 120 to 350 ° C. In the latter stage of the reaction, the reaction system is decompressed to about 1.33 × 10 ^{3 to} 13.3 Pa to facilitate the distillation of the alcohol or phenol produced. The reaction time is usually about 1 to 4 hours.
Examples of the carbonate ester include esters such as an aryl group having 6 to 10 carbon atoms, an aralkyl group, or an alkyl group having 1 to 4 carbon atoms which may have a substituent. Among them, diphenyl carbonate is preferable.

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

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

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

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

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

In addition, when measuring the viscosity average molecular weight in the resin composition of this invention, it carries out in the following way. That is, the resin composition is dissolved in 20 to 30 times its weight of methylene chloride, and the soluble component is collected by Celite filtration, and then the solution is removed and dried sufficiently to obtain a solid component soluble in methylene chloride. . A specific viscosity (η _SP ) at 20 ° C. is determined from a solution obtained by dissolving 0.7 g of the solid in 100 ml of methylene chloride using an Ostwald viscometer, and the viscosity average molecular weight M is calculated by the above formula.

<About B component>
The modified methyl methacrylate polymer used in the present invention comprises at least one chain transfer agent selected from the group consisting of mercaptoesters, cycloalkyl thiols, substituted cycloalkyl thiols, hydroxyl thiols, aryl thiols, substituted aryl thiols and aminoalkyl thiols. A modified methyl methacrylate homopolymer or a modified methyl methacrylate copolymer obtained by the above reaction.

  The modified methyl methacrylate polymer uses a chain transfer agent during the polymerization. The chain transfer agent is added during the free radical polymerization process. The use of chain transfer agents that terminate at the ends of polymer chains and their mechanism of action are well known to those skilled in the art. Chain transfer agents affect the interaction between polymethylmethacrylate and polycarbonate and affect excellent scratch resistance and impact properties. When a modified methyl methacrylate polymer using a compound other than the above compounds as a chain transfer agent is used, the scratch resistance due to impact strength and friction coefficient reduction is not improved.

  Mercaptoesters used as chain transfer agents have an HS-X-C (= O) OR or HS-X-OC (= O) R moiety, where X is at least a divalent substituted or non-valent A substituted hydrocarbyl group, wherein R is alkyl or aryl; As an embodiment of the present invention, at least one mercapto ester can be used. Mercaptoesters include, but are not limited to, butyl mercaptopropionate, methyl mercaptopropionate, 2-ethylhexyl thioglycolate, methyl thioglycolate, ethyl thioglycolate, mercaptoethyl oleate, mercaptoethyl tartrate. The

The cycloalkyl thiol and the substituted cycloalkyl thiol are represented by, but not limited to, furfuryl mercaptan, cyclohexane thiol, and 2-furanmethane thiol.
Aryl thiols and substituted aryl thiols include, but are not limited to, benzene thiol, benzyl mercaptan, 2or4-bromobenzyl mercaptan, 2,4,6-trimethylbenzyl mercaptan, 2or4-aminothiophenol, thiophenol.
Hydroxyl thiol is represented by, but not limited to, 6-mercapto-1-hexanol, 4-mercapto-1-butanol, 8-mercapto-1-octanol, 1-thioglycerol, and mercaptoethanol.
The aminoalkyl thiol is typified by, but not limited to, 4-acetamidothiophenol and aminoethanethiol.

  The chain transfer agent is preferably used in an amount of 0.2 to 10% by weight based on the total amount of the modified methyl methacrylate polymer. Examples of the range showing further excellent characteristics at 0.2 to 10% by weight include, for example, a lower limit of 0.2, 0.5, 1, 2, 4, 6, 8, 9% by weight, and an upper limit of 1, 3, 5, 7, 9, 10% by weight. For example, the amount of the chain transfer agent is 0.5 to 10% by weight, further 2 to 10% by weight, further 5 to 10% by weight or 1 to 5% by weight.

  The modified methyl methacrylate copolymer which is the B component of the present invention is at least selected from methyl methacrylate monomer, (cyclo) alkyl (meth) acrylate, alkyl (meth) acrylate, aryl (meth) acrylate, styrene, and styrene-substituted base monomer. It is preferred to include one or more comonomers. Among them, it is produced from at least one comonomer selected from the group consisting of cyclohexyl methacrylate, isobornyl methacrylate, tetrahydrofurfuryl methacrylate, cyclopentyl methacrylate, trifluoroethyl methacrylate, hydroxyethyl methacrylate and dicyclopentadienyl methacrylate. It is particularly preferable that the unit is composed of units.

  The methyl methacrylate copolymer is preferably composed of 70% by weight or more of methyl methacrylate units and 30% by weight or less of at least one comonomer unit. For example, 70, 75, 80, 85, 90, 95% by weight or more may be used as a range exhibiting more excellent characteristics in at least 70% by weight or more of methyl methacrylate units. Examples of the range showing further excellent characteristics in at least one comonomer unit of 30% by weight or less include a lower limit of 1.5, 5, 10, 20, 25% by weight, and an upper limit of 2, 7.5, 15, 25, 29% by weight.

  Content of B component is 5-100 weight part with respect to 100 weight part of A component, Preferably it is 10-80 weight part, More preferably, it is 20-70 weight part. If the content is less than 5 parts by weight, the fluidity and pencil hardness are not improved, so it is easily scratched when reciprocating with a hard object such as a metal ball, and the content exceeds 100 parts by weight. When doing so, the impact properties are reduced.

<About component C>
The polycarbonate resin composition of the present invention contains a silicone-based core-shell copolymer as the C component. The type of the silicone-based core-shell copolymer used in the present invention is not particularly limited and may be prepared by a method known in the art. For example, the silicone-based core-shell copolymer is obtained by polymerizing a silicone rubber, and then styrene, α-methylstyrene, halogen or alkyl-substituted styrene, acrylonitrile, methacrylonitrile, C1-C8 alkyl methacrylate, C1-C8. It can be prepared by grafting to the rubber one or more compounds selected from the group consisting of alkyl acrylates, maleic anhydride, C1-C4 alkyls and phenyl N-substituted maleimides.

  The C1 to C8 methacrylic acid alkyl ester and the C1 to C8 acrylic acid alkyl ester belong to esters of methacrylic acid and acrylic acid, respectively, and are esters produced from monohydryl alcohol having 1 to 8 carbon atoms. Specific examples thereof include methacrylic acid methyl ester, methacrylic acid ethyl ester and methacrylic acid propyl ester. Of these, methacrylic acid methyl ester is the most preferred ester.

  The silicone rubber core can be made of cyclosiloxane, examples of which include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenyl. Examples thereof include cyclotrisiloxane, tetramethyltetraphenylcyclotetrosiloxane, and octaphenylcyclotetrasiloxane. Silicone rubber may be prepared by mixing one or more curing agents with the siloxane. Examples of the curing agent include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane and the like.

The silicone content of the rubber part constituting the core of the composition in the present invention is preferably 20 to 95% by weight. When the silicone content of the rubber part is less than 20% by weight, the effect of improving the scratch resistance by reducing the friction coefficient may be reduced. On the other hand, when the silicone content exceeds 95% by weight, the impact resistance of the composition is hindered, and the impact strength required for the product may not be ensured.
In addition, the silicone content based on the total silicone-based core-shell graft copolymer may be 6-85.5 wt%. More preferably, the silicone content based on the total silicone-based core-shell graft copolymer is 50 to 85% by weight in terms of scratch resistance and impact strength.

  Content of C component is 1-10 weight part with respect to 100 weight part of A component, 3-10 weight part is preferable and 5-10 weight part is more preferable. When the content is less than 1 part by weight, the scratch resistance due to impact strength and friction coefficient reduction is not improved, and when the content exceeds 10 parts by weight, the mechanical strength such as flexural modulus is low. In addition, the colorability when colored with carbon black or the like is lowered.

<About D component>
The polycarbonate resin composition of the present invention contains a sliding property improving agent as the D component. Examples of the slidability improver include fatty acid ester, polyolefin wax, silicone oil, polytetrafluoroethylene, polyalkylene glycol and the like. Among them, at least one selected from the group consisting of fatty acid ester, polyolefin wax and silicone oil is used. preferable.

  The polyolefin wax used in the present invention is an ethylene homopolymer having a molecular weight of 1,000 to 10,000, a homopolymer or copolymer of an α-olefin having 3 to 60 carbon atoms, or ethylene and carbon atoms. A copolymer with an α-olefin of 3 to 60 is preferable, and an ethylene homopolymer or a copolymer of ethylene and an α-olefin with 3 to 60 carbon atoms is more preferable. Here, the proportion of the α-olefin having 3 to 60 carbon atoms in the polymer is preferably 20 mol% or less, more preferably 10 mol% or less, based on 100 mol% of all the structural units of the polymer. It is. Such molecular weight is a number average molecular weight measured by GPC (gel hermization chromatography) method. The upper limit of the number average molecular weight is more preferably 6,000, and still more preferably 3,000. If the molecular weight is less than 1,000, the properties of the wax are insufficient. On the other hand, if the molecular weight exceeds 10,000, it is difficult to move to the surface of the molded product, and the slidability may be insufficient. . Furthermore, when the molecular weight exceeds 10,000, the appearance may be deteriorated. A molded article having excellent appearance, impact strength and weld strength can be obtained by the polyolefin wax having the molecular weight range.

Such GPC measurement was performed in a clean air environment at a temperature of 23 ° C. and a relative humidity of 50%, Shodex AC800P and (Shodex K-805L × 2) as a column, chloroform as a mobile phase, standard polystyrene as a standard substance, and a detector. As a measurement method, a GPC measurement apparatus comprising a differential refractometer is used, chloroform is used as a developing solvent, and the column temperature is 40 ° C. and the flow rate is 1 ml / min.
The carbon number of the α-olefin component is preferably 60 or less, more preferably 40 or less. More preferred specific examples include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene and the like.

Moreover, the molecular weight distribution shown by a weight average molecular weight / number average molecular weight becomes like this. Preferably it is 1-10, More preferably, it is 1.2-5, More preferably, it is the range of 1.5-4. If the molecular weight distribution is too wide, low molecular weight components tend to cause defects such as stickiness on the surface of the molded product. The density is preferably in the range of 0.880 to 0.965 g / cm ³ . The lower limit is more preferably 0.890, and still more preferably 0.920. Higher density tends to be advantageous in terms of sliding characteristics at high loads. The melting point is preferably in the range of 80 to 135 ° C, more preferably in the range of 100 to 130 ° C. The degree of branching is not particularly limited. The polyolefin wax may be a mixture of two or more, and polar groups such as an acidic functional group, an ester bond-containing functional group, and an epoxy group may be introduced. The preferable level of the amount introduced is, for example, an acidic functional group, and the acid value (JIS K5902) is preferably 20 mgKOH / g or less (more preferably 10 mgKOH / g or less, more preferably 2 mgKOH / g or less). . It is preferable that other functional groups have the same content.

  The polyolefin wax can be produced by a known method, and can be produced by a polymerization method such as solution polymerization, slurry polymerization, and gas phase polymerization using a known Ziegler catalyst, Phillips catalyst, or metallocene catalyst. . Furthermore, it can also be produced by thermally decomposing a high molecular weight polyolefin produced by such a production method, or by separating and purifying its low molecular weight component.

  The fatty acid ester used in the present invention is preferably an ester compound of pentaerythritol and an aliphatic carboxylic acid, and the aliphatic carboxylic acid preferably has 3 to 32 carbon atoms, particularly 10 to 22 carbon atoms. Aliphatic carboxylic acids are preferred. Examples of the aliphatic carboxylic acid include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid (palmitic acid), heptadecanoic acid, octadecanoic acid (stearic acid), nonadecanoic acid, behenic acid, Mention may be made of saturated aliphatic carboxylic acids such as icosanoic acid and docosanoic acid, and unsaturated aliphatic carboxylic acids such as palmitoleic acid, oleic acid, linoleic acid, linolenic acid, eicosenoic acid, eicosapentaenoic acid, and cetreic acid . Among the above, aliphatic carboxylic acids having 14 to 20 carbon atoms are preferable. Of these, saturated aliphatic carboxylic acids are preferred. In particular, stearic acid and palmitic acid are preferred. The above aliphatic carboxylic acids such as stearic acid and palmitic acid are usually produced from natural fats and oils such as animal fats such as beef tallow and lard and vegetable oils such as palm oil and sunflower oil. Therefore, these aliphatic carboxylic acids are usually a mixture containing other carboxylic acid components having different numbers of carbon atoms. Accordingly, in the production of the fatty acid ester of the present invention, aliphatic carboxylic acids produced from such natural fats and oils and in the form of a mixture containing other carboxylic acid components, particularly stearic acid and palmitic acid are preferably used.

  The pentaerythritol ester used in the present invention may be either a partial ester or a total ester (full ester). However, partial esters are more preferably full esters because they usually have a high hydroxyl value and tend to induce decomposition of the resin at high temperatures.

The acid value in the fatty acid ester used in the present invention is preferably 30 or less, more preferably in the range of 4 to 20, and still more preferably in the range of 4 to 12, from the viewpoint of thermal stability. The acid value can be substantially zero. The hydroxyl value of the pentaerythritol ester is preferably in the range of 0.1-30. Further, the iodine value is preferably 10 or less. The iodine value can be substantially zero. These characteristics can be obtained by a method defined in JIS K 0070.
The TGA 5% weight loss temperature in the fatty acid ester used in the present invention is preferably 200 ° C. or higher, more preferably 250 ° C. or higher, from the viewpoint of thermal stability.

  The silicone oil used in the present invention is not particularly limited, and can be arbitrarily selected from known silicone oils. Silicone oil has a siloxane bond as a main chain and an organic group in a side chain. Examples of the organic group include a methyl group, a vinyl group, an ethyl group, a propyl group, and a phenyl group. Specifically, examples of the silicone oil include dimethylpolysiloxane, methylethylpolysiloxane, methyloctylpolysiloxane, methylvinylpolysiloxane, methylphenylpolysiloxane, methyl (3,3,3-trifluoropropyl) polysiloxane. Can be mentioned.

The silicone oil used in the present invention is particularly high viscosity among silicone oils, preferably a polyorganosiloxane having a number average molecular weight of about 100,000 to 1,000,000, and further contains inorganic oxide particles. preferable. The inorganic oxide particles may be inorganic oxide particles containing silicon (Si) atoms, and may be inorganic composite oxide particles containing aluminum (Al) atoms or magnesium (Mg) atoms in addition to Si atoms. Good. Examples of such inorganic oxide particles include SiO ₂ , SiO, aluminosilicate, MgSiO _{3 and the} like. Among these, SiO ₂ is preferable from the viewpoint of compatibility with silicone oil.

  Content of D component is 0.1-6 weight part with respect to 100 weight part of A component, Preferably it is 0.5-5 weight part, More preferably, it is 1-4 weight part. When the content is less than 0.1 parts by weight, the scratch resistance due to the reduction of the friction coefficient is not improved, and when the content exceeds 6 parts by weight, the mechanical strength such as bending elastic modulus and molding Sex is reduced.

<About E component>
The polycarbonate resin composition of the present invention can contain a polyester resin as the E component. Of the dicarboxylic acid component and diol component forming the polyester, the polyester resin is 70 mol% or more, preferably 90 mol% or more, and most preferably 99 mol% or more of 100 mol% of the dicarboxylic acid component is aromatic dicarboxylic acid. Polyester is preferred.

  Examples of this dicarboxylic acid include terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbene dicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid. Acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, bisbenzoic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4-diphenyl ether dicarboxylic acid 4,4-diphenoxyethanedicarboxylic acid Acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid and the like. These dicarboxylic acids can be used alone or in admixture of two or more.

  In addition to the above aromatic dicarboxylic acid, the polyester resin of the present invention can be copolymerized with an aliphatic dicarboxylic acid component of less than 30 mol%. Specific examples thereof include adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid and the like.

  Examples of the diol component of the present invention include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, trans- or cis-2,2, 4,4-tetramethyl-1,3-cyclobutanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 1,3 -Cyclohexanedimethanol, decamethylene glycol, cyclohexanediol, p-xylenediol, bisphenol A, tetrabromobisphenol A, tetrabromobisphenol A-bis (2-hydroxyethyl ether) and the like. Further, an aromatic polyester resin slightly copolymerized with polyethylene glycol can be used as the diol component. The molecular weight of polyethylene glycol is preferably in the range of 150 to 6,000. These can be used alone or in admixture of two or more. In addition, it is preferable that the dihydric phenol in a diol component is 30 mol% or less.

  Specific aromatic polyester resins include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), polyhexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1, In addition to 2-bis (phenoxy) ethane-4,4′-dicarboxylate, copolymer polyesters such as polyethylene isophthalate / terephthalate copolymer, polybutylene terephthalate / isophthalate copolymer, and the like can be given.

  In addition, the terminal group structure of the polyester resin used in the present invention is not particularly limited, and even when the ratio of the hydroxyl group and the carboxyl group in the terminal group is substantially the same, Good. Moreover, those terminal groups may be sealed by reacting a compound having reactivity with such terminal groups.

  For the production method of the polyester resin used in the present invention, in accordance with a conventional method, in the presence of a polycondensation catalyst containing titanium, germanium, antimony and the like, the dicarboxylic acid component and the diol component are polymerized while heating, By discharging water or lower alcohol produced as a by-product out of the system. For example, germanium-based polymerization catalysts include germanium oxides, hydroxides, halides, alcoholates, phenolates, and the like. More specifically, germanium oxide, germanium hydroxide, germanium tetrachloride, tetramethoxygermanium, etc. Can be illustrated. For example, as an organic titanium compound that is a titanium-based polymerization catalyst, preferred examples include titanium tetrabutoxide, titanium isopropoxide, titanium oxalate, titanium acetate, titanium benzoate, titanium trimellitic acid, tetrabutyl titanate and trimellitic anhydride. And the like. The amount of the organic titanium compound used is preferably such that the titanium atom is 3 to 12 mg atom% with respect to the acid component constituting the aromatic polyester resin.

Further, in the present invention, compounds such as manganese, zinc, calcium, magnesium, etc., which are used in a transesterification reaction that is a prior stage of a conventionally known polycondensation, can be used in combination, and phosphoric acid or phosphorous after completion of the transesterification reaction. Such a catalyst can be deactivated and polycondensed with an acid compound or the like. Furthermore, the production method of the aromatic polyester resin can be either batch type or continuous polymerization type. Moreover, various stabilizers and modifiers can be blended in the obtained polyester resin. The molecular weight of the polyester resin of the present invention is not particularly limited, but the intrinsic viscosity measured at 35 ° C. using o-chlorophenol as a solvent is preferably in the range of 0.4 to 1.5 dl / g, particularly preferably 0. The range is from 45 to 1.2 dl / g.
Furthermore, among the polyester resins, polybutylene terephthalate and polyethylene terephthalate are preferable.

The polybutylene terephthalate of the present invention is a polymer obtained by polycondensation reaction from terephthalic acid or a derivative thereof and 1,4-butanediol or a derivative thereof, but as described above, other dicarboxylic acid components and other alkylenes. Includes copolymerized glycol components.
The end group structure of polybutylene terephthalate is not particularly limited, as described above, but more preferably it has less terminal carboxyl groups than terminal hydroxyl groups.

  Moreover, although the above-mentioned various methods can be taken also about a manufacturing method, Preferably it is the following. The production method is more preferably a continuous polymerization type. This is because the quality stability is high and the cost is advantageous. Further, an organic titanium compound is preferably used as the polymerization catalyst. This is because the influence on the transesterification reaction tends to be small.

  The polyethylene terephthalate of the present invention (hereinafter sometimes abbreviated as “PET”) is mainly composed of ethylene terephthalate, the dicarboxylic acid component of which is 85 mol% or more, and the diol component is 85 of ethylene glycol. Polyester containing at least mol%. PET preferably contains 90 mol% or more, more preferably 95 mol% or more of a terephthalic acid component as a dicarboxylic acid component. PET preferably contains 90 mol% or more, more preferably 95 mol% or more of ethylene glycol as a diol component.

  Among the above, PET is preferably a polyester which does not contain any other copolymer component and is produced substantially only from a terephthalic acid component and an ethylene glycol component. However, even in such a polyester, about 0.5 mol% or more of a diethylene glycol component is usually contained in 100 mol% of the diol component as a side reaction product during polymerization. Accordingly, PET may contain a small amount of a diethylene glycol component. The diethylene glycol component is preferably 6 mol% or less, more preferably 5 mol% or less, and still more preferably 4 mol% or less, in 100 mol% of the diol component.

  The molecular weight of the PET is preferably such that the intrinsic viscosity measured at 35 ° C. using o-chlorophenol as a solvent is in the range of 0.4 to 1.3 dl / g, and 0.45 to 1.2 dl / g. The range of is more preferable. The terminal carboxyl group amount is not particularly limited, but is preferably 30 eq / ton or less, and more preferably 25 eq / ton or less. As a lower limit, 1 eq / ton or more is practically appropriate.

  The content of component E is preferably 10 to 100 parts by weight, more preferably 10 to 80 parts by weight, and still more preferably 15 to 70 parts by weight with respect to 100 parts by weight of component A. When the content is less than 10 parts by weight, it may not be possible to expect further improvement in scratch resistance by reducing the friction coefficient. When the content exceeds 100 parts by weight, the flexural modulus and impact resistance are not expected. May decrease.

<Other ingredients>
<Heat stabilizer>
Various stabilizers can be used in the polycarbonate resin composition of the present invention in order to stabilize the molecular weight and hue during molding. Examples of such stabilizers include phosphorus stabilizers and hindered phenol stabilizers.

(Phosphorus stabilizer)
Examples of the phosphorus stabilizer used in the present invention include phosphorous acid, phosphoric acid, phosphonous acid, phosphonic acid and esters thereof, and tertiary phosphine.
Specifically, as the phosphite compound, for example, triphenyl phosphite, tris (nonylphenyl) phosphite, tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl monophenyl Phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, tris (diethylphenyl) phosphite, tris (di-iso-propylphenyl) phosphite, tris (di -N-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,6-di-tert-butylphenyl) phosphite, dis Allyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-ethylphenyl) pentaerythritol diphosphite, bis {2,4-bis (1-methyl-1-phenylethyl) phenyl} pentaerythritol diphosphite, phenylbisphenol A Examples include pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, and dicyclohexyl pentaerythritol diphosphite.

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

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

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

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

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

  The phosphorus stabilizers can be used alone or in combination of two or more. Among the phosphorus stabilizers, phosphonite compounds or phosphite compounds represented by the following general formula (1) are preferable.

（式（１）中、ＲおよびＲ’は炭素数６〜３０のアルキル基または炭素数６〜３０のアリール基を表し、互いに同一であっても異なっていてもよい。）

(In formula (1), R and R ′ represent an alkyl group having 6 to 30 carbon atoms or an aryl group having 6 to 30 carbon atoms, and may be the same or different from each other.)

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

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

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

(Hindered phenolic antioxidant)
As the hindered phenol-based antioxidant used in the present invention, various compounds that are usually blended in a resin can be used. Examples of such hindered phenol-based antioxidants include α-tocopherol, butylhydroxytoluene, sinapir alcohol, vitamin E, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2-tert-butyl-6- (3′-tert-butyl-5′-methyl-2′-hydroxybenzyl) -4-methylphenyl acrylate, 2,6-di-tert-butyl-4- (N, N -Dimethylaminomethyl) phenol, 3,5-di-tert-butyl-4-hydroxybenzylphosphonate diethyl ester, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis ( 4-ethyl-6-tert-butylphenol), 4,4′-methylenebis ( , 6-di-tert-butylphenol), 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-dimethylene-bis (6-α-methyl-benzyl-p-cresol), 2 2,2′-ethylidene-bis (4,6-di-tert-butylphenol), 2,2′-butylidene-bis (4-methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-) 6-tert-butylphenol), triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4-methyl 6- (3-ter -Butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1 , -Dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-thiobis (3 -Methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4 '-Di-thiobis (2,6-di-tert-butylphenol), 4,4'-tri-thiobis (2,6-di-tert-butylphenol), 2,2-thi Diethylenebis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di-tert -Butylanilino) -1,3,5-triazine, N, N'-hexamethylenebis- (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N'-bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5- Trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) ) Isocyanurate, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanate 1,3,5-tris 2 [3 (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] ethyl isocyanurate, tetrakis [methylene-3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionate] methane, triethylene glycol-N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, triethylene glycol-N-bis-3- ( 3-tert-butyl-4-hydroxy-5-methylphenyl) acetate, 3,9-bi [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) acetyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] Undecane, tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, 1,3,5-trimethyl-2,4,6-tris (3-tert-butyl- Examples thereof include 4-hydroxy-5-methylbenzyl) benzene and tris (3-tert-butyl-4-hydroxy-5-methylbenzyl) isocyanurate.

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

  As an antioxidant based on tetrakis [methylene-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] methane, commercially available as Irganox 1010 (trademark, manufactured by CHIBA SPECIALTY CHEMICALS). Available. Antioxidants based on octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate include Irganox 1076 (trademark, manufactured by CHIBA SPECIALTY CHEMICALS) and Adeka Stab AO-18 (trademark, Asahi) It is commercially available as Denka Kogyo Co., Ltd.) and any of them can be used. 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] An antioxidant mainly composed of undecane is commercially available as AO-80 (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.) and can be used.

  The phosphorus stabilizer and / or hindered phenol antioxidant is preferably 0.0001 to 1 part by weight, more preferably 0.001 to 0.1 part by weight, and still more preferably 100 parts by weight of component A. It mix | blends in the ratio of 0.005-0.1 weight part. When these are used in combination, 0.01 to 0.3 parts by weight of a phosphorus stabilizer and 0.01 to 0.3 parts by weight of a hindered phenol antioxidant are added to 100 parts by weight of component A. It is preferred that

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

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

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

  Specific examples of the ultraviolet absorber include benzotriazole-based compounds such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 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) benzo Triazole, 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 copolymer with the monomer 2 such as a copolymer with a possible vinyl monomer and a copolymer of 2- (2′-hydroxy-5-acryloxyethylphenyl) -2H-benzotriazole with a vinyl monomer copolymerizable with the monomer. Examples include polymers having a -hydroxyphenyl-2H-benzotriazole skeleton.

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

As the ultraviolet absorber, specifically, in the cyclic imino ester type, for example, 2,2′-p-phenylenebis (3,1-benzoxazin-4-one), 2,2 ′-(4,4′-diphenylene) ) Bis (3,1-benzoxazin-4-one), 2,2 ′-(2,6-naphthalene) bis (3,1-benzoxazin-4-one) and the like.
Further, as the ultraviolet absorber, specifically, for cyanoacrylate, for example, 1,3-bis-[(2′-cyano-3 ′, 3′-diphenylacryloyl) oxy] -2,2-bis [(2- Examples include cyano-3,3-diphenylacryloyl) oxy] methyl) propane and 1,3-bis-[(2-cyano-3,3-diphenylacryloyl) oxy] benzene.

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

Among them, benzotriazole and hydroxyphenyltriazine are preferable from the viewpoint of ultraviolet absorption ability, and cyclic imino ester and cyanoacrylate are preferable from the viewpoint of heat resistance and hue. You may use the said ultraviolet absorber individually or in mixture of 2 or more types.
The content of the ultraviolet absorber is preferably 0.01 to 2 parts by weight, more preferably 0.03 to 2 parts by weight, still more preferably 0.04 to 1 part by weight, particularly preferably 100 parts by weight of component A. Is 0.05 to 0.5 parts by weight.

(Flame retardants)
Various compounds known as flame retardants for polycarbonate resins may be blended in the polycarbonate resin composition of the present invention. The compounding of the compound used as the flame retardant not only improves the flame retardancy but also provides, for example, an improvement in antistatic properties, fluidity, rigidity, and thermal stability based on the properties of each compound.

  Examples of such flame retardants include (i) organometallic salt flame retardants (for example, alkali (earth) organic sulfonate metal salts, borate metal salt flame retardants, stannate metal salt flame retardants, etc.), and (ii) Organophosphorous flame retardants (for example, monophosphate compounds, phosphate oligomer compounds, phosphonate oligomer compounds, phosphonitrile oligomer compounds, and phosphonic acid amide compounds), (iii) silicone flame retardants comprising silicone compounds, and (iv) halogens And flame retardant (for example, brominated epoxy resin, brominated polystyrene, brominated polycarbonate (including oligomers), brominated polyacrylate, chlorinated polyethylene, etc.).

The content of the organometallic salt flame retardant is preferably 0.001 to 1 part by weight, more preferably 0.005 to 0.5 part by weight, and still more preferably 0.01 to 0 part based on 100 parts by weight of the component A. .1 part by weight.
The content of the organophosphorus flame retardant is preferably 0.1 to 30 parts by weight, more preferably 1 to 25 parts by weight, and still more preferably 5 to 20 parts by weight based on 100 parts by weight of the component A.
The content of the silicone flame retardant is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, still more preferably 1 to 5 parts by weight, based on 100 parts by weight of the component A.

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

  Polytetrafluoroethylene (fibrillated PTFE) having fibril-forming ability has a very high molecular weight, and exhibits a tendency to bind PTFE to each other by an external action such as shearing force to form a fiber. Its number average molecular weight ranges from 1.5 million to tens of millions. The lower limit is more preferably 3 million. The number average molecular weight is calculated based on the melt viscosity of polytetrafluoroethylene at 380 ° C. as disclosed in JP-A-6-145520. That is, the fibrillated PTFE has a melt viscosity at 380 ° C. measured by the method described in the above publication of preferably 107 to 1013 poise, more preferably 108 to 1012 poise.

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

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

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

In order to more effectively utilize the good mechanical properties and surface appearance properties of the polycarbonate resin composition of the present invention, the fibrillated PTFE is preferably finely dispersed as much as possible. As a means of achieving such fine dispersion, the above mixed form of fibrillated PTFE is advantageous. A method of directly supplying an aqueous dispersion in a melt kneader is also advantageous for fine dispersion. However, in the case of the aqueous dispersion form, consideration is required in that the hue is slightly deteriorated. The proportion of fibrillated PTFE in the mixed form is preferably 10 to 80% by weight, more preferably 15 to 75% by weight, in 100% by weight of the mixture. When the ratio of fibrillated PTFE is in such a range, good dispersibility of fibrillated PTFE can be achieved.
The content of fibrillated PTFE is preferably 0.001 to 1 part by weight, more preferably 0.1 to 0.7 part by weight, based on 100 parts by weight of component A.

(Antistatic agent)
The polycarbonate resin composition of the present invention may be required to have antistatic performance. In such a case, it is preferable to include an antistatic agent. Examples of the antistatic agent include (1) aryl sulfonic acid phosphonium salts represented by dodecylbenzenesulfonic acid phosphonium salts, organic sulfonic acid phosphonium salts such as alkyl sulfonic acid phosphonium salts, and tetrafluoroboric acid phosphonium salts. Examples thereof include phosphonium borate salts. The content of the phosphonium salt is suitably 5 parts by weight or less based on 100 parts by weight of component A, preferably 0.05 to 5 parts by weight, more preferably 1 to 3.5 parts by weight, and still more preferably 1 part. The range is from 5 to 3 parts by weight.

  Examples of the antistatic agent include: (2) lithium organic sulfonate, organic sodium sulfonate, organic potassium sulfonate, cesium organic sulfonate, rubidium organic sulfonate, calcium organic sulfonate, magnesium organic sulfonate, and barium organic sulfonate. And organic sulfonate alkali (earth) metal salts. Such metal salts are also used as flame retardants as described above. More specific examples of such metal salts include metal salts of dodecylbenzene sulfonic acid and metal salts of perfluoroalkane sulfonic acid. The content of the organic sulfonate alkali (earth) metal salt is suitably 0.5 parts by weight or less based on 100 parts by weight of component A, preferably 0.001 to 0.3 parts by weight, more preferably 0. 0.005 to 0.2 parts by weight. In particular, alkali metal salts such as potassium, cesium, and rubidium are preferable.

  Examples of the antistatic agent include (3) organic sulfonic acid ammonium salts such as alkyl sulfonic acid ammonium salt and aryl sulfonic acid ammonium salt. The ammonium salt is suitably 0.05 parts by weight or less based on 100 parts by weight of component A. Examples of the antistatic agent include (4) a polymer containing a poly (oxyalkylene) glycol component such as polyether ester amide as a constituent component. The polymer is suitably 5 parts by weight or less based on 100 parts by weight of component A.

(Pigment)
The polycarbonate resin composition of the present invention can contain carbon black as a pigment. The content of carbon black is preferably 0.1 to 5 parts by weight, more preferably 0.2 to 4.5 parts by weight with respect to 100 parts by weight of component A, and 0.3 to 4 parts. More preferably, it is part by weight. If the content is less than 0.1 parts by weight, sufficient colorability may not be obtained, and if it exceeds 5 parts by weight, mechanical properties may be deteriorated.

<Manufacture of polycarbonate resin composition and molded product>
Arbitrary methods are employ | adopted in order to manufacture the polycarbonate resin composition of this invention. For example, component A, component B, component C and component D, and optionally component E and other additives are sufficiently mixed using premixing means such as a V-type blender, Henschel mixer, mechanochemical apparatus, extrusion mixer, etc. After that, if necessary, granulate the pre-mixture with an extrusion granulator or briquetting machine, and then melt and knead it with a melt kneader represented by a vent type twin screw extruder, and then with a pelletizer. The method of pelletizing is mentioned.

  In addition, a method of supplying each component independently to a melt kneader represented by a vent type twin screw extruder, or a part of each component is premixed and then supplied to the melt kneader independently of the remaining components. The method of doing is also mentioned. Examples of the method of premixing a part of each component include a method in which components other than the component A are premixed in advance and then the aromatic polycarbonate resin of the component A is mixed or directly supplied to the extruder. As a premixing method, for example, when a component having a powder form is included as the component A, a part of the powder and an additive to be blended are mixed to produce a master batch of the additive diluted with the powder. A method using a master batch can be mentioned. Furthermore, the method etc. which supply one component independently from the middle of a melt extruder are mentioned. In addition, when there exists a liquid thing in the component to mix | blend, what is called a liquid injection apparatus or a liquid addition apparatus can be used for supply to a melt extruder.

  As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gas generated from the melt-kneaded resin can be preferably used. 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. Examples of the melt kneader include a banbury mixer, a kneading roll, a single screw extruder, a multi-screw extruder having three or more axes, in addition to a twin screw 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. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Furthermore, in the manufacture of such pellets, various methods already proposed for polycarbonate resin for optical discs are used to narrow the shape distribution of pellets, reduce miscuts, and reduce fine powder generated during transportation or transportation. In addition, it is possible to appropriately reduce bubbles (vacuum bubbles) generated inside the strands and pellets. By these prescriptions, it is possible to increase the molding cycle and reduce the occurrence rate of defects such as silver. Moreover, although the shape of a pellet can take common shapes, such as a cylinder, a prism, and a spherical shape, 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.

  The polycarbonate resin composition of the present invention can be produced in various products by usually injection-molding the pellets produced as described above to obtain molded products. In such injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including a method of injecting a supercritical fluid), insert molding, in-mold coating molding, heat insulation Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, sandwich molding, and ultra-high speed injection molding. 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 extruded products, sheets, films, etc. by extrusion molding. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can also be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. Further, the polycarbonate resin composition of the present invention can be formed into a molded product by rotational molding or blow molding.

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

The following examples further illustrate the present invention.
(1) Preparation of resin composition [Examples 1 to 12, Comparative Examples 1 to 10]
After mixing various additives shown in Table 1 and Table 2 with blenders in respective blending amounts with 100 parts by weight of polycarbonate resin powder produced from bisphenol A and phosgene by an interfacial condensation polymerization method, a vent type twin screw extruder was used. Used to melt and knead to obtain pellets. The additives to be added to the polycarbonate resin were preliminarily prepared with a polycarbonate resin in advance with a concentration of 10 to 100 times the blending amount as a guide, and then the whole was mixed by a blender. As the extruder, a vent type twin screw extruder (Kobe Steel Works KTX-30) having a diameter of 30 mmφ was used. The extrusion conditions were a discharge rate of 20 kg / h, a screw rotation speed of 120 rpm, and a vent vacuum of 3 kPa, and the extrusion temperature was 260 ° C. from the first supply port to the die part.
The obtained pellets were dried with a hot air circulation dryer at 120 ° C. for 5 hours, and then an injection molding machine [SG260M-HP manufactured by Sumitomo Heavy Industries, Ltd.] was used. Using a mold having a cavity surface with an arithmetic average roughness (Ra) of 0.03 μm under conditions of 70 ° C. and a shooting speed of 20 mm / sec, the width is 50 mm, the length is 90 mm, and the thickness is 3 mm from the gate side ( A three-stage plate having a length of 20 mm, 2 mm (length of 45 mm), and 1 mm (length of 25 mm) was molded. Tables 1 and 2 show the evaluation results of the obtained molded plate.

(A component)
A-1: Polycarbonate resin powder having a viscosity average molecular weight of 19,700 produced from bisphenol A and phosgene by an interfacial condensation polymerization method (manufactured by Teijin Limited: Panlite L-1225WX)
(B component)
B-1: Modified methyl methacrylate copolymer [Modified methyl methacrylate copolymer using butyl mercaptopropionate as a chain transfer agent, manufactured by Dow Chemical Japan Ltd .: ULTRALOID AS-8001]
(C component)
C-1: Silicone core-shell copolymer having a silicone content of 60 to 70% by weight (manufactured by Kaneka Corporation: KANEACE MR-01)
(D component)
D-1: Polyolefin wax having a number average molecular weight of 1,510 (Mitsui Chemicals, Inc .: High Wax 310MP)
D-2: Silicone oil (Asahi Kasei Wacker Silicone Co., Ltd. product: GENIOPLAST Pellet S)
D-3: Fatty acid ester: full ester of pentaerythritol and aliphatic carboxylic acid (manufactured by Riken Vitamin Co., Ltd .: Riquester EW-400)
(E component)
E-1: Polyethylene terephthalate resin (manufactured by Teijin Limited: TRN-8550FF)
(Other ingredients)
(UV absorber)
F-1: Benzotriazole-based ultraviolet absorber (manufactured by Ciba Specialty Chemicals: Tinuvin 234)
(Coloring agent)
G-1: Carbon black master (Koshigaya Kasei Co., Ltd .: ROYALBLACK961S)
(Comparative example)
B-2: Modified methyl methacrylate copolymer [Aromatic acrylate-methyl methacrylate copolymer using n-octyl mercaptan as a chain transfer agent, manufactured by Mitsubishi Rayon Co., Ltd .: Metabrene H-880]
B-3: Modified methyl methacrylate copolymer [Methyl methacrylate-methyl acrylate copolymer using alkyl mercaptan as chain transfer agent, manufactured by Mitsubishi Rayon Co., Ltd .: Acrypet VH001]
B-4: Modified methyl methacrylate copolymer [modified methyl methacrylate copolymer using n-dodecyl mercaptan as a chain transfer agent]

Each characteristic of the molded product was measured by the following method.
(1) Pencil hardness Pencil hardness was measured according to JIS K5600.

(2) Scratch resistance (2-1)
A reciprocating friction and wear tester AFT-15M manufactured by Orientec Co., Ltd. was used as an evaluation device. A pin-shaped test piece (material: steel) having a spherical surface at the tip, in which a hemisphere with a diameter of 3 mmφ and a cylinder with a diameter of 5 mmφ and a length of 30 mmφ were combined at a circular cross section, was mounted on a fixed-side test piece holder. On the other hand, a three-stage plate having a width of 50 mm, a length of 90 mm, and a thickness of 3 mm (length 20 mm), 2 mm (length 45 mm), and 1 mm (length 25 mm) from the resin compositions of Examples and Comparative Examples. It was prepared by injection molding under the above conditions, and fixed on a pedestal that reciprocated. A load of 4.9 N is applied with the spherical surface at the tip of the pin-shaped test piece in the state where the cylindrical axis direction of the pin-shaped test piece is parallel to the plane normal direction of the flat test piece. It contacted in the state which applied. In such a contact state, a capacity connected to the pin-shaped test piece side by reciprocating 100 times a distance of 20 mm one way on a straight line in the plane at a rate of 2 seconds per reciprocation in an atmosphere of 23 ° C. and relative humidity 50% RH. The frictional force after 100 operations was measured with a 49N load cell, and the dynamic friction coefficient was calculated from the relationship with the load. Moreover, it determined by the following reference | standards visually.
○: Scraping does not occur in the molded product.
X: Scraping occurs in the molded product.

(2-2)
A reciprocating friction and wear tester AFT-15M manufactured by Orientec Co., Ltd. was used as an evaluation device. To the pin-shaped test piece of the same shape as (2-1) mounted on the fixed-side test piece holder, a plate having a width of 10 mm, a length of 10 mm, and a thickness of 2 mm is adhered, and further covered with a cotton cloth to be fixed. A test specimen was obtained. Kanakin No. 3 specified by the Japanese Standards Association was used for the cotton cloth. On the other hand, a three-stage plate having a width of 50 mm, a length of 90 mm, and a thickness of 3 mm (length 20 mm), 2 mm (length 45 mm), and 1 mm (length 25 mm) from the resin compositions of Examples and Comparative Examples. It was prepared by injection molding under the above conditions, and fixed on a pedestal that reciprocated. In a state where a load of 4.9 N is applied to the plane portion of the pin-shaped test piece in a state where the cylindrical axis direction of the pin-shaped test piece and the plane normal direction of the flat plate-shaped test piece are parallel to each other. Made contact. In such a contact state, a capacity connected to the pin-shaped test piece side by reciprocating 500 times a distance of 20 mm one way on a straight line in a plane at a rate of 2 seconds per reciprocation in an atmosphere of 23 ° C. and relative humidity 50% RH. The frictional force after 100 operations was measured with a 49N load cell, and the dynamic friction coefficient was calculated from the relationship with the load. Moreover, it determined by the following reference | standards visually.
○: No scratches are attached.
Δ: Slightly scratched
X: Scratches are marked.

(3) Fluidity (melt volume rate (MVR))
In conformity with JIS K-7210, using a Techno Seven Co. L251-11 type MFR measuring instrument, Tg + 280 ℃, indicated by the amount of polymer flowing out to 10 minutes under a load of 2.16 kg (cm ^3).

(4) Impact characteristics (4-1) Charpy impact strength According to ISO 179, the Charpy impact strength with a notch was measured.
(4-2) High-speed surface impact test It was carried out in accordance with ISO6603. Using Shimadzu Hydroshot HTM-1 with a test speed of 7 m / sec, impact core radius of 6.4 mm, and using five three-stage plates obtained at the time of pencil hardness measurement, The impact energy was measured and the fracture form was observed visually. The evaluation was performed according to the following criteria. It must be ductile or ductile / brittle.
Ductility: All five sheets showed ductile fracture.
Ductile / brittleness: Ductile fracture and brittle fracture occurred randomly in 5 sheets.
Brittle: All five sheets exhibited brittle fracture.

(5) Colorability Colorability evaluation was performed by color difference evaluation. The hue (L, a, b) of a molded product (three-stage plate, 2 mm thickness) obtained from a composition containing carbon black was subjected to C light source reflection using SE-2000 manufactured by Nippon Denshoku Co., Ltd. It was measured by. When the color difference L is 3.0 or more and 13.0 or less, the colorability is excellent.

(6) Flexural modulus The flexural modulus was measured according to ISO 178. In the present invention, the flexural modulus is preferably 2200 MPa or more.

From the results of the examples and comparative examples, the following can be understood.
In Examples 1 to 12, the blending ratio of the D component to the B component was changed within the prescribed range of the present invention, but the comparative example 1 in which the B component was not prescribed and the comparative example with less B component than prescribed. Compared to 2, the fluidity and pencil hardness are excellent, and it can be seen that there is no scratch in the reciprocating friction test using a steel ball, and the impact characteristics are excellent compared to Comparative Example 3 where the B component is more than specified. I understand that Moreover, compared with Comparative Examples 4, 5 and 6 using B-2, B-3 and B-4 components which are outside the specified range of the B component of the present invention, they are excellent in scratch resistance and excellent in impact characteristics. I understand that. Moreover, it turns out that it is excellent in the flaw resistance and the impact characteristic compared with the comparative example 7 which did not use C component of this invention. Moreover, it turns out that it is excellent in coloring property and the bending characteristic compared with the comparative example 8 with more C components than regulation. Moreover, it turns out that it is excellent in damage resistance compared with the comparative example 9 which did not use D component of this invention. In Comparative Example 10 in which a large amount of the D component of the present invention was blended outside the specified range, the moldability deteriorated and the molding could not be performed, and thus each data could not be taken.

  Therefore, from the above examples and comparative examples, an aromatic polycarbonate resin composition and a molded article excellent in pencil hardness, improved in scratch resistance due to reduction in friction coefficient, and excellent in fluidity and impact properties are obtained according to the present invention. It was confirmed that it was obtained for the first time by the configuration.

  Since the aromatic polycarbonate resin composition of the present invention is excellent in scratch resistance and also in impact characteristics, the molded product thereof has a car navigation or car audio casing, front panel, knob volume, etc. Includes a wide range of instrument panel parts, console box parts, automotive interior parts such as door trims, flat display panels, personal computers, PDAs, televisions, videos, cameras, printers, FAX, and other electrical / electronic / OA equipment housings. It can be used in the field and has very high industrial applicability.

Claims (7)

  (A) 5 to 100 parts by weight of (B) modified methyl methacrylate polymer (B component) with respect to 100 parts by weight of aromatic polycarbonate resin (A component), (C) silicone-based core-shell copolymer (C component) 1) to 10 parts by weight, (D) 0.1 to 6 parts by weight of a slidability improver (component D), and the modified methyl methacrylate polymer is a modified methyl methacrylate homopolymer or modified methyl methacrylate copolymer. And obtained by reaction with at least one chain transfer agent selected from the group consisting of mercaptoesters, cycloalkylthiols, substituted cycloalkylthiols, hydroxylthiols, arylthiols, substituted arylthiols and aminoalkylthiols. An aromatic polycarbonate resin composition characterized by the above.   The aromatic polycarbonate resin composition according to claim 1, wherein 10 to 100 parts by weight of (E) polyester resin (E component) is contained with respect to 100 parts by weight of component A.   The aromatic polycarbonate resin composition according to claim 1, wherein the component D is at least one selected from the group consisting of fatty acid esters, polyolefin waxes, and silicone oils.   The aromatic polycarbonate resin composition according to any one of claims 1 to 3, wherein the component D is a polyolefin wax having a molecular weight of 1,000 to 10,000.   The molded article obtained from the aromatic polycarbonate resin composition in any one of Claims 1-4.   The molded product according to claim 5 obtained by injection molding.   The molded article according to claim 5, which is a member for an automobile.