JP5880307B2 - Aromatic polycarbonate resin composition and molded article thereof - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition. Specifically, an aromatic polycarbonate resin composition that gives a molded article having excellent moldability (fluidity), surface hardness, impact resistance, appearance, and jet blackness, and this aromatic polycarbonate resin composition are molded. It relates to molded products.

  Aromatic polycarbonate resin is excellent in transparency, impact resistance, heat resistance, etc., and the resulting molded product is also excellent in dimensional stability etc., so housings for electrical and electronic equipment, automotive parts, It is widely used as a raw material resin for the production of precision molded products such as optical disk related parts. In particular, in a case of a home appliance, an electronic device, an image display device, or the like, a product with high commercial value can be obtained by making use of its beautiful appearance.

  On the other hand, although polymethyl methacrylate has problems in dimensional stability, impact resistance, etc., it is excellent in transparency, surface hardness, weather resistance, etc., so an acrylic compound such as polymethyl methacrylate is added to an aromatic polycarbonate resin. To obtain a resin composition having excellent surface hardness. Further, by blending a copolymerized acrylic compound and an acrylic compound with a controlled three-dimensional structure into a polycarbonate, it is possible to provide a resin composition that is further excellent in surface hardness and transparency. For example, Patent Document 1 proposes a resin composition in which an aromatic polycarbonate resin is mixed with syndiotactic polymethyl methacrylate in which at least 50% of all methyl methacrylate units are in a syndiotactic arrangement. Describes that the aromatic polycarbonate resin and the syndiotactic polymethyl methacrylate are excellent in compatibility and become a transparent single phase in all ratios. In addition, in this patent document 1, although it describes as the range of 30,000-300,000 about the molecular weight of the syndiotactic polymethylmethacrylate mix | blended with polymethylmethacrylate, this molecular weight is not a critical thing. The molecular weight of the syndiotactic polymethyl methacrylate used in the examples is not clarified.

JP-A-6-128475

  Although the effect of improving the surface hardness can be obtained by blending the syndiotactic polymethyl methacrylate described in Patent Document 1, the resin composition described in Patent Document 1 shows that the molded product obtained can be obtained by studying the present inventors. In some cases, the impact resistance and the appearance were inferior. Moreover, in patent document 1, in order to provide the jetness to a molded article, the blackness quality at the time of mix | blending carbon black, impact resistance, etc. were not examined at all.

  The present invention solves the above-mentioned problems of the resin composition of Patent Document 1 and provides a molded product having excellent heat resistance, moldability (fluidity), and excellent surface hardness, impact resistance, and appearance. An aromatic polycarbonate resin composition capable of imparting good jetness without impairing impact resistance when carbon black is blended, and this aromatic polycarbonate resin composition It is an object of the present invention to provide a molded product obtained by molding

  As a result of intensive studies to solve the above problems, the present inventor is an acrylic compound having a high syndiotactic ratio as an acrylic compound to be blended with an aromatic polycarbonate resin for improving surface hardness, and has a specific weight average. By using an acrylic compound having a molecular weight in a predetermined ratio, it is possible to obtain a molded article excellent in appearance with good moldability (fluidity) without impairing the impact resistance of the aromatic polycarbonate resin. It has been found that a molded article having excellent jetness can be obtained by blending carbon black having a predetermined particle size.

  The present invention has been achieved based on such findings, and the gist thereof is as follows.

[1] As a resin component, (A) 50 to 90 parts by mass of an aromatic polycarbonate resin having a viscosity average molecular weight of 15,000 to 40,000, and (B) a weight average molecular weight of 60,000 to 80,000, 100 parts by mass in total of 10 to 50 parts by mass of an acrylic compound having a tic ratio of 55% or more, and (C) 0.1% of carbon black having an average particle size of 15 to 20 nm with respect to 100 parts by mass of the resin component Aromatic polycarbonate resin composition characterized by containing ~ 2.0 parts by mass.

[2] The aromatic polycarbonate resin composition according to [1], wherein the acrylic compound (B) is polymethyl methacrylate.

[3] An aromatic polycarbonate resin molded article obtained by molding the aromatic polycarbonate resin composition according to [1] or [2].

  According to the present invention, as a resin component, (A) an aromatic polycarbonate resin having a viscosity average molecular weight of 15,000 to 40,000, (B) a weight average molecular weight of 60,000 to 80,000, and a syndiotactic ratio Is an aromatic polycarbonate resin composition that provides a molded product having excellent heat resistance, moldability (fluidity), surface hardness, impact resistance, and appearance by blending an acrylic compound having a content of 55% or more at a predetermined ratio. In addition, by blending carbon black having a predetermined particle size range, a molded product having excellent jetness, high quality, and high commercial value can be obtained.

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the embodiments and examples described below, and may be arbitrarily selected without departing from the scope of the present invention. You can change it to

[Overview]
The aromatic polycarbonate resin composition of the present invention comprises (A) an aromatic polycarbonate resin and (B) a resin component formed by blending a specific weight average molecular weight high syndiotactic ratio acrylic compound at a predetermined ratio. The carbon black having an average particle size of 1 is contained in a predetermined ratio, and may further contain other components as necessary.

In the aromatic polycarbonate resin composition of the present invention, since the (B) acrylic compound to be blended with the (A) aromatic polycarbonate resin is an acrylic compound having a high syndiotactic ratio, the phase with the (A) aromatic polycarbonate resin. Since it is excellent in solubility, it is possible to obtain a molded product having excellent moldability (fluidity) and excellent appearance without pearly luster or gloss unevenness. Furthermore, extremely good jet blackness can be obtained by blending carbon black having a predetermined particle diameter.
In addition, the (B) acrylic compound used in the present invention has a limited specific weight average molecular weight. By having this specific range of weight average molecular weight, the (A) aromatic polycarbonate resin inherently excellent Without impairing the impact resistance, it is possible to obtain a molded product that contributes to the improvement of the surface hardness and has both the impact resistance and the surface hardness.

[Aromatic polycarbonate resin (A)]
The aromatic polycarbonate resin (A) used in the present invention (hereinafter sometimes referred to as “component (A)”) reacts an aromatic dihydroxy compound or a small amount thereof with phosgene or a carbonic acid diester. It is the thermoplastic polymer or copolymer which may be branched and is obtained by making it. The production method of the aromatic polycarbonate resin is not particularly limited, and those produced by a conventionally known phosgene method (interfacial polymerization method) or melting method (transesterification method) can be used. Moreover, when the melting method is used, an aromatic polycarbonate resin in which the amount of OH groups in the terminal groups is adjusted can be used.

  As the raw material aromatic dihydroxy compound, 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A), tetramethylbisphenol A, bis (4-hydroxyphenyl) -p-diisopropylbenzene, hydroquinone, resorcinol, 4 , 4-dihydroxydiphenyl and the like, preferably bisphenol A. In addition, a compound in which one or more tetraalkylphosphonium sulfonates are bonded to the above aromatic dihydroxy compound can also be used.

  In order to obtain a branched aromatic polycarbonate resin, a part of the above-mentioned aromatic dihydroxy compound is mixed with the following branching agents, that is, phloroglucin, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl). Heptene-2,4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) heptane, 2,6-dimethyl-2,4,6-tri (4-hydroxyphenylheptene-3,1, Polyhydroxy compounds such as 3,5-tri (4-hydroxyphenyl) benzene and 1,1,1-tri (4-hydroxyphenyl) ethane, and 3,3-bis (4-hydroxyaryl) oxindole (= isa) Tin bisphenol), 5-chloruisatin, 5,7-dichloroisatin, 5-bromoisatin, etc. Dose, the aromatic dihydroxy compound is usually 0.01 to 10 mol%, preferably 0.1 to 2 mol%.

  As aromatic polycarbonate resin (A), among the above-mentioned, polycarbonate resin derived from 2,2-bis (4-hydroxyphenyl) propane, or 2,2-bis (4-hydroxyphenyl) propane and other Polycarbonate copolymers derived from aromatic dihydroxy compounds are preferred. Further, it may be a copolymer mainly composed of a polycarbonate resin, such as a copolymer with a polymer or oligomer having a siloxane structure.

  The aromatic polycarbonate resin mentioned above may be used individually by 1 type, and 2 or more types may be mixed and used for it.

  In order to adjust the molecular weight of the aromatic polycarbonate resin, a monovalent aromatic hydroxy compound may be used. Examples of the monovalent aromatic hydroxy compound include m- and p-methylphenol, m- and p-. And propylphenol, p-tert-butylphenol, p-long chain alkyl-substituted phenol and the like.

The molecular weight of the aromatic polycarbonate resin (A) used in the present invention is arbitrary depending on the use and may be appropriately selected and determined. From the viewpoint of moldability, strength, etc., the molecular weight of the aromatic polycarbonate resin (A) is determined by viscosity. The average molecular weight [Mv] is 15,000 to 40,000, preferably 15,000 to 30,000. As described above, when the viscosity average molecular weight is 15,000 or more, the mechanical strength tends to be further improved, which is more preferable in the case of use in applications requiring high mechanical strength. On the other hand, when the viscosity average molecular weight is 40,000 or less, a decrease in fluidity tends to be suppressed and improved, which is more preferable from the viewpoint of easy molding processability. The viscosity average molecular weight [Mv] here is the viscosity average molecular weight [Mv] converted from the solution viscosity, using methylene chloride as a solvent, and using an Ubbelohde viscometer, the intrinsic viscosity [η] (unit dl / g) is obtained and means a value (viscosity average molecular weight: Mv) calculated from Schnell's viscosity formula, that is, η = 1.23 × 10 ⁻⁴ M ^0.83 . Here, the intrinsic viscosity [η] is a value calculated from the following equation by measuring the specific viscosity [η _sp ] at each solution concentration [C] (g / dl).

  The viscosity average molecular weight of the aromatic polycarbonate resin (A) is preferably 17,000 to 30,000, particularly preferably 19,000 to 27,000. Two or more types of aromatic polycarbonate resins having different viscosity average molecular weights may be mixed. In this case, an aromatic polycarbonate resin having a viscosity average molecular weight outside the above-mentioned preferred range may be mixed. In this case, the viscosity average molecular weight of the mixture is preferably within the above range.

[(B) Acrylic compound]
In the present invention, the (B) acrylic compound (hereinafter sometimes referred to as “component (B)”) blended for improving the surface hardness of the molded product has a weight average molecular weight of 60,000 to 80,000. An acrylic compound having a syndiotactic ratio of 55% or more.

  (B) When the weight average molecular weight of an acrylic compound is higher than the said upper limit, it will be inferior to impact resistance and a molded article external appearance. Further, when the weight average molecular weight of the (B) acrylic compound is lower than the lower limit, the impact resistance is inferior. (B) The weight average molecular weight of the acrylic compound is more preferably 65,000 to 75,000, particularly preferably 65,000 to 70,000. In addition, the weight average molecular weight of (B) acrylic compound is the value of polystyrene conversion by a gel permeation chromatography (GPC), and is specifically measured by the method described in the section of the examples described later.

  On the other hand, if the syndiotactic ratio of the (B) acrylic compound is low, the compatibility with the (A) aromatic polycarbonate resin is lowered and the appearance of the molded product is impaired. In addition, the impact resistance of the molded product is inferior. (B) The higher the syndiotactic ratio of the acrylic compound, the higher the compatibility with the (A) aromatic polycarbonate resin, which is preferably 55% or more, particularly preferably 60% or more. Usually, the upper limit is about 70%.

In addition, the syndiotactic ratio of the (B) acrylic compound can be confirmed by ¹ H-NMR, and specifically, the syndiotactic ratio is analyzed by the method described in the Examples section below. Can do.

  Examples of the (B) acrylic compound used in the present invention include polymers obtained by polymerizing or copolymerizing one or more polymerizable monomers including methyl methacrylate. Here, as the polymerizable monomer copolymerized with methyl methacrylate, phenyl (meth) acrylate, benzyl (meth) acrylate (where “(meth) acrylate” is one of “methacrylate” and “acrylate”, or One or two or more types of aromatic (meth) acrylates such as the above) may be mentioned, and those having a high methyl methacrylate content are preferred in terms of the effect of improving the surface hardness, and most preferably polymethyl methacrylate. Acrylate.

[Blending ratio of component (A) and component (B)]
In the present invention, (A) aromatic polycarbonate resin and (B) acrylic compound, (A) 50 to 90 parts by mass of aromatic polycarbonate resin and (B) 10 to 50 parts by mass of acrylic compound are 100 masses in total. It mix | blends so that it may become a part.
When the amount of the component (A) is larger than the above range and the amount of the component (B) is small, the effect of improving the surface hardness due to the blending of the component (B) cannot be sufficiently obtained. When there are many (B) components, there exists a possibility that impact resistance and a molded article external appearance may be impaired.

  A more preferable blending ratio of (A) aromatic polycarbonate resin and (B) acrylic compound is (B) acrylic compound 20-40 parts by mass with respect to (A) aromatic polycarbonate resin 80-60 parts by mass, and more preferably. (A) 30 to 40 parts by mass of (B) acrylic compound with respect to 70 to 60 parts by mass of aromatic polycarbonate resin (however, 100 mass in total of (A) aromatic polycarbonate resin and (B) acrylic compound Part).

[(C) Carbon black]
The aromatic polycarbonate resin composition of the present invention contains (C) carbon black, and the molded product can be colored black with (C) carbon black. The carbon black (C) used in the present invention is a carbon black having an average particle diameter of 15 to 20 nm because it is excellent in jetness and appearance of the molded product obtained. (C) When the average particle diameter of carbon black is larger than the above upper limit, jet blackness is inferior, and when it is smaller than the lower limit, impact resistance and jet blackness are deteriorated due to poor dispersion of carbon black. (C) The average particle diameter of carbon black is an average value of 100 primary particle diameters (average of major axis and minor axis) measured by a transmission electron microscope (TEM), but when commercially available carbon black is used. The average value is the catalog value.

  In this invention, the compounding quantity of (C) carbon black is 0.1-2.0 mass parts with respect to a total of 100 mass parts of (A) aromatic polycarbonate resin which is a resin component, and (B) acrylic compound, Preferably it is 0.3-1.0 mass part. (C) If the blending amount of carbon black is less than the above lower limit, desired coloring (jet blackness) cannot be obtained, and if it exceeds the lower limit, jet blackness and impact resistance are impaired due to poor dispersion of carbon black. .

  In the present invention, (C) carbon black is preferably blended in advance as a masterbatch containing carbon black at a high concentration in order to improve the handling property during production of the resin composition and the uniform dispersibility in the resin composition. . In this case, the resin used for the carbon black masterbatch may be an aromatic polycarbonate resin as the component (A), a polycarbonate resin other than the component (A), or a resin other than the polycarbonate resin. There may be. It is preferable to use a styrene-based resin from the viewpoint that a high concentration of carbon black can be easily dispersed and can be easily formed into a master batch. Moreover, it is preferable to use (A) aromatic polycarbonate resin in the point which raises the amount of (A) component in a resin composition.

  The carbon black concentration of the carbon black masterbatch is usually about 20 to 50% by mass.

[Other additives]
The aromatic polycarbonate resin composition of the present invention is within the range not impairing the effects of the present invention, in addition to (A) aromatic polycarbonate resin and (B) acrylic compound, (C) carbon black and other components and various An additive may be contained. Examples of such other components and additives include phosphorus heat stabilizers, antioxidants, mold release agents, ultraviolet absorbers, flame retardants, anti-dripping agents, inorganic fillers, (C) dyes and pigments other than carbon black, Examples thereof include an antistatic agent, an anti-dripping agent, a molded product appearance improving agent, and other resin components.

<Phosphorus heat stabilizer>
The aromatic polycarbonate resin composition of the present invention can contain a phosphorus heat stabilizer. Phosphorus heat stabilizers are generally effective in improving the residence stability at high temperatures and the heat resistance stability when using resin molded products when melt-kneading resin components.

  Examples of the phosphorus-based heat stabilizer used in the present invention include phosphorous acid, phosphoric acid, phosphorous acid ester, phosphoric acid ester, etc. Among them, trivalent phosphorus is included, and it is easy to express a discoloration suppressing effect. Phosphites such as phosphites and phosphonites are preferred.

  Examples of the phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tris (tridecyl) phosphite. Phyto, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyldipropylene glycol diphosphite, tetraphenyltetra (tridecyl) pentaerythritol tetraphosphite, water Bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butyl) Ruphenyldi (tridecyl) phosphite) tetra (tridecyl) 4,4'-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilaurylpentaerythritol diphos Phyto, distearyl pentaerythritol diphosphite, tris (4-tert-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite, hydrogenated bisphenol A pentaerythritol phosphite polymer, bis ( 2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, , 2'-methylenebis (4,6-di -tert- butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite and the like.

  Examples of phosphonites include tetrakis (2,4-di-iso-propylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,4-di-n-butylphenyl) -4,4′-biphenyl. Range phosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite, tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphospho Knight, tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylenediphosphonite, tetrakis (2,6-di-iso-propylphenyl) -4,4'-biphenylenediphosphonite, Tetrakis (2,6-di-n-butylphenyl) -4,4′-biphenylenediphosphonite, tetrakis (2,6- -Tert-butylphenyl) -4,4'-biphenylenediphosphonite, tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite, tetrakis (2,6-di-tert) -Butylphenyl) -3,3'-biphenylenediphosphonite and the like.

  Examples of the acid phosphate include methyl acid phosphate, ethyl acid phosphate, propyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, butoxyethyl acid phosphate, octyl acid phosphate, 2-ethylhexyl acid phosphate, decyl acid phosphate, and lauryl phosphate. Phosphate, stearyl acid phosphate, oleyl acid phosphate, behenyl acid phosphate, phenyl acid phosphate, nonyl phenyl acid phosphate, cyclohexyl acid phosphate, phenoxyethyl acid phosphate, alkoxy polyethylene glycol acid phosphate, bisphenol A acid Sulfate, dimethyl acid phosphate, diethyl acid phosphate, dipropyl acid phosphate, diisopropyl acid phosphate, dibutyl acid phosphate, dioctyl acid phosphate, di-2-ethylhexyl acid phosphate, dioctyl acid phosphate, dilauryl acid phosphate, distearyl acid phenyl Acid phosphate, bisnonylphenyl acid phosphate, etc. are mentioned.

  Among the phosphites, distearyl pentaerythritol diphosphite, tris (2,4-di-tert-butylphenyl) phosphite, bis (2,6-di-tert-butyl-4-methylphenyl) penta Erythritol diphosphite, 2,2′-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, bis (2,4-dicumylphenyl) pentaerythritol diphosphite are preferable, and heat resistance is good. Tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred in that it is difficult to hydrolyze.

  These phosphorus heat stabilizers may be used alone or in combination of two or more.

  When the aromatic polycarbonate resin composition of the present invention includes a phosphorus-based heat stabilizer, the content thereof is based on a total of 100 parts by mass of the resin component (A) aromatic polycarbonate resin and (B) acrylic compound. Usually, 0.001 parts by mass or more, preferably 0.003 parts by mass or more, more preferably 0.005 parts by mass or more, and usually 0.1 parts by mass or less, preferably 0.08 parts by mass or less, more preferably 0.06 parts by mass or less. If the content of the phosphorus-based heat stabilizer is less than the lower limit of the above range, the thermal stability effect may be insufficient, and if the content of the phosphorus-based heat stabilizer exceeds the upper limit of the above range , There is a possibility that the effect will reach its peak and become less economical.

<Antioxidant>
The aromatic polycarbonate resin composition of the present invention preferably contains an antioxidant as desired. By containing the antioxidant, it is possible to suppress hue deterioration and deterioration of mechanical properties during heat retention.

  Examples of the antioxidant include hindered phenol-based antioxidants. Specific examples thereof include pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, thiodiethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexane-1,6-diylbis [3- (3,5-di-) tert-butyl-4-hydroxyphenylpropionamide), 2,4-dimethyl-6- (1-methylpentadecyl) phenol, diethyl [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl ] Methyl] phosphoate, 3,3 ′, 3 ″, 5,5 ′, 5 ″ -hexa-tert-butyl-a, a ′, ''-(Mesitylene-2,4,6-triyl) tri-p-cresol, 4,6-bis (octylthiomethyl) -o-cresol, ethylenebis (oxyethylene) bis [3- (5-tert- Butyl-4-hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 1,3,5-tris (3,5- Di-tert-butyl-4-hydroxybenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,6-di-tert-butyl-4- (4 6-bis (octylthio) -1,3,5-triazin-2-ylamino) phenol and the like.

  Among them, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate preferable. Examples of such commercially available phenolic antioxidants include “Irganox 1010”, “Irganox 1076” manufactured by BASF, “Adekastab AO-50”, “Adekastab AO-60” manufactured by Adeka, and the like. It is done.

  In addition, 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  When the aromatic polycarbonate resin composition of the present invention contains an antioxidant, the content thereof is relative to 100 parts by mass in total of the resin component (A) aromatic polycarbonate resin and (B) acrylic compound. Usually 0.0001 parts by mass or more, preferably 0.001 parts by mass or more, more preferably 0.01 parts by mass or more, and usually 3 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass. It is not more than part by mass, more preferably not more than 0.3 part by mass. When the content of the antioxidant is less than the lower limit of the above range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the above range, There is a possibility that the effect reaches its peak and is not economical.

<Release agent>
The aromatic polycarbonate resin composition of the present invention may contain a release agent, and a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid is preferably used as the release agent.

  Examples of the aliphatic carboxylic acid constituting the fully esterified product include saturated or unsaturated aliphatic monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid. Here, the aliphatic carboxylic acid also includes an alicyclic carboxylic acid. Among these, preferable aliphatic carboxylic acids are mono- or dicarboxylic acids having 6 to 36 carbon atoms, and aliphatic saturated monocarboxylic acids having 6 to 36 carbon atoms are more preferable. Specific examples of such aliphatic carboxylic acids include palmitic acid, stearic acid, valeric acid, caproic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, melicic acid, tetratriacontanoic acid. , Montanic acid, glutaric acid, adipic acid, azelaic acid and the like.

  On the other hand, examples of the aliphatic alcohol component constituting the fully esterified product include saturated or unsaturated monohydric alcohols, saturated or unsaturated polyhydric alcohols, and the like. These alcohols may have a substituent such as a fluorine atom or an aryl group. Among these alcohols, monovalent or polyvalent saturated alcohols having 30 or less carbon atoms are preferable, and aliphatic saturated monohydric alcohols or polyhydric alcohols having 30 or less carbon atoms are more preferable. Here, the aliphatic alcohol also includes an alicyclic alcohol.

  Specific examples of these alcohols include octanol, decanol, dodecanol, stearyl alcohol, behenyl alcohol, ethylene glycol, diethylene glycol, glycerin, pentaerythritol, 2,2-dihydroxyperfluoropropanol, neopentylene glycol, ditrimethylolpropane, dipentaerythritol. Etc.

  In addition, the esterification rate of the full esterified product of the aliphatic alcohol and the aliphatic carboxylic acid is not necessarily 100%, and may be 80% or more. The esterification rate of the full esterified product according to the present invention is preferably 85% or more, particularly preferably 90% or more.

  The full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid used in the present invention is, in particular, one or more of a full esterified product of a monoaliphatic alcohol and a monoaliphatic carboxylic acid, and a polyhydric aliphatic alcohol. It is preferable to contain 1 type, or 2 or more types of the full esterification product of a mono-aliphatic carboxylic acid, a full esterification product of a mono-aliphatic alcohol and a mono-aliphatic carboxylic acid, Combined use with a fully esterified product with an aliphatic carboxylic acid improves the mold release effect, suppresses gas generation during melt kneading, and reduces the mold deposit.

  As a full esterified product of monoaliphatic alcohol and monoaliphatic carboxylic acid, a full esterified product of stearyl alcohol and stearic acid (stearyl stearate), a full esterified product of behenyl alcohol and behenic acid (behenyl behenate) is preferable. As a full esterified product of a polyaliphatic alcohol and a monoaliphatic carboxylic acid, a full esterified product of glycerol serine and stearic acid (glycerol tristearate), a full esterified product of pentaerythritol and stearic acid (pentaerythritol tetra) Stearylate) is preferred, and pentaerythritol tetrastearate is particularly preferred.

  The full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid may contain an aliphatic carboxylic acid and / or alcohol as an impurity, or may be a mixture of a plurality of compounds.

  When the aromatic polycarbonate resin composition of the present invention contains a release agent such as a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid, the content is a resin component (A) aromatic polycarbonate resin And (B) The amount is usually 2 parts by mass or less, preferably 1 part by mass or less, with respect to 100 parts by mass in total of the acrylic compound. When there is too much content of a mold release agent, there exist problems, such as a fall of hydrolysis resistance and mold contamination at the time of injection molding.

  When a full esterified product of a monoaliphatic alcohol and a monoaliphatic carboxylic acid and a full esterified product of a polyaliphatic alcohol and a monoaliphatic carboxylic acid are used in combination as a mold release agent, the use ratio (mass) Ratio) is a full esterified product of a monoaliphatic alcohol and a monoaliphatic carboxylic acid: a full esterified product of a polyaliphatic alcohol and a monoaliphatic carboxylic acid = 1: 1 to 10 in combination. It is preferable to obtain the above-mentioned effect with certainty.

<Ultraviolet absorber>
The aromatic polycarbonate resin composition of the present invention preferably contains a UV absorber as desired. By containing the ultraviolet absorber, the weather resistance of the aromatic polycarbonate resin composition of the present invention can be improved.

  Examples of the ultraviolet absorber include inorganic ultraviolet absorbers such as cerium oxide and zinc oxide; organics such as benzotriazole compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, triazine compounds, oxanilide compounds, malonic ester compounds, hindered amine compounds, etc. Examples include ultraviolet absorbers. In these, an organic ultraviolet absorber is preferable and a benzotriazole compound is more preferable. By selecting the organic ultraviolet absorber, the mechanical properties of the aromatic polycarbonate resin composition of the present invention are improved.

  Specific examples of the benzotriazole compound include, for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- [2′-hydroxy-3 ′, 5′-bis (α, α-dimethylbenzyl). ) Phenyl] -benzotriazole, 2- (2′-hydroxy-3 ′, 5′-di-tert-butyl-phenyl) -benzotriazole, 2- (2′-hydroxy-3′-tert-butyl-5 ′) -Methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl-phenyl) -5-chlorobenzotriazole), 2- (2'-hydroxy-3 ', 5'-di-tert-amyl) -benzotriazole, 2- (2'-hydroxy-5'-tert-octylphenyl) benzotriazole, 2 2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] and the like, among others 2- (2'-hydroxy- 5′-tert-octylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2N-benzotriazol-2-yl) phenol] are preferred. In particular, 2- (2′-hydroxy-5′-tert-octylphenyl) benzotriazole is preferred. Specific examples of such a benzotriazole compound include “Seesorb 701”, “Seesorb 705”, “Seesorb 703”, “Seesorb 702”, “Seesorb 704”, and “Seesorb 709” manufactured by Sipro Kasei Co., Ltd. “Biosorb 520”, “Biosorb 582”, “Biosorb 580”, “Biosorb 583” manufactured by Yakuhin Kagaku Co., Ltd. “Chemisorb 71”, “Chemisorb 72” manufactured by Chemipro Kasei Co., Ltd. “Siasorb UV5411” manufactured by Cytec Industries, Inc. “ “LA-32”, “LA-38”, “LA-36”, “LA-34”, “LA-31”, “Tinuvin P”, “Tinubin 234”, “Tinubin 326” manufactured by Ciba Specialty Chemicals, “Tinuvin 327”, “Tinuvin 328” and the like can be mentioned.

  Specific examples of the benzophenone compound include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid, 2-hydroxy-4-n-octoxy Benzophenone, 2-hydroxy-n-dodecyloxybenzophenone, bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4 4,4′-dimethoxybenzophenone and the like. Specific examples of such a benzophenone compound include “Seesorb 100”, “Seesorb 101”, “Seesorb 101S”, “Seesorb 102”, and “Seesorb 102” manufactured by Cypro Kasei Co., Ltd. Seesorb 103 ", joint medicine “Biosorb 100”, “Biosorb 110”, “Biosorb 130”, manufactured by Kemipro Kasei Co., Ltd. “Chemisorb 10”, “Chemisorb 11”, “Chemisorb 11S”, “Chemisorb 12”, “Chemsorb 13”, “Chemisorb 111” BASF “Ubinur 400”, BASF “Ubinur M-40”, BASF “Ubinur MS-40”, Cytec Industries “Thiasorb UV9”, “Thiasorb UV284”, “Thiasorb UV531”, “Thiasorb” UV24 "," ADEKA STAB 1413 "," ADEKA STAB LA-51 "manufactured by Adeka Corporation and the like.

  Specific examples of the salicylate compound include phenyl salicylate and 4-tert-butylphenyl salicylate. Specific examples of such a salicylate compound include, for example, “Seesorb 201” and “Seesorb” manufactured by Sipro Kasei Co., Ltd. 202 ”,“ Kemisorb 21 ”,“ Kemisorb 22 ”manufactured by Chemipro Kasei Co., Ltd., and the like.

  Specific examples of the cyanoacrylate compound include, for example, ethyl-2-cyano-3,3-diphenyl acrylate, 2-ethylhexyl-2-cyano-3,3-diphenyl acrylate, and the like. Specifically, for example, “Seasorb 501” manufactured by Sipro Kasei Co., Ltd., “Biosorb 910” manufactured by Kyodo Yakuhin Co., Ltd., “Ubisolator 300” manufactured by Daiichi Kasei Co., Ltd., “Ubinur N-35” manufactured by BASF, 539 "and the like.

  Specific examples of the oxanilide compound include, for example, 2-ethoxy-2′-ethyl oxalinic acid bis-arinide and the like. Specific examples of such oxalinide compound include “Sanduboa” manufactured by Clariant Corporation. VSU "etc. are mentioned.

  As the malonic acid ester compound, 2- (alkylidene) malonic acid esters are preferable, and 2- (1-arylalkylidene) malonic acid esters are more preferable. Specific examples of such a malonic ester compound include “PR-25” manufactured by Clariant Japan, “B-CAP” manufactured by Ciba Specialty Chemicals, and the like.

When the aromatic polycarbonate resin composition of the present invention contains an ultraviolet absorber, the content thereof is based on a total of 100 parts by mass of the resin component (A) aromatic polycarbonate resin and (B) acrylic compound. Usually 0.001 part by mass or more, preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, and usually 3 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass. It is not more than part by mass, more preferably not more than 0.4 part by mass. If the content of the UV absorber is below the lower limit of the above range, the effect of improving the weather resistance may be insufficient, and if the content of the UV absorber exceeds the upper limit of the above range, the mold Debogit etc. may occur and cause mold contamination.
In addition, 1 type may contain the ultraviolet absorber and 2 or more types may contain it by arbitrary combinations and a ratio.

<Flame retardant and anti-dripping agent>
The aromatic polycarbonate resin composition of the present invention may contain a flame retardant and a dripping inhibitor.

  Examples of the flame retardant include halogenated bisphenol A polycarbonate, brominated bisphenol epoxy resin, brominated bisphenol phenoxy resin, halogenated flame retardant such as brominated polystyrene, phosphate ester flame retardant, diphenylsulfone-3,3 ′. -Organic metal salt flame retardants such as dipotassium disulfonate, potassium diphenylsulfone-3-sulfonate and potassium perfluorobutanesulfonate, polyorganosiloxane flame retardants and the like, and phosphate ester flame retardants are particularly preferable.

  Specific examples of the phosphate ester flame retardant include triphenyl phosphate, resorcinol bis (dixylenyl phosphate), hydroquinone bis (dixylenyl phosphate), 4,4′-biphenol bis (dixylenyl phosphate), bisphenol A Bis (dixylenyl phosphate), resorcinol bis (diphenyl phosphate), hydroquinone bis (diphenyl phosphate), 4,4'-biphenol bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), and the like. These may be used alone or in combination of two or more. Among these, resorcinol bis (dixylenyl phosphate) and bisphenol A bis (diphenyl phosphate) are preferable.

  When the aromatic polycarbonate resin composition of the present invention contains a phosphate ester flame retardant, the content of the phosphate ester flame retardant is (A) an aromatic polycarbonate resin and (B) an acrylic compound as resin components. The total amount is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, and particularly preferably 5 to 20 parts by mass. If the content of the phosphate ester flame retardant is less than the above lower limit, the flame retardancy may not be sufficient, whereas if it exceeds the upper limit, the heat resistance may not be sufficient.

  Examples of the anti-dripping agent include fluorinated polyolefins such as polyfluoroethylene, and preferably polytetrafluoroethylene having fibril forming ability. This shows the tendency to disperse | distribute easily in a polymer and to make a fibrous material by couple | bonding polymers. Polytetrafluoroethylene having fibril-forming ability is classified as type 3 according to the ASTM standard. Polytetrafluoroethylene can be used in solid form or in the form of an aqueous dispersion. Examples of polytetrafluoroethylene having fibril-forming ability include, for example, Mitsui DuPont Fluorochemical Co., Ltd., Teflon (registered trademark) 6J or Teflon (registered trademark) 30J, or Daikin Industries, Ltd. Is commercially available.

  When the aromatic polycarbonate resin composition of the present invention contains an anti-drip agent, the content of the anti-drip agent is 100 parts by mass in total of the resin component (A) aromatic polycarbonate resin and (B) acrylic compound. On the other hand, it is preferably 0.02 to 4 parts by mass, and more preferably 0.03 to 3 parts by mass. If the blending amount of the dripping inhibitor exceeds the above upper limit, the appearance of the molded product may be deteriorated.

<Inorganic filler>
The aromatic polycarbonate resin composition of the present invention can contain an inorganic filler for the purpose of improving rigidity and strength. Specific examples of inorganic fillers include glass fillers such as glass fibers (chopped strands), short glass fibers (milled fibers), glass flakes, and glass beads, carbon fillers such as carbon fibers, carbon short fibers, carbon nanotubes, and graphite. , Whiskers such as potassium titanate and aluminum borate, talc, mica, wollastonite, kaolinite, zonotlite, sepiolite, attabalgite, montmorillonite, bentonite, smectite and other silicate compounds, silica, alumina, calcium carbonate, etc. . These may be used alone or in combination of two or more. Among the above, glass fiber (chopped strand), short glass fiber (milled fiber), glass flake, talc, mica, wollastonite, and kaolinite are particularly preferable.

  When the aromatic polycarbonate resin composition of the present invention contains an inorganic filler, the content of the inorganic filler is relative to 100 parts by mass in total of the resin component (A) aromatic polycarbonate resin and (B) acrylic compound. Preferably it is 1-150 mass parts, More preferably, it is 3-100 mass parts, Most preferably, it is 5-60 mass parts. If the content of the inorganic filler is less than the above lower limit, the reinforcing effect may not be sufficient. Conversely, if the content exceeds the upper limit, the appearance of the molded product, impact resistance, and fluidity may not be sufficient.

<Dye and pigment>
The aromatic polycarbonate resin composition of the present invention may contain (C) a dye / pigment other than carbon black, if desired. By containing the dye / pigment, the concealability and weather resistance of the aromatic polycarbonate resin composition of the present invention can be improved, and the design of the molded product obtained by molding the aromatic polycarbonate resin composition of the present invention is improved. Can be made.

  Examples of the dye / pigment include inorganic pigments, organic pigments, and organic dyes.

  Examples of inorganic pigments include sulfide pigments such as cadmium red and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc-iron brown , Titanium Cobalt Green, Cobalt Green, Cobalt Blue, Oxide Pigment such as Copper-Chromium Black, Copper-Iron Black, Chromic Acid Pigment such as Yellow Lead and Molybdate Orange; Ferrocyan Pigment such as Bitumen Etc.

  Examples of organic pigments and organic dyes include phthalocyanine dyes such as copper phthalocyanine blue and copper phthalocyanine green; azo dyes such as nickel azo yellow; thioindigo, perinone, perylene, quinacridone, dioxazine, iso Examples thereof include condensed polycyclic dyes such as indolinone and quinophthalone; anthraquinone, heterocyclic and methyl dyes.

  Of these, titanium oxide, carbon black, cyanine-based, quinoline-based, anthraquinone-based, and phthalocyanine-based compounds are preferable from the viewpoint of thermal stability.

In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio.
The dyed pigment may be used as a masterbatch for the purpose of improving the handleability during extrusion and improving the dispersibility in the resin composition.

  When the aromatic polycarbonate resin composition of the present invention contains (C) a dye / pigment other than carbon black, its content may be appropriately selected according to the required design properties, but it is a resin component (A) It is usually 0.001 parts by mass or more, preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more with respect to 100 parts by mass in total of the aromatic polycarbonate resin and (B) acrylic compound. The amount is usually 3 parts by mass or less, preferably 2 parts by mass or less, more preferably 1 part by mass or less, and still more preferably 0.5 parts by mass or less. When the content of the dye / pigment is less than or equal to the lower limit of the above range, the coloring effect may not be sufficiently obtained, and when the content of the dye / pigment exceeds the upper limit of the above range, a mold deposit or the like occurs. , May cause mold contamination.

<Antistatic agent>
The aromatic polycarbonate resin composition of the present invention may contain an antistatic agent as desired. The antistatic agent is not particularly limited, but is preferably a sulfonic acid phosphonium salt represented by the following general formula (I).

(In the general formula (I), R ¹¹ is an alkyl group having 1 to 40 carbon atoms or an aryl group, and may have a substituent, and R ^{12 to} R ¹⁵ are each independently a hydrogen atom or carbon. (It is an alkyl group or an aryl group of formulas 1 to 10, and these may be the same or different.)

R ¹¹ in the general formula (I) is an alkyl group having 1 to 40 carbon atoms or an aryl group, and an aryl group is preferable from the viewpoint of transparency, heat resistance, and compatibility with a polycarbonate resin. A group derived from an alkylbenzene or alkylnaphthalene ring substituted with an alkyl group of 1 to 34, preferably 5 to 20, particularly 10 to 15 is preferable. In general formula (I) R ¹² ~R ¹⁵ each independently denote a hydrogen atom or an alkyl group or aryl group having 1 to 10 carbon atoms, preferably alkyl of 2 to 8 carbon atoms, More preferably, it is a 3-6 alkyl group, and especially a butyl group is preferable.

Specific examples of such phosphonium sulfonates include tetrabutylphosphonium dodecylsulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tributyloctylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, tetraethylphosphonium octadecylbenzenesulfonate. , Tributylmethylphosphonium dibutylbenzenesulfonate, triphenylphosphonium dibutylnaphthylsulfonate, trioctylmethylphosphonium diisopropylnaphthylsulfonate, and the like. Of these, tetrabutylphosphonium dodecylbenzenesulfonate is preferred because it is compatible with polycarbonate and easily available.
These may be used alone or in combination of two or more.

  When the aromatic polycarbonate resin composition of the present invention contains an antistatic agent, the content thereof is relative to 100 parts by mass in total of the resin component (A) aromatic polycarbonate resin and (B) acrylic compound. It is preferably 0.1 to 5.0 parts by mass, more preferably 0.2 to 3.0 parts by mass, still more preferably 0.3 to 2.0 parts by mass, and particularly preferably 0.5 to 1. parts by mass. 8 parts by mass. If the content of the antistatic agent is less than 0.1 parts by mass, the antistatic effect cannot be obtained, and if it exceeds 5.0 parts by mass, the transparency and mechanical strength are reduced, and the surface of the molded product has silver and peeling. This is likely to cause poor appearance.

<Molded product appearance improver>
The aromatic polycarbonate resin composition of the present invention may further contain a thermoplastic elastomer as a molded product appearance improving agent as necessary, and by mixing the thermoplastic elastomer, the resin components are mixed unevenly. It is possible to prevent appearance defects such as uneven color on the surface of the molded product and the appearance of pearly luster, and obtain a molded product with excellent appearance.

  The thermoplastic elastomer is preferably a copolymer obtained by graft copolymerizing a rubber component with a monomer component copolymerizable therewith. Such a graft copolymer may be produced by any production method such as bulk polymerization, solution polymerization, suspension polymerization, emulsion polymerization, and the copolymerization method may be a single-stage graft or a multi-stage graft. Also good.

  The rubber component generally has a glass transition temperature of 0 ° C. or lower, preferably −20 ° C. or lower, more preferably −30 ° C. or lower. Specific examples of the rubber component include polybutadiene rubber, polyisoprene rubber, polybutyl acrylate and poly (2-ethylhexyl acrylate), polyalkyl acrylate rubber such as butyl acrylate / 2-ethyl hexyl acrylate copolymer, and polyorganosiloxane rubber. Silicone rubber, butadiene-acrylic composite rubber, IPN (interpenetrating polymer network) composite rubber composed of polyorganosiloxane rubber and polyalkylacrylate rubber, styrene-butadiene rubber, ethylene-propylene rubber, ethylene-butene rubber, ethylene-octene rubber, etc. And ethylene-α-olefin rubber, ethylene-acrylic rubber, fluororubber, and the like. These may be used alone or in admixture of two or more. Among these, in view of mechanical properties and surface appearance, polybutadiene rubber, polyalkyl acrylate rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber, and styrene-butadiene rubber are preferable.

  Specific examples of monomer components that can be graft copolymerized with the rubber component include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, (meth) acrylic acid compounds, glycidyl (meth) acrylates, and the like. Epoxy group-containing (meth) acrylic acid ester compounds; maleimide compounds such as maleimide, N-methylmaleimide and N-phenylmaleimide; α, β-unsaturated carboxylic acid compounds such as maleic acid, phthalic acid and itaconic acid and their anhydrides (For example, maleic anhydride, etc.). These monomer components may be used alone or in combination of two or more. Among these, aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, and (meth) acrylic acid compounds are preferable from the viewpoint of mechanical properties and surface appearance, and (meth) acrylic acid esters are more preferable. A compound. Specific examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, octyl (meth) acrylate, and the like. be able to. Here, “(meth) acryl” refers to one or both of “acryl” and “methacryl”. The same applies to “(meth) acrylate”.

  The thermoplastic elastomer used in the present invention is preferably of the core / shell type graft copolymer type from the viewpoint of impact resistance and surface appearance. In particular, at least one rubber component selected from polybutadiene-containing rubber, polybutyl acrylate-containing rubber, IPN type composite rubber composed of polyorganosiloxane rubber and polyalkyl acrylate rubber is used as a core layer, and (meth) acrylic acid ester around it. Particularly preferred is a core / shell type graft copolymer comprising a shell layer formed by copolymerizing. The core / shell type graft copolymer preferably contains 40% by mass or more of a rubber component, and more preferably contains 60% by mass or more. Moreover, what contains 10 mass% or more of (meth) acrylic acid components is preferable.

  Preferable specific examples of these core / shell type graft copolymers include methyl methacrylate-butadiene-styrene copolymer (MBS), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), and methyl methacrylate-butadiene copolymer. Copolymer (MB), methyl methacrylate-acrylic rubber copolymer (MA), methyl methacrylate-acrylic rubber-styrene copolymer (MAS), methyl methacrylate-acrylic-butadiene rubber copolymer, methyl methacrylate-acrylic-butadiene rubber- Examples thereof include styrene copolymers and methyl methacrylate- (acryl / silicone IPN rubber) copolymers. Such rubbery polymers may be used alone or in combination of two or more.

  Examples of such commercially available core / shell type graft copolymers include the EXL series such as Paraloid EXL2315, EXL2602, and EXL2603 manufactured by Rohm and Haas Japan, the KM series such as KM330 and KM336P, and the KCZ201. No. KCZ series, Metablene S-2001, SRK-200 manufactured by Mitsubishi Rayon Co., Ltd., and the like.

  When the aromatic polycarbonate resin composition of the present invention contains the thermoplastic elastomer as described above as a molded article appearance improving agent, the molded article appearance improving agent, that is, the thermoplastic elastomer is a resin component (A) aromatic polycarbonate It is preferable to contain 1-10 mass parts with respect to a total of 100 mass parts of resin and (B) acrylic compound, especially 2-8 mass parts, especially 3-6 mass parts. If the content of the molded product appearance improver in the aromatic polycarbonate resin composition is too small, the effect of improving the molded product surface appearance by blending the molded product appearance improver cannot be sufficiently obtained, and if too much Surface hardness, heat resistance and rigidity tend to decrease.

<Other resin components>
The aromatic polycarbonate resin composition of the present invention may contain a resin component other than (A) an aromatic polycarbonate resin and (B) an acrylic compound, as long as the object of the present invention is not impaired. Good. As other resin components that can be blended, for example, polystyrene resin, high impact polystyrene resin, hydrogenated polystyrene resin, polyacryl styrene resin, ABS resin, AS resin, AES resin, ASA resin, SMA resin, polyalkyl methacrylate resin, (B) acrylic resin other than component, polyphenyl ether resin, polycarbonate resin other than component (A), amorphous polyalkylene terephthalate resin, polyester resin, amorphous polyamide resin, poly-4-methylpentene-1, cyclic Polyolefin resin, amorphous polyarylate resin, polyether sulfone and the like can be mentioned, preferably, other than polystyrene resin, ABS resin, AS resin, AES resin, ASA resin, polyphenylene ether resin, polyester resin, (B) component acrylic Such as butter, and the like.

These may be used alone or in admixture of two or more. In order to obtain the effects of the present invention by using (A) an aromatic polycarbonate resin and (B) an acrylic compound. These other resin components are preferably 40 parts by mass or less with respect to a total of 100 parts by mass of the resin component (A) aromatic polycarbonate resin and (B) acrylic compound.
As described above, when (C) carbon black is masterbatched and compounded, and when (C) a resin other than the components (A) and (B) is used for masterbatch of carbon black, the resin is It corresponds to said other resin component in the aromatic polycarbonate resin composition of invention.

<Other additives>
The aromatic polycarbonate resin composition of the present invention may contain other additives in addition to those described above, if necessary, as long as desired physical properties are not significantly impaired. Examples of other additives include various resin additives such as an antifogging agent, an antiblocking agent, a fluidity improver, a sliding property modifier, a plasticizer, a dispersant, and an antibacterial agent. One of these resin additives may be contained, or two or more thereof may be contained in any combination and ratio.

[Method for producing aromatic polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the aromatic polycarbonate resin composition of this invention, The manufacturing method of a well-known aromatic polycarbonate resin composition can be employ | adopted widely.

  Specific examples thereof include (A) aromatic polycarbonate resin, (B) acrylic compound, and (C) carbon black according to the present invention, and other components blended as necessary, such as tumbler or Henschel. Examples include a method of performing kneading using a mixer such as a Banbury mixer, a roll, a Brabender, a single-screw kneading extruder, a twin-screw kneading extruder, or a kneader after mixing in advance using various mixers such as a mixer and a super mixer. .

  Also, for example, without mixing each component in advance, or only a part of the components are mixed in advance, and fed to an extruder using a feeder, and melt-kneaded, the aromatic polycarbonate resin composition of the present invention It can also be manufactured.

Also, for example, by mixing a part of the components in advance and supplying the resulting mixture to an extruder and melt-kneading it as a master batch, this master batch is again mixed with the remaining components and melt-kneaded. The aromatic polycarbonate resin composition of the present invention can also be produced.
As described above, (C) carbon black is preferably kneaded as a master batch.
In addition, for example, when mixing a component that is difficult to disperse, the component that is difficult to disperse is dissolved or dispersed in a solvent such as water or an organic solvent in advance, and kneaded with the solution or the dispersion. It can also improve sex.

  Examples of a method for melt-kneading after mixing each component in advance by the above method include a method using a Banbury mixer, roll, Brabender, single-screw kneading extruder, twin-screw kneading extruder, kneader and the like.

[Flame retardant aromatic polycarbonate resin molded product]
The aromatic polycarbonate resin composition of the present invention is usually molded into an arbitrary shape and used as an aromatic polycarbonate resin molded article. There are no restrictions on the shape, pattern, color, size, etc. of the molded product, and it may be set arbitrarily according to the application of the molded product.

  The manufacturing method of the aromatic polycarbonate resin molded article of the present invention is not particularly limited, and a molding method generally employed for the aromatic polycarbonate resin composition can be arbitrarily adopted. For example, injection molding method, ultra-high speed injection molding method, injection compression molding method, two-color molding method, hollow molding method such as gas assist, molding method using heat insulating mold, rapid heating mold were used. Molding method, foam molding (including supercritical fluid), insert molding, IMC (in-mold coating molding) molding method, extrusion molding method, sheet molding method, thermoforming method, rotational molding method, laminate molding method, press molding method, etc. Is mentioned. A molding method using a hot runner method can also be used.

  Examples of application of the molded article of the present invention thus manufactured include electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods and miscellaneous goods. And parts such as automobile interior equipment. Among these, the molded product of the present invention is used particularly for parts such as electric and electronic equipment, OA equipment, information terminal equipment, home appliances, and automobile interior equipment because of its excellent surface appearance, surface hardness, and impact resistance. It is suitable, and is particularly suitable for use in parts of electrical and electronic equipment and automobile interior equipment.

  Examples of the electric and electronic devices include display devices such as personal computers, game machines, televisions, car navigation systems, and electronic paper, printers, copiers, scanners, fax machines, electronic notebooks and PDAs, electronic desk calculators, electronic dictionaries, cameras, Examples include a video camera, a mobile phone, a battery pack, a recording medium drive and reading device, a mouse, a numeric keypad, a CD player, an MD player, and a portable radio / audio player. Especially, it can use suitably for the designable parts of housing | casings, such as a television, a personal computer, a car navigation system, and electronic paper.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and can be arbitrarily modified and implemented without departing from the gist of the present invention. In the following description, “parts” means “parts by mass” based on mass standards unless otherwise specified.

  Measurement / evaluation methods and materials used in the following Examples and Comparative Examples are as follows.

[Measurement and evaluation method]
<Measurement / Calculation of Mass Average Molecular Weight (Mw) of Acrylic Compound>
First, the average molecular weight was measured under the following conditions by gel permeation chromatography (GPC) using polystyrene (PS) as a standard polymer.
Apparatus: Alliance made by Waters
Column: Tosoh "TSKgel SuperHZM-M (4)"
Detector; UV detector 254 nm
Eluent: Chloroform Next, after GPC measurement, the relationship between the elution time and the molecular weight of polystyrene was determined by a universal calibration method to obtain a calibration curve. The elution curve (chromatogram) of the acrylic compound was measured under the same conditions as in the calibration curve, and the mass average molecular weight was determined from the elution time (molecular weight) and the peak area (number of molecules) of the elution time.
The mass average molecular weight (Mw) is Mw = Σ (NiMi ² ) / Σ (NiMi) where Ni is the number of molecules of the molecular weight Mi.
It is represented by

<Analysis of syndiotactic ratio of acrylic compounds>
It was carried out by ¹ H-NMR measurement (Bruker BioSpin AVANCE III, 500 MHz) of a solution in which an acrylic compound was dissolved in CDCl ₃ . The syndiotactic ratio was calculated from the area ratio of isotactic, atactic and syndiotactic, paying attention to the signal derived from the methyl group in the methacrylate part.

<Fluidity evaluation>
After drying the resin composition pellets at 100 ° C. for 4 hours or more, using a high load type flow tester, the effluent Q value per unit time (unit: 280 ° C., load 160 kgf / cm ² ) : × 10 ⁻² cc / sec) was measured to evaluate the fluidity. An orifice having a diameter of 1 mm and a length of 10 mm was used.

<Evaluation of surface hardness (pencil hardness)>
A 2 mm-thick plate test piece was subjected to five scratch tests in accordance with JIS K5400 to determine hardness.

<Evaluation of impact resistance (Charpy impact strength)>
The impact resistance was evaluated by a notched Charpy impact test (edgewise impact test according to ISO-179). The measurement was performed using a Charpy impact test piece having a width of 10 mm and a thickness of 3 mm using a weight of 15 J at the maximum. A specimen that was only deformed without breaking was denoted as NB.

<Appearance of molded product appearance (jet black feeling)>
The surface appearance (jet blackness) of the test piece was visually observed and evaluated visually according to the following criteria.
◎: Extremely good jetness ○: Good jetness ×: No jetness or abnormal appearance such as irregularities

<Evaluation of heat resistance (DTUL)>
As a heat resistance index, the deflection temperature under load (load 1.8 MPa) in accordance with ISO75-1 was measured.

[Materials used]
<(A) Aromatic polycarbonate resin>
(A-1) Product name “Iupilon (registered trademark) S-3000” manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight: 22,000, pencil hardness: 2B

<(B) Acrylic compound>
As the acrylic compound having a high syndiotactic ratio, those synthesized by the living anion method described in Macromolecules, 14, 1599-1601 (1981), for example, those synthesized by Polymer Source and commercially available can be used. . As the acrylic compounds (B-1) to (B-7), polymethyl methacrylate synthesized according to the above-described method was used. Commercial products were used for (B-8) to (B-10). Table 1 shows the weight average molecular weight and syndiotactic ratio of each acrylic compound.

<(C) Carbon black>
The following carbon black was compounded as a master batch in which 40% by mass of carbon black and 60% by mass of polystyrene resin were mixed and dispersed using a twin screw extruder.
(C-1): Product name “Color Black FW18” manufactured by Evonik Degussa
Average particle size 15nm
(C-2): Product name “Color Black S170” manufactured by Evonik Degussa
Average particle size 17nm
(C-3): Product name “Color Black S160” manufactured by Evonik Degussa
Average particle size 20nm
(C-4): Product name “Color Black FW200” manufactured by Evonik Degussa
Average particle size 13nm
(C-5): Product name “Special Black 4” manufactured by Evonik Degussa
Average particle size 25nm

<Phosphorus heat stabilizer>
Tris (2,4-di-tert-butylphenyl) phosphite: product name “Adeka Stub 2112” manufactured by Adeka Company

[Examples 1 to 12, Comparative Examples 1 to 13]
{Manufacture of resin pellets}
Each of the above components were blended in the mass ratios shown in Tables 2-3, mixed for 20 minutes with a tumbler, then supplied to Nippon Steel Works (TEX30HSST) equipped with 1 vent, screw rotation speed 200 rpm, discharge The molten resin kneaded under the conditions of an amount of 20 kg / hour and a barrel temperature of 260 ° C. and extruded into a strand shape was rapidly cooled in a water tank and pelletized using a pelletizer to obtain pellets of an aromatic polycarbonate resin composition.

{Preparation of test piece}
<Preparation of 2 mm thick plate specimen>
After the pellets obtained by the above-described production method were dried at 100 ° C. for 5 hours, the cylinder temperature was 270 ° C. using a steel mold in an injection molding machine (“M150AII-SJ” manufactured by Meiki Seisakusho). Injection molding was performed under the conditions of a mold temperature of 80 ° C. and a molding cycle of 50 seconds to produce a plate test piece having a thickness of 100 × 100 × 2 mm. The obtained test piece was used for pencil hardness evaluation and appearance evaluation.

<Preparation of Charpy impact test piece>
After the pellets obtained by the above production method were dried at 100 ° C. for 5 hours, the cylinder temperature was 280 ° C. using a steel mold in an injection molding machine (“SG75Mk-II” manufactured by Sumitomo Heavy Industries, Ltd.). Then, injection molding was carried out under the conditions of a mold temperature of 80 ° C. and a molding cycle of 50 seconds to produce a Charpy impact test piece having a thickness of 3 mm.

<Preparation of DTUL test piece>
After drying the pellets obtained by the above-mentioned production method at 100 ° C. for 5 hours, with an injection molding machine (“SG75Mk-II” manufactured by Sumitomo Heavy Industries, Ltd.), the cylinder temperature is 270 ° C., the mold temperature is 60 ° C., Injection molding was performed under the condition of a molding cycle of 50 seconds to produce an ISO multipurpose test piece (4 mm thickness).

[Evaluation results]
The evaluation results of each example are shown in Tables 2-3.

The following can be seen from the results in Tables 2-3.
The aromatic polycarbonate resin compositions of Examples 1 to 12 are excellent in surface hardness and impact resistance and excellent in jetness.

  Since the comparative example 1 has a large particle size of carbon black, jet blackness is inferior. Since the comparative example 2 produces the dispersion | distribution defect of carbon black because the particle size of carbon black is small, impact resistance and jet blackness are inferior. In Comparative Example 3, the amount of carbon black added is large, resulting in poor dispersion of carbon black, resulting in inferior jetness and impact resistance. In Comparative Examples 4 and 5, the amount of carbon black added is small or not added, so the jetness is inferior. Comparative Examples 6 and 7 have poor impact resistance due to the low molecular weight of the acrylic compound. In Comparative Examples 8 to 12, since the acrylic compound has a high molecular weight or a low syndiotactic ratio, the molded article appearance and impact resistance are poor. In Comparative Example 13, the surface hardness is inferior because no acrylic compound is added.

  As described above, the aromatic polycarbonate resin composition of the present invention has high surface hardness and excellent impact resistance as compared with conventional aromatic polycarbonate resin compositions. In addition, the appearance of the molded product can be said to be a suitable material for automobile interior equipment, exterior parts of electric and electronic equipment, etc. because jet blackness is improved by the use of specific carbon black. Therefore, the industrial value of the present invention is remarkable.

Claims (3)

  As the resin component, (A) 50 to 90 parts by mass of an aromatic polycarbonate resin having a viscosity average molecular weight of 15,000 to 40,000, and (B) a weight average molecular weight of 60,000 to 80,000 and a syndiotactic ratio. A total of 100 parts by mass of 55% or more of an acrylic compound of 10 to 50 parts by mass, and (C) carbon black having an average particle diameter of 15 to 20 nm is 0.1 to 2 parts per 100 parts by mass of the resin component. An aromatic polycarbonate resin composition comprising 0 part by mass.   (B) The aromatic polycarbonate resin composition according to claim 1, wherein the acrylic compound is polymethyl methacrylate.   An aromatic polycarbonate resin molded article obtained by molding the aromatic polycarbonate resin composition according to claim 1 or 2.