JP5655765B2 - Aromatic polycarbonate resin composition and molded article comprising the same - Google Patents

Description

  The present invention relates to an aromatic polycarbonate resin composition. Specifically, in an aromatic polycarbonate resin composition in which polyglycolic acid is blended with an aromatic polycarbonate resin to improve chemical resistance and surface hardness, an aromatic polycarbonate resin composition further improved in impact resistance, and the aromatic polycarbonate resin composition The present invention relates to a molded article formed by molding a polycarbonate resin composition.

  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.

  Conventionally, for the purpose of improving the chemical resistance of an aromatic polycarbonate resin, it is known to blend a polyester resin excellent in chemical resistance such as polybutylene terephthalate (Patent Document 1), but the polyester resin is blended. In the resin composition, although the chemical resistance is improved, there is a drawback that the surface hardness and the heat resistance are inferior.

  As a technique for improving the surface hardness of an aromatic polycarbonate resin, an aromatic polycarbonate resin blended with an acrylic resin such as polymethylmethacrylate has been proposed (Patent Document 2). There is a disadvantage that it is inferior in chemical resistance.

  In addition, although proposals have been made for blending a biodegradable polymer such as polylactic acid with an aromatic polycarbonate resin (Patent Documents 3 to 5), either of them is polylactic acid (homopolymer of lactic acid) or lactic acid. A resin composition that uses a polylactic acid copolymer as a main component and a small amount of a comonomer other than lactic acid and has good chemical resistance, heat resistance, surface hardness, rigidity, and surface appearance is provided. It has not been.

The present inventor has found an aromatic polycarbonate resin composition in which polyglycolic acid is blended with an aromatic polycarbonate resin at a predetermined ratio as a solution to such problems of the prior art. Applied (Patent Document 6).
With the aromatic polycarbonate resin composition of Patent Document 6, chemical resistance and surface hardness can be obtained without impairing the heat resistance of the aromatic polycarbonate resin by blending polyglycolic acid with the aromatic polycarbonate resin at a predetermined ratio. It is possible to realize an aromatic polycarbonate resin composition that is excellent in chemical resistance and heat resistance, and has a high surface hardness and gives a molded article having excellent rigidity.

JP 2002-294060 A JP 62-131056 A JP 2006-199743 A JP 2006-131828 A JP 2007-191622 A Japanese Patent Application No. 2011-156678

  However, according to further studies by the present inventors, the aromatic polycarbonate resin composition of Patent Document 6 can be obtained by increasing the flow value (Q value) of the aromatic polycarbonate resin composition resulting from the decomposition of polyglycolic acid. It has been found that the impact resistance of the molded article may be a problem.

  The present invention further improves the appearance and impact resistance of the molded article of the aromatic polycarbonate resin composition of Patent Document 6 as described above, and has excellent physical property balance such as chemical resistance, heat resistance, surface hardness, rigidity, It is an object of the present invention to provide an aromatic polycarbonate resin composition that gives a molded article excellent in impact resistance and an aromatic polycarbonate resin molded article formed by molding the aromatic polycarbonate resin composition.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have added polycaprolactone to the aromatic polycarbonate resin and polyglycolic acid at a predetermined ratio, so that the polycaprolactone prevents the polyglycolic acid from being decomposed. It has been found that impact resistance can be improved by suppressing an increase in flow value (Q value) resulting from the decomposition of glycolic acid.

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

[1] (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) polyglycolic acid 10 having a repeating unit represented by the following formula (I) 0.1 to 10 parts by mass of (C) polycaprolactone is contained with respect to 100 parts by mass in total with 50 parts by mass , and (B) polyglycolic acid is a glycolic acid homopolymer or glycolic acid the aromatic polycarbonate resin composition number of repeating units and wherein the polyglycolic acid copolymer der Rukoto of 70 mass% or more.

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

  According to the present invention, (A) an aromatic polycarbonate resin composition containing (B) polyglycolic acid and (B) polyglycolic acid to improve chemical resistance and increase surface hardness. Aromatic polycarbonate that improves impact resistance, has a high surface hardness, and has excellent balance of physical properties such as impact resistance, heat resistance, chemical resistance, and rigidity. A resin molded product can be provided.

  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 at least (A) an aromatic polycarbonate resin, (B) polyglycolic acid, and (C) polycaprolactone in a specific ratio. Moreover, the aromatic polycarbonate resin composition of this invention may contain the other component further as needed.

According to the present invention, (A) the aromatic polycarbonate resin is blended with (B) polyglycolic acid at a predetermined ratio, so that the chemical resistance and the surface can be obtained without impairing the heat resistance of the (A) aromatic polycarbonate resin. Hardness and rigidity can be improved.
Further, by blending (C) polycaprolactone in a predetermined ratio to such an aromatic polycarbonate resin composition, (C) polycaprolactone prevents (B) polyglycolic acid from being decomposed, Impact resistance can be improved by suppressing an increase in flow value (Q value) resulting from the decomposition of glycolic acid.

[(A) aromatic polycarbonate resin]
The (A) aromatic polycarbonate resin 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%.

  (A) As aromatic polycarbonate resin, 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 (A) aromatic polycarbonate resin used in the present invention is arbitrary depending on the application and may be appropriately selected and determined. From the viewpoint of moldability, strength, etc., the molecular weight of the (A) aromatic polycarbonate resin is determined by viscosity. The average molecular weight [Mw] 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).

  (A) The viscosity average molecular weight of the aromatic polycarbonate resin 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) Polyglycolic acid]
In order to improve chemical resistance and surface hardness (rigidity), the aromatic polycarbonate resin composition of the present invention is (B) a polyglycolic acid having a repeating unit represented by the following formula (I) (hereinafter referred to as “(B ) Component ").)). Here, the “repeating unit” refers to a structural portion derived from a raw material monomer used in producing polyglycolic acid by polymerizing or copolymerizing monomers.

  The (B) polyglycolic acid used in the present invention is not limited to a homopolymer of glycolic acid consisting only of the repeating units of glycolic acid represented by the above formula (I), but also a polyglycolic acid and other comonomers. A glycolic acid copolymer may be used.

  Comonomers that are copolymerized with glycolic acid monomers to give polyglycolic acid copolymers include, for example, ethylene oxalate (1,4-dioxane-2,3-dione); lactides; β-propiolactone, β Lactones such as butyrolactone, β-pivalolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, and ε-caprolactone; carbonates such as trimethylene carbonate; ethers such as 1,3-dioxane Ether esters such as dioxanone; cyclic monomers such as amides such as ε-caprolactam; hydroxycarboxylic acids such as lactic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, and 6-hydroxycaproic acid Or an alkyl ester thereof; ethylene glycol, 1, - aliphatic diols such as butanediol; succinic acid, one or more of such aliphatic dicarboxylic acids or their alkyl esters such as adipic acid.

However, in terms of improving chemical resistance, surface hardness, and rigidity, (B) polyglycolic acid is a homopolymer of glycolic acid or a polyglycolic acid copolymer having a glycolic acid repeating unit number of 70% by mass or more. a polymer, most preferably a homopolymer of glycolic acid.

  Polyglycolic acid itself has excellent chemical resistance and is effective in improving the chemical resistance of aromatic polycarbonate resin compositions, but by adding chemical resistance to aromatic polycarbonate resin, surface hardness and rigidity are improved. The fact that the effect is obtained has not been known in the past, and is a finding confirmed for the first time by the present inventors.

The degree of molecular weight of (B) polyglycolic acid used in the present invention can be expressed in terms of melt viscosity, which is a melt viscosity measured at 280 ° C. and a shear rate of 10 ³ sec ⁻¹ at 10 to 10 ⁴ Pa · sec. It is preferable to be 10 ² to 10 ³ Pa · sec. (B) If the melt viscosity of polyglycolic acid is low and the molecular weight is too small, the effect of improving chemical resistance, surface hardness and rigidity cannot be obtained sufficiently, the melt viscosity is high, and the molecular weight is high (B) Polyglycolic acid is inferior in molding processability due to a decrease in fluidity.

  A commercial item can be used as such (B) polyglycolic acid, for example, "Kuredux (trademark) 100R60" "Kuredux (trademark) 100T60" by Kureha Co., Ltd. etc. can be used.

  (B) A polyglycolic acid may be used individually by 1 type, and may use together 2 or more types of what differs in the melt viscosity, the presence or absence of a comonomer, and the ratio.

[Contents of (A) aromatic polycarbonate resin and (B) polyglycolic acid]
The aromatic polycarbonate resin composition of the present invention comprises (B) polyglycolic acid in a total of 100 parts by mass of (A) aromatic polycarbonate resin and (B) polyglycolic acid, preferably 10 to 50 parts by mass, preferably It contains 15 to 45 parts by mass, more preferably 20 to 40 parts by mass, and (A) 50 to 90 parts by mass, preferably 55 to 85 parts by mass, more preferably 60 to 80 parts by mass of the aromatic polycarbonate resin. When the content of (B) polyglycolic acid in the aromatic polycarbonate resin composition is less than the above lower limit, and (A) the content of the aromatic polycarbonate resin is greater than the above upper limit, (B) polyglycolic acid was blended. The chemical resistance, surface hardness, and rigidity cannot be sufficiently improved, and the content of (B) polyglycolic acid is more than the above upper limit, and the content of (A) aromatic polycarbonate resin is the above If it is less than the lower limit, the heat resistance and the surface appearance of the molded product tend to deteriorate.

[(C) Polycaprolactone]
The aromatic polycarbonate resin composition of the present invention is characterized by containing (C) polycaprolactone (hereinafter sometimes referred to as “component (C)”) in order to improve impact resistance.

  (C) The polycaprolactone is a polymer or copolymer containing at least 70% by mass, preferably 75% by mass or more, and more preferably 80% by mass or more of a structural unit derived from ε-caprolactone in the polymer. .

  (C) When polycaprolactone is a copolymer of ε-caprolactone and other monomers, monomers that copolymerize with ε-caprolactone include lactone monomers such as β-propiolactone, pivalolactone, and butyrolactone. , Ethylene oxide, 1,2-propion oxide, 1,3-propylene oxide, alkylene oxides such as tetrahydrofuran, unsaturated monomers such as styrene, methyl methacrylate, and butadiene, and coupling agents such as dimethyl terephthalate and diphenyl carbonate. Can be mentioned. These may be used alone or in combination of two or more.

  (C) As polycaprolactone, a part of the hydrogen atom of the methylene chain of the ε-caprolactone unit may be substituted with a halogen atom or a hydrocarbon group, and the end of polycaprolactone is terminal-modified by esterification, etherification, etc. May be.

  (C) Although it does not specifically limit as a manufacturing method of polycaprolactone, The method of carrying out ring-opening polymerization of (epsilon) -caprolactone using suitable initiators, such as alcohol, glycol, water, and catalysts, such as titanium tetrabutoxide and a tin chloride, is. Used.

  The molecular weight of (C) polycaprolactone used in the present invention is preferably 1000 to 100,000 in terms of polystyrene-reduced number average molecular weight by gel permeation chromatography (GPC). If the number average molecular weight is less than 1000, the effect of improving the impact resistance is not sufficiently obtained, and if it exceeds 100,000, the workability and the transparency tend to be lowered. From the viewpoint of improving impact resistance and transparency, the number average molecular weight of (C) polycaprolactone is preferably 4000 to 50000, more preferably 8000 to 30000.

  These (C) polycaprolactones may be used alone or in a combination of two or more.

[(C) Polycaprolactone content]
The aromatic polycarbonate resin composition of the present invention comprises 0.1 to 10 mass of (C) polycaprolactone with respect to 100 mass parts in total of (A) (A) aromatic polycarbonate resin and (B) polyglycolic acid. Part, preferably 1 to 8 parts by weight, more preferably 2 to 6 parts by weight. If the content of (C) polycaprolactone in the aromatic polycarbonate resin composition is less than the above lower limit, the effect of improving impact resistance due to the blending of (C) polycaprolactone cannot be sufficiently obtained, and the above upper limit If it is more, the heat resistance and surface hardness tend to decrease, and the impact resistance also decreases.

  Although the details of the mechanism of action by which (C) polycaprolactone is blended to obtain an effect of improving impact resistance are not clear, (C) polycaprolactone reacts with the OH group of (B) polyglycolic acid. (B) prevents the decomposition of polyglycolic acid and (B) suppresses the increase in the flow value (Q value) resulting from the decomposition of polyglycolic acid.

[Other ingredients]
The aromatic polycarbonate resin composition of the present invention may contain other components as required in addition to the above (A) aromatic polycarbonate resin, (B) polyglycolic acid and (C) polycaprolactone. Examples of other components that can be contained in the aromatic polycarbonate resin composition of the present invention include the following.

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

  Examples of the phosphorus heat stabilizer (D) used in the present invention include phosphorous acid, phosphoric acid, phosphite ester, phosphate ester, etc. Among them, trivalent phosphorus is included, and a discoloration suppressing effect is easily exhibited. In this respect, phosphites such as phosphites and phosphonites are preferable.

  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 (D) phosphorus heat stabilizers may be used alone or in combination of two or more.

  When the aromatic polycarbonate resin composition of the present invention contains (D) a phosphorus-based heat stabilizer, the content thereof is based on a total of 100 parts by mass of (A) the aromatic polycarbonate resin and (B) polyglycolic acid. 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, usually 0.1 parts by mass or less, preferably 0.08 parts by mass or less, more preferably 0. 0.06 parts by mass or less. (D) When the content of the phosphorus-based heat stabilizer is less than the lower limit of the above range, the heat-stabilizing effect may be insufficient, and (D) the content of the phosphorus-based heat stabilizer is within the above range. If the upper limit is exceeded, the effect may reach its peak and may not be economical.

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

  (E) As antioxidant, a hindered phenolic antioxidant is mentioned, for example. 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 Ciba, “Adekastab AO-50”, “Adekastab AO-60” manufactured by Adeka, and the like. It is done.

  In addition, (E) antioxidant may contain 1 type 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 (E) an antioxidant, the content is usually based on 100 parts by mass of the total of (A) aromatic polycarbonate resin and (B) polyglycolic acid. 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. Part or less, more preferably 0.3 part by weight or less. (E) When content of antioxidant is less than the lower limit of the said range, the effect as an antioxidant may become inadequate, and (E) content of antioxidant is the upper limit of the said range. If the value is exceeded, the effect may reach its peak and not economical.

<Other additives>
The aromatic polycarbonate resin composition of the present invention may further contain various additives as long as the effects of the present invention are not impaired. Examples of such additives include mold release agents, ultraviolet absorbers, inorganic fillers, dyes and pigments, antistatic agents, flame retardants, anti-dripping agents, molded product appearance improvers, and components other than (A) to (C). And the like.

(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) an aromatic polycarbonate resin and (B). It is 2 mass parts or less normally with respect to a total of 100 mass parts of polyglycolic acid, Preferably it is 1 mass part or less. 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.

(UV 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 ultraviolet absorbers 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, and hindered amine compounds. 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.

  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”, “Ubinur N-N-” manufactured by BASF Corporation. 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 an 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 usually 0.001 with respect to 100 parts by mass in total of (A) aromatic polycarbonate resin and (B) polyglycolic acid. 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 or less, More preferably, it is 0.4 mass part or less. 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.

(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 preferably 1 to 100 parts by mass in total of (A) the aromatic polycarbonate resin and (B) polyglycolic acid. 150 parts by mass, more preferably 3 to 100 parts by mass, and particularly preferably 5 to 60 parts by mass. 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 a dye / pigment 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 carbon black, cadmium red, and cadmium yellow; silicate pigments such as ultramarine blue; titanium oxide, zinc white, petal, chromium oxide, iron black, titanium yellow, zinc- Oxide pigments such as iron brown, titanium cobalt green, cobalt green, cobalt blue, copper-chromium black and copper-iron black; chromic pigments such as chrome lead and molybdate orange; Examples include Russian pigments.

  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.
In addition, dyes and pigments may be masterbatched with (A) aromatic polycarbonate resin or (B) polyglycolic acid for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. It may be used.

  When the aromatic polycarbonate resin composition of the present invention contains a dye / pigment, the content may be appropriately selected according to the required design properties. (A) Aromatic polycarbonate resin and (B) polyglycolic acid 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, and usually 3 parts by mass or less, preferably 2 parts by mass. Part or less, more preferably 1 part by weight or less, and still more preferably 0.5 part by weight 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 (1).

(In General Formula (1), R ¹ is an alkyl group having 1 to 40 carbon atoms or an aryl group, and may have a substituent, and R ^{2 to} R ⁵ 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 ¹ in the general formula (1) 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 ^{(5) R} 2 ~R 5 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 0.1 to 100 parts by mass in total of (A) the aromatic polycarbonate resin and (B) polyglycolic acid. The amount is preferably 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 1.8 parts by mass. is there. 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.

(Flame retardant, 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 100 mass in total of (A) aromatic polycarbonate resin and (B) polyglycolic acid. The 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 with respect to parts. 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 a dripping inhibitor, the content of the dripping inhibitor is preferably based on 100 parts by mass of the total of (A) aromatic polycarbonate resin and (B) polyglycolic acid. Is 0.02 to 4 parts by mass, 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.

(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 converted into (A) an aromatic polycarbonate resin and (B ) It is preferable to contain 1 to 15 parts by mass, particularly 2 to 10 parts by mass, especially 3 to 8 parts by mass with respect to 100 parts by mass in total with polyglycolic acid. 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)
Unless the objective of this invention is impaired, the aromatic polycarbonate resin composition of this invention is (A) aromatic polycarbonate resin, (B) polyglycolic acid, and (C) other than polycaprolactone as a resin component. A resin component may be contained. 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, Polymethacryl methacrylate resin, polyphenyl ether resin, polycarbonate resin other than component (A), amorphous polyalkylene terephthalate resin, polyester resin other than component (B), amorphous polyamide resin, poly-4-methylpentene-1 , Cyclic polyolefin resin, amorphous polyarylate resin, polyether sulfone, etc., preferably polystyrene resin, ABS resin, AS resin, AES resin, ASA resin, polyphenylene ether resin, polymethacryl methacrylate. Over preparative resin, and polyester resin other than component (B).

  These may be used singly or in combination of two or more, but (A) aromatic polycarbonate resin, (B) polyglycolic acid and (C) polycaprolactone in a specific ratio. In order to acquire the effect of this invention by using, these other resin components shall be 40 mass parts or less with respect to 100 mass parts in total of (A) aromatic polycarbonate resin and (B) polyglycolic acid. Is preferred.

(Other ingredients)
The aromatic polycarbonate resin composition of the present invention may contain other components in addition to those described above as needed, as long as the desired physical properties are not significantly impaired. Examples of the other components 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 and (B) polyglycolic acid, (C) polycaprolactone according to the present invention, and (D) a phosphorus-based heat stabilizer blended as necessary. (E) Antioxidants and other components are mixed in advance using various mixers such as a tumbler, a Henschel mixer, and a super mixer, and then Banbury mixer, roll, brabender, single-screw kneading extruder, two Examples thereof include a melt kneading method using a mixer such as a shaft kneading extruder or a kneader.

  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.
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.

[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 lighting equipment. Among these, the molded article of the present invention is particularly excellent in chemical properties, heat resistance, impact resistance, surface hardness, rigidity, and other mechanical physical properties, and in particular, electrical and electronic equipment, OA equipment, information terminal equipment, and home appliances. It is suitable for use in parts such as lighting equipment, and is particularly suitable for use in electrical and electronic equipment, parts of lighting equipment, and sheet members.

  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.

  As a component of the above-mentioned lighting device, it can be suitably used for a cover of LED lighting, EL lighting or the like.

  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]
<Evaluation of flow value (Q value)>
The pellet flow value (Q value) was evaluated by the method described in JIS K7210 Appendix C. Measurement was performed using a flow tester CFD500D manufactured by Shimadzu Corporation, using a die having a hole diameter of 1.0 mmφ and a length of 10 mm, a test resin at a test temperature of 280 ° C., a test force of 160 kg / cm ² and a preheating time of 420 seconds. The amount (× 0.01 cc / sec) was measured.

<Impact resistance (Charpy impact strength (no notch) evaluation>
Based on the ISO-179 standard, Charpy impact strength (no notch) was measured. In the Charpy impact test, when it did not break, it was described as NB (non-breaking).

<Evaluation of surface hardness (pencil hardness)>
According to JIS K5400, the test piece was subjected to five scratch tests to evaluate pencil hardness.

<Measurement 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>
Bisphenol A type aromatic polycarbonate produced by interfacial polymerization ("Iupilon (registered trademark) S-3000FN" manufactured by Mitsubishi Engineering Plastics Co., Ltd., viscosity average molecular weight 25000)

<(B) Polyglycolic acid>
Polyglycolic acid ("Kuredux (registered trademark) 100R60" manufactured by Kureha Co., Ltd., melt viscosity 2 × 10 ² Pa · sec measured at 280 ° C. and shear rate 10 ³ sec ⁻¹ )

<(C) Polycaprolactone>
C-1: Polycaprolactone ("Plexel H1P" manufactured by Daicel Corporation, number average molecular weight 10,000)
C-2: Polycaprolactone ("Placcel H5" manufactured by Daicel Corporation, number average molecular weight 50000)
C-3: Polycaprolactone ("Placcel H7" manufactured by Daicel Corporation, number average molecular weight 70000)

<(D) Phosphorus heat stabilizer>
D-1: Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol phosphite (“ADEKA STAB PEP36” manufactured by ADEKA)
D-2: mono- and distearyl acid phosphate ("ADEKA STAB AX-71" manufactured by ADEKA)

<(E) Antioxidant>
Pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (“Irganox 1010” manufactured by BASF Japan Ltd.)

[Examples 1-8, Comparative Examples 1-5]
<Preparation of resin composition>
Each of the above components was blended in the mass ratios shown in Tables 1 and 2, 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 270 ° 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>
After drying the pellets obtained by the above production method at 120 ° 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 90 ° 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). The obtained test piece was used for the impact resistance evaluation, surface hardness evaluation, and heat resistance evaluation.

[Evaluation results]

From the results in Tables 1 and 2, the following can be understood.
The compositions of Examples 1 to 8 of the present invention are excellent in balance in all of the flow value (Q value), impact resistance, surface hardness, and heat resistance.
On the other hand, Comparative Example 1 in which (B) polyglycolic acid is not blended has inferior surface hardness. (C) In Comparative Example 2 in which no polycaprolactone is blended, the flow value (Q value) is large and the impact resistance is poor. Since the comparative example 3 has too much compounding quantity of (C) polycaprolactone, heat resistance is bad and impact resistance is also inferior. Since comparative example 4 has too much compounding quantity of (B) polyglycolic acid, it is inferior to impact resistance and heat resistance. In Comparative Example 5, since the blending amount of (B) polyglycolic acid is too small, the surface hardness is low.

Claims (2)

(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) 10 to 50 parts by mass of polyglycolic acid having a repeating unit represented by the following formula (I) And 0.1 to 10 parts by mass of (C) polycaprolactone , and (B) the polyglycolic acid is a homopolymer of glycolic acid or the number of repeating units of glycolic acid There aromatic polycarbonate resin composition characterized polyglycolic acid copolymer der Rukoto of 70 mass% or more.

  An aromatic polycarbonate resin molded article obtained by molding the aromatic polycarbonate resin composition according to claim 1.