JP2012025790A - Aromatic polycarbonate resin composition and molded article comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aromatic polycarbonate resin composition which is excellent in transparency and shock resistance and has high surface hardness and good scratch resistance; and to provide a molded body prepared by molding the composition.SOLUTION: The composition comprises: 100 pts.mass of total of resin components (A) and (B) consisting of 40-95 mass% of the aromatic polycarbonate resin (A) with a mass-average molecular of 15,000-40,000 and 5-60 mass% of the (meth)acrylate copolymer (B) with a mass% ratio (b1/b2) of an aromatic (meth)acrylate unit (b1) to a methyl methacrylate unit (b2) of 5-80/20-95 and a mass-average molecular mass of 5,000-30,000; 0.001-1 pt.mass of a phosphorus stabilizer (C); and 0.001-1 pt.mass of a fully esterified product (D) of aliphatic alcohol with aliphatic carboxylic acid.

Description

  The present invention relates to an aromatic polycarbonate resin composition. More specifically, the present invention relates to an aromatic polycarbonate resin composition having good surface hardness while maintaining transparency, and a molded article comprising the same.

Conventionally, aromatic polycarbonate resins have excellent transparency, impact resistance, heat resistance, etc., and the resulting molded products are also excellent in dimensional stability, etc., so housings for electrical and electronic equipment, automotive parts, etc. It is widely used as a raw material resin for manufacturing precision molded products such as optical disc-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.
However, molded products made of aromatic polycarbonate resin alone have a lower surface hardness compared to products made of metal or glass, so they are inferior in scratch resistance, and when they are wiped with cloth or handled roughly, It has the disadvantage of being easily scratched.

  On the other hand, a method for forming a coating film with high surface hardness on the surface of a product using an aromatic polycarbonate resin has been proposed, and as a film material, for example, a coating agent of silicon resin or acrylic resin is known. However, these have a problem in the adhesion of the coating film, and it is difficult to coat a product having a complicated shape, the price is expensive, and there is a limit to industrial use. In addition, a method of painting the product surface is also known, but this method, like coating, is difficult to obtain a uniform coating film depending on the product shape. If the coating film thickness is not thick, the effect of improving the surface hardness is low. Furthermore, there exists a fault which impairs an external appearance by peeling of a coating surface or a coating-film surface.

  Also known is a method of blending a polycarbonate resin with a high hardness inorganic compound, but this method has a slight effect of improving the surface hardness, and when an inorganic compound is added, the refractive index of the additive And the refractive index of the aromatic polycarbonate resin are different, there is a drawback that transparency, which is a major characteristic of the aromatic polycarbonate resin, is impaired.

  On the other hand, in order to obtain an aromatic polycarbonate resin having excellent transparency and rigidity, a method of adding a compound selected from the group of biphenyl compounds, terphenyl compounds and polycaprolactones to aromatic polycarbonate resins has been proposed (for example, patents). References 1-3). However, according to the results of the study by the present inventors, this method cannot satisfy the requirement for high scratch resistance and is still insufficient for use in the above-mentioned industrial products.

In addition, many scratch-resistant compositions in which an aromatic polycarbonate resin is mixed with an acrylate such as methyl methacrylate or an ABS resin have been proposed.
For example, Patent Document 4 describes that a vinyl cyanide compound-aromatic vinyl compound copolymer and methyl methacrylate are blended. Patent Document 5 describes a resin composition comprising a polyester resin and an ABS resin, a polycarbonate resin, and polymethyl methacrylate. Patent Document 6 describes blending a copolymer composed of a vinyl monomer that is reactive with (meth) alkyl acrylate-aromatic vinyl-polycarbonate resin. Further, Patent Document 7 proposes blending a rubber-modified graft copolymer such as ABS resin and a vinyl monomer copolymer such as polymethyl methacrylate.

  However, it is difficult to say that these methods are resin compositions having an excellent balance of physical properties of impact resistance, hardness, and transparency.

Japanese Patent Laid-Open No. 03-143950 Japanese Patent Laid-Open No. 05-257002 JP 2000-169695 A JP 2001-49072 A JP 2001-234040 A JP 2008-56798 A WO2009 / 128601

  The present invention has been made in view of the above problems, and relates to an aromatic polycarbonate resin composition having high surface hardness while maintaining transparency without impairing the high heat resistance inherent in the polycarbonate resin.

In order to solve the above problems, the inventor of the present invention paid attention to a specific acrylic resin and intensively studied.
As a result, the aromatic polycarbonate resin contains a specific (meth) acrylic copolymer, a phosphorus stabilizer, a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid, without impairing heat resistance, The inventors have found that an aromatic polycarbonate resin composition having a high surface hardness can be obtained while maintaining transparency, and completed the present invention.

That is, according to the first invention of the present invention, the aromatic polycarbonate resin (A) having a mass average molecular weight of 15,000 to 40,000 is 40 to 95% by mass, the aromatic (meth) acrylate unit (b1) and methyl. (Meth) acrylate copolymer (B) 5-60 having a mass% ratio (b1 / b2) of the methacrylate unit (b2) of 5-80 / 20-95 and a weight average molecular weight of 5,000-30,000. % Of the resin component of (A) and (B) consisting of 100% by mass, phosphorus stabilizer (C) 0.001 to 1 part by mass, full ester of aliphatic alcohol and aliphatic carboxylic acid An aromatic polycarbonate resin composition comprising 0.001 to 1 part by mass of a compound (D) is provided.

According to the second invention of the present invention, in the first invention, the full esterified product (D) of an aliphatic alcohol and an aliphatic carboxylic acid is a full ester of a monoaliphatic alcohol and a monoaliphatic carboxylic acid. There is provided a resin composition comprising an esterified product (D1) and a full esterified product (D2) of a polyhydric aliphatic alcohol and a monoaliphatic carboxylic acid.

According to the third invention of the present invention, in the second invention, a full esterified product (D1) of monoaliphatic alcohol and monoaliphatic carboxylic acid is a full esterified product of stearyl alcohol and stearic acid (stearyl). There is provided a resin composition characterized in that it is at least one selected from stearates) and full esterified products of behenyl alcohol and behenic acid (behenyl behenate).

According to the fourth invention of the present invention, in the second invention, the full esterified product (D2) of polyhydric aliphatic alcohol and monoaliphatic carboxylic acid is a full esterified product of pentaerythritol and stearic acid. A resin composition characterized by being (pentaerythritol tetrastearate) is provided.

  Furthermore, according to 5th invention of this invention, the molded article which consists of a resin composition which concerns on any one of 1st-4th invention is 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

[1. Overview]
The aromatic polycarbonate resin composition of the present invention comprises at least an aromatic polycarbonate resin, a specific (meth) acrylate copolymer, a phosphorus stabilizer, a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid. It contains. Moreover, the polycarbonate resin composition of this invention may contain the other component as needed.

  Thus, by including a specific (meth) acrylate copolymer in the aromatic polycarbonate resin, the surface hardness is improved while maintaining transparency without impairing both impact resistance and heat resistance, that is, Scratch resistance can be improved.

[2. Aromatic polycarbonate resin]
The (A) aromatic polycarbonate resin used in the present invention is a thermoplastic heavy chain which may be branched, obtained by reacting an aromatic dihydroxy compound or a small amount thereof with a phosgene or a carbonic acid diester. It is a coalescence or copolymer. 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. Further, when the melting method is used, a polycarbonate resin in which the amount of OH groups of 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 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. Furthermore, you may mix and use 2 or more types of the aromatic polycarbonate resin mentioned above.

In order to adjust the molecular weight of the aromatic polycarbonate resin, a monovalent aromatic hydroxy compound may be used. For example, m- and p-methylphenol, m- and p-propylphenol, p-tert-butylphenol, p- Long chain alkyl substituted phenols and the like.

The molecular weight of the (A) aromatic polycarbonate resin 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 (A) aromatic polycarbonate resin is gel A polycarbonate (PC) equivalent weight average molecular weight [Mw] measured by permeation chromatography is preferably 15,000 to 40,000, more preferably 15,000 to 30,000. As described above, when the mass 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, by setting it as 40,000 or less, there exists a tendency to suppress and improve fluidity | liquidity fall more, and it is more preferable from a viewpoint of easy moldability.

  Among them, the mass average molecular weight is preferably 17,000 to 30,000, particularly preferably 19,000 to 27,000. In addition, two or more types of aromatic polycarbonate resins having different mass average molecular weights may be mixed. In this case, an aromatic polycarbonate resin having a mass average molecular weight outside the above preferred range may be mixed. In this case, the mass average molecular weight of the mixture is preferably within the above range.

[3. (Meth) acrylate copolymer]
The (meth) acrylate copolymer (B) of the present invention contains an aromatic (meth) acrylate unit (b1) and a methyl methacrylate unit (b2). In the present invention, (meth) acrylate represents acrylate or methacrylate.

The aromatic (meth) acrylate constituting the aromatic (meth) acrylate unit (b1) refers to a (meth) acrylate having an aromatic group in the ester moiety. Examples of the aromatic (meth) acrylate include phenyl (meth) acrylate and benzyl (meth) acrylate. These can be used alone or in combination of two or more. Of these, phenyl methacrylate and benzyl methacrylate are preferable, and phenyl methacrylate is more preferable. By having the aromatic (meth) acrylate unit (b1), the transparency of the molded body mixed with the aromatic polycarbonate resin can be improved.

The monomer constituting the methyl methacrylate unit (b2) is methyl methacrylate. The methyl methacrylate unit (b2) has an effect of being well dispersed with the polycarbonate resin, and moves to the surface of the molded body, so that the surface hardness of the molded body can be improved.

The (meth) acrylate copolymer (B) contains 5 to 80% by mass of the aromatic (meth) acrylate unit (b1) and 20 to 95% by mass of the methyl methacrylate unit (b2) (provided that (b1) and ( The sum of b2) is 100% by mass). If the content of the aromatic (meth) acrylate unit (b1) in the (meth) acrylate copolymer (B) is 5% by mass or more, it is transparent in the high addition region of the (meth) acrylate copolymer (B). If the property is maintained and the amount is 80% by mass or less, the compatibility with the aromatic polycarbonate is not too high, and the migration to the surface of the molded article does not decrease, so the surface hardness does not decrease.

Moreover, in the high addition area | region of (meth) acrylate copolymer (B), since high surface hardness is expressed maintaining transparency, (meth) acrylate copolymer (B) is aromatic (meth). It is preferable to contain 20-70 mass% of acrylate units (b1) and 30-80 mass% of methyl methacrylate units (b2).

If the content of the aromatic (meth) acrylate unit (b1) in the (meth) acrylate copolymer (B) is 5% by mass or more, it is transparent in the high addition region of the (meth) acrylate copolymer (B). If the property is maintained and the content is 79.9% by mass or less, the compatibility with the aromatic polycarbonate is not too high, and the migration to the surface of the molded article does not decrease, so the surface hardness does not decrease.

If the content of the methyl methacrylate unit (b2) in the (meth) acrylate copolymer (B) is 20% by mass or more, the compatibility with the aromatic polycarbonate is not too high, and the migration to the surface of the molded product is achieved. Therefore, if the surface hardness does not decrease and is 94.9% by mass or less, the transparency is maintained in the high addition region of the (meth) acrylate copolymer (B).

As a polymerization method of the monomer for obtaining the surface hardness improver, a known method such as an emulsion polymerization method, a suspension polymerization method, a solution polymerization method, a bulk polymerization method, or the like can be used. A suspension polymerization method and a bulk polymerization method are preferable, and a suspension polymerization method is more preferable. Further, additives necessary for the polymerization can be appropriately added as necessary, and examples thereof include a polymerization initiator, an emulsifier, a dispersant, and a chain transfer agent.

The mass average molecular weight of the (meth) acrylate copolymer (B) is 5,000 to 30,000, preferably 10,000 to 25,000, and particularly preferably 13,000 to 20,000. When the weight average molecular weight is 5,000 to 30,000, the compatibility with the aromatic polycarbonate is good, and the effect of improving the surface hardness is excellent. The weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) of the (meth) acrylate copolymer (B) are gel permeation using chloroform or tetrahydrofuran (THF) as a solvent. Measurements can be made using an association chromatography. The molecular weight is a value in terms of polystyrene (PS).

In the present invention, the mass ratio of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B) is such that the (A) component is 40 to 95% by mass, and the (B) component is 5 to 60%. % By mass. Preferably, the component (B) is 10 to 50% by mass with respect to the component (A) 50 to 90% by mass, and more preferably the component (B) is 15 to 45% by mass with respect to 55 to 85% by mass. . When the mass ratio is in this range, the aromatic polycarbonate resin composition of the present invention can maintain the physical property balance and improve the surface hardness while maintaining transparency.

[4. Phosphorus stabilizer]
The aromatic polycarbonate resin composition of the present invention further contains a phosphorus stabilizer. Phosphorus stabilizers are generally effective in improving the residence stability at high temperatures and the heat resistance stability when using a resin molding when melt-kneading a polycarbonate resin.

  Examples of the phosphorus compound used in the present invention include phosphorous acid, phosphoric acid, phosphite ester, phosphate ester, etc. Among them, phosphite contains trivalent phosphorus and easily exhibits a discoloration suppressing effect. Phosphites such as phosphonite are preferred.

  Specific examples of the phosphite include triphenyl phosphite, tris (nonylphenyl) phosphite, dilauryl hydrogen phosphite, triethyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, and tris. (Tridecyl) phosphite, tristearyl phosphite, diphenyl monodecyl phosphite, monophenyl didecyl phosphite, diphenyl mono (tridecyl) phosphite, tetraphenyl dipropylene glycol diphosphite, tetraphenyl tetra (tridecyl) pentaerythritol tetra Phosphite, hydrogenated bisphenol A phenol phosphite polymer, diphenyl hydrogen phosphite, 4,4′-butylidene-bis (3-methyl-6-t rt-butylphenyldi (tridecyl) phosphite) tetra (tridecyl) 4,4'-isopropylidenediphenyldiphosphite, bis (tridecyl) pentaerythritol diphosphite, bis (nonylphenyl) pentaerythritol diphosphite, dilauryl Pentaerythritol diphosphite, 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 diphos Aito, 2,2'-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, and tetrakis (2,6-di-) tert-butylphenyl) -3,3′-biphenylenediphosphonite.

  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.

  The content of the phosphorus stabilizer (C) used in the present invention is usually 0.001 with respect to a total of 100 parts by mass of the resin components of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B). Parts by mass or more, preferably 0.003 parts by mass or more, more preferably 0.005 parts by mass or more, 0.1 parts by mass or less, preferably 0.08 parts by mass or less, more preferably 0.06 parts by mass or less. It is. If the content of the phosphorus stabilizer is less than or equal to the lower limit of the range, the thermal stability effect may be insufficient, and if the content of the phosphorus stabilizer exceeds the upper limit of the range, the effect May stop and become economical.

[5. Full esterified product of aliphatic alcohol and aliphatic carboxylic acid]
The aromatic polycarbonate resin composition of the present invention further contains a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid.

  Examples of the aliphatic carboxylic acid constituting the full 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. Of these, preferred 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 preferred. 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. Of 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. These aliphatic carboxylic acid esters may contain an aliphatic carboxylic acid and / or alcohol as impurities, and may be a mixture of a plurality of compounds.

  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.

  Further, a full esterified product of an aliphatic alcohol and an aliphatic carboxylic acid includes 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. It is preferable to contain.

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. ,
Examples of the full esterified product of a polyhydric aliphatic alcohol and a monoaliphatic carboxylic acid include a fully esterified product of glycerin serine and stearic acid (glycerin tristearate), a full esterified product of pentaerythritol and stearic acid (pentaerythritol tetrastearate). Rate) is preferable, and pentaerythritol tetrastearate is particularly preferable.

  The content of the full esterified product (D) of the aliphatic alcohol and the aliphatic carboxylic acid is based on 100 parts by mass in total of the resin components of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B). 2 parts by mass or less, preferably 1 part by mass or less. When the amount exceeds 2 parts by mass, there are problems such as degradation of hydrolysis resistance and mold contamination during injection molding.

[6. Antioxidant]
The 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. Specific examples of such phenolic antioxidants include “Irganox 1010”, “Irganox 1076” manufactured by Ciba, “Adekastab AO-50”, “Adekastab AO-60” manufactured by Adeka, and the like. Is mentioned.
In addition, 1 type may contain antioxidant and 2 or more types may contain it by arbitrary combinations and a ratio.

  Content of antioxidant is 0.0001 mass part or more normally with respect to the total 100 mass parts of the resin component of aromatic polycarbonate resin (A) and (meth) acrylate copolymer (B), Preferably it is 0.00. 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 or less, still more preferably 0.3 parts by mass. It is as follows. When the content of the antioxidant is less than or equal to the lower limit of the range, the effect as an antioxidant may be insufficient, and when the content of the antioxidant exceeds the upper limit of the range, There is a possibility that the effect reaches its peak and is not economical.

[7. UV absorber]
The polycarbonate resin composition of the present invention preferably contains an ultraviolet absorber as desired. By containing the ultraviolet absorber, the weather resistance of the 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 polycarbonate resin composition of the present invention has good transparency and mechanical properties.

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 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.

  Content of a ultraviolet absorber is 0.001 mass part or more normally with respect to 100 mass parts in total of the resin component of an aromatic polycarbonate resin (A) and a (meth) acrylate copolymer (B), Preferably it is 0.00. 01 parts by mass or more, more preferably 0.1 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 or less, and further preferably 0.4 parts by mass. It is as follows. 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.

[8. Dyeing pigment]
The polycarbonate resin composition of the present invention preferably contains a dye / pigment if desired. By containing the dye / pigment, the concealability and weather resistance of the polycarbonate resin composition of the present invention can be improved, and the design of a molded article obtained by molding the polycarbonate resin composition of the present invention is improved.

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 used as masterbatches with polystyrene resins, polycarbonate resins, and acrylic resins for the purpose of improving handling during extrusion and improving dispersibility in the resin composition. Good.

The content of the dye / pigment may be appropriately selected according to the required design properties, but with respect to a total of 100 parts by mass of the resin components of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B). 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 2 parts by mass or less, more preferably 1 part by mass. Part or less, more preferably 0.5 part by weight or less. If the content of the dye / pigment is less than or equal to the lower limit of the range, the effect may not be sufficiently obtained, and if the content of the dye / pigment exceeds the upper limit of the range, a mold deposit or the like occurs, May cause mold contamination. In addition, 1 type may contain the dye / pigment, and 2 or more types may contain it by arbitrary combinations and a ratio.

[9. Antistatic agent]
The aromatic polycarbonate resin composition of the present invention preferably contains 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).

（一般式（１）中、Ｒ^１は炭素数１〜４０のアルキル基又はアリール基であり、置換基を有していても良く、Ｒ^２〜Ｒ^５は、各々独立して水素原子、炭素数１〜１０のアルキル基又はアリール基であり、これらは同じでも異なっていてもよい。）

(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. Further, ^R 2 to R ⁵ of the general formula (1), each independently represent 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 the sulfonic acid phosphonium salt (b) of the present invention include tetrabutylphosphonium dodecylsulfonate, tetrabutylphosphonium dodecylbenzenesulfonate, tributyloctylphosphonium dodecylbenzenesulfonate, tetraoctylphosphonium dodecylbenzenesulfonate, octadecylbenzenesulfone. Examples include tetraethylphosphonium acid, tributylmethylphosphonium dibutylbenzenesulfonate, triphenylphosphonium dibutylnaphthylsulfonate, and trioctylmethylphosphonium diisopropylnaphthylsulfonate. Of these, tetrabutylphosphonium dodecylbenzenesulfonate is preferred because it is compatible with polycarbonate and easily available.

  The content of the antistatic agent is 0.1 to 5.0 parts by mass with respect to 100 parts by mass in total of the resin components of the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B). However, it is preferably 0.2 to 3.0 parts by mass, more preferably 0.3 to 2.0 parts by mass, and particularly preferably 0.5 to 1.8 parts by mass. If it 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 lowered, and silver or peeling occurs on the surface of the molded product, which easily causes poor appearance. .

[10. Other ingredients]
The polycarbonate resin composition of the present invention may contain other components in addition to those described above as necessary, as long as the desired physical properties are not significantly impaired. Examples of other components include various resin additives. In addition, 1 type may contain other components and 2 or more types may contain them by arbitrary combinations and ratios.

・ ・ Resin additives Resin additives include, for example, phosphorus-based, metal salt-based, and silicon-based flame retardants, anti-dripping agents such as fluoropolymers, anti-fogging agents, anti-blocking agents, fluidity improvers, and sliding properties. Examples include modifiers, plasticizers, dispersants, and antibacterial agents. In addition, 1 type may contain resin additive and 2 or more types may contain it by arbitrary combinations and a ratio.

[11. Production method of polycarbonate resin composition]
There is no restriction | limiting in the manufacturing method of the polycarbonate resin composition of this invention, The manufacturing method of a well-known polycarbonate resin composition can be employ | adopted widely.
Specific examples include aromatic polycarbonate resin (A), (meth) acrylate copolymer (B), phosphorus stabilizer (C), and full esterified product of aliphatic alcohol and aliphatic carboxylic acid according to the present invention. (D) and other components to be blended as necessary 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 extrusion And a melt kneading method using a mixer such as a machine, a twin-screw 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 to obtain 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.

[12. Molded body]
The aromatic polycarbonate resin composition of the present invention is usually molded into an arbitrary shape and used as a molded body (resin composition molded body). There is no restriction | limiting in the shape, pattern, color, dimension, etc. of this molded object, What is necessary is just to set arbitrarily according to the use of the molded object.

  Examples of the molded body include parts such as electrical and electronic equipment, OA equipment, information terminal equipment, machine parts, home appliances, vehicle parts, building members, various containers, leisure goods / miscellaneous goods, and lighting equipment. Among these, it is particularly suitable for use in parts such as electrical and electronic equipment, OA equipment, information terminal equipment, home appliances, and lighting equipment, and 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, Video cameras, mobile phones, battery packs, recording medium drives and reading devices, mice, numeric keys, CD players, MD players, portable radio / audio players, and the like. 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.

The manufacturing method of a molded object is not specifically limited, The molding method generally employ | adopted about the polycarbonate resin composition can be employ | adopted arbitrarily. 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.
The obtained molded product of the present invention can be used as a practical molded product having high surface hardness while maintaining transparency without impairing the excellent properties of the polycarbonate resin as described above.

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.
The measurement / evaluation methods used in the examples and comparative examples are as follows.

[1. Weight average molecular weight of aromatic polycarbonate resin (Mw)]
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: Showa Denko "Shodex K-805L" (two)
Detector; UV detector 254 nm
Eluent: Chloroform

  Next, after the GPC measurement, the relationship between the elution time and the molecular weight of polycarbonate (PC) was determined by the universal calibration method to obtain a calibration curve. The elution curve (chromatogram) of PC 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

The following formula was used as the conversion formula. In the calculation formula, MPC represents the molecular weight of PC, and MPS represents the molecular weight of PS. The calculation formula is obtained from the following Mark-Houwink formula representing the relationship between the intrinsic viscosity [η] and the molecular weight M. However, the values of K and α are values of K: 1.11 × 10 ⁻⁴ and α: 0.725 in the case of PS and K: 3.89 × 10 ⁻⁴ and α: 0.700 in the case of PC. It was used.

(Conversion formula)
MPC = 0.47822MPS ^1.01470
MPS = 2.0689 ^{MPC 0.98551}
[Η] = KM ^α

  Then, the polycarbonate elution curve (chromatogram) is measured under the same conditions as in the calibration curve, and the mass average molecular weight of the aromatic polycarbonate resin is calculated from the elution time (molecular weight) and the peak area (number of molecules) of the elution time. Asked. This value is in terms of polycarbonate (PC).

[2. Fluidity evaluation]
After drying the pellets obtained by the production method described later at 100 ° C. for 4 hours or more, using a high load type flow tester, the effluent Q value per unit time of the composition under the conditions of 280 ° C. and a load of 160 kgf ( (Unit: × 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. The results are shown in Tables 1 and 2. In the table, it is expressed as “fluidity”.

[3. Impact resistance evaluation]
Impact resistance (Izod impact strength) (unit: J / m):
In accordance with ASTM D256, an Izod impact strength (unit: J / m) was measured at a temperature of 23 ° C. for a notched specimen having a thickness of 3.2 mm formed by the method described later. The larger the value, the better the impact resistance. The results are shown in Tables 1 and 2. In the table, “Izod” is used.

[4. Heat resistance evaluation]
DTUL (deflection temperature under load) (unit: ° C):
Using an ISO multi-purpose test piece molded by the method described later, the measurement was performed in accordance with ISO 75-1 & 2 under the condition of a load of 1.80 MPa (Method A). The results are shown in Tables 1 and 2. In the table, “DTUL” is used.

[5. Transparency evaluation]
Haze (haze value) (unit:%):
In accordance with JIS K-7105, a flat test piece (3 mm thickness) described later was used as a test piece, and a haze value (unit “%”) was measured with an NDH-2000 type haze meter manufactured by Nippon Denshoku Industries Co., Ltd. The haze is a value used as a measure of the turbidity of the resin, and the smaller the numerical value, the higher the transparency. The results are shown in Tables 1 and 2. In the table, “Haze” is used.

[6. Hue evaluation]
YI value:
A flat test piece (3 mm thick) described later is used as a test piece, and in accordance with JIS K-7105, a Y2000 (Yellow Index) is obtained by a transmission method using a SE2000 type spectrocolorimeter manufactured by Nippon Denshoku Industries Co., Ltd. It was measured. A smaller YI value is preferable because the degree of yellowing of the resin is lower. The results are shown in Tables 1 and 2. In the table, “YI” is used.

[7. Surface hardness evaluation]
Pencil hardness:
According to JIS K5400, a scratch test was performed 5 times on a 3 mm-thick flat plate test piece molded by the method described below to evaluate the hardness. Results are shown in Tables 1 and 2. In the table, it is expressed as “pencil hardness”.

(Examples 1-6, Comparative Examples 1-6)
[Production of resin pellets]
Each component to be described later is blended in the ratios (mass ratios) shown in Tables 1 and 2 and mixed for 20 minutes with a tumbler, then supplied to Nippon Steel Works (TEX30HSST) equipped with 1 vent, and screw Kneaded under the conditions of a rotation speed of 200 rpm, a discharge rate of 20 kg / hour, and a barrel temperature of 260 ° C., the molten resin extruded into a strand is quenched in a water tank and pelletized using a pelletizer to obtain a pellet of a polycarbonate resin composition It was.

[Preparation of test piece]
After the pellets obtained by the above-described production method were dried at 100 ° C. for 5 hours, the cylinder temperature was 260 ° C., the mold temperature was 80 ° C., and the molding cycle was performed with an injection molding machine (“M150AII-SJ” manufactured by Meiki Seisakusho). Injection molding was performed under the condition of 50 seconds, and Izod impact test pieces and flat plate test pieces having a thickness of 50 × 90 × 3 mm were prepared.
Moreover, after drying the pellet obtained by the above-mentioned manufacturing method at 100 ° C. for 5 hours, the cylinder temperature was 260 ° C. using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., Cycap M-2, clamping force 75T). Then, injection molding was performed under the conditions of a mold temperature of 80 ° C. and a molding cycle of 50 seconds to produce an ISO multipurpose test piece, which was used for DTUL (heat resistance) evaluation.

  The used materials are as follows. The pencil hardness of each material used as the aromatic polycarbonate resin (A) and the (meth) acrylate copolymer (B) is [7. [Surface hardness evaluation]

[Materials used]
(A) Aromatic polycarbonate resin:
(A-1) Mitsubishi Engineering Plastics, trade name “Iupilon (registered trademark) S-3000”, mass average molecular weight 26,800, pencil hardness 2B
(A-2) Made by Mitsubishi Engineering Plastics, trade name “Iupilon (registered trademark) E-2000”, mass average molecular weight 35,500, pencil hardness 2B
(The mass average molecular weights of (A-1) and (A-2) are values in terms of polycarbonate)

(B) (Meth) acrylate copolymer:
In a heatable reaction vessel equipped with a thermometer, a nitrogen inlet tube, a reflux condenser, and a stirrer, 200 parts of deionized water, 0.3 part of a dispersant, 0.5 part of sodium sulfate, 2,2′- Charge 0.3 parts of azobisisobutyronitrile, 33 parts of phenyl methacrylate, 66 parts of methyl methacrylate, 1 part of methyl acrylate, and 1.8 parts of n-octyl mercaptan. The inside of the reaction vessel was replaced with nitrogen, and the temperature was raised to 80 ° C. Warm up. After stirring for 4 hours, the resulting bead polymer was washed with water and dried to obtain a (meth) acrylate copolymer. The pencil hardness was 2H and the mass average molecular weight was 15,000. This mass average molecular weight is a polystyrene (PS) equivalent value measured using gel permeation chromatography with chloroform as a solvent.

In addition, 70 parts of potassium methacrylate and 30 parts of methyl methacrylate were copolymerized as a dispersant, and 65 parts of sodium 2-sulfoethyl methacrylate, 10 parts of potassium methacrylate, and 25 parts of methyl methacrylate were copolymerized by mass ratio. The mixture was mixed 1: 1 and a 10% aqueous solution of the mixed polymer was used.
(C) Phosphorus heat stabilizer:
Tris (2,4-di-tert-butylphenyl) phosphite manufactured by Adeka Co., Ltd., trade name “ADK STAB 2112”
(D) Full esterified product (release agent) of aliphatic alcohol and aliphatic carboxylic acid:
(D-1) Stearyl stearate, made by NOF Corporation, trade name “Unistar M9676”
(D-2) Pentaerythritol tetrastearate manufactured by Cognis Japan, trade name “Roxyol VPG861”

(E) Antioxidant:
Pentaerystol-tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate]
Product name “Irganox 1010” manufactured by Ciba
(F) UV absorber:
2- (2′-Hydroxy-5′-tert-octylphenyl) -2H-benzotriazole manufactured by Cypro Kasei Co., Ltd., trade name “Seesorb 709”
(G) Acrylic resin:
“Acrypet VH-001” manufactured by Mitsubishi Rayon Co., Ltd., pencil hardness 2H, mass average molecular weight 60,000 (polystyrene conversion).
(H) Release agent other than D component, manufactured by Clariant Japan, trade name “LICOWAX PE520POWDER”,
Number average molecular weight 2,000 (polystyrene conversion).

It can be seen that the aromatic polycarbonate resin compositions described in the Examples have good surface hardness and good hue while maintaining transparency.
On the other hand, since Comparative Example 1 does not contain the (meth) acrylate copolymer of the present invention, the surface hardness is insufficient, and Comparative Examples 2 and 3 do not contain additives within the scope of the present invention. Therefore, the hue is inferior or the transparency is impaired.
In addition, Comparative Examples 4 and 5 contain an acrylic resin that is insufficiently compatible with the aromatic polycarbonate resin, so that the surface hardness is good but it is opaque. Moreover, in comparative example 6, since there is too much content of the (meth) acrylate copolymer of this invention, fluidity | liquidity is too high and impact resistance is inferior.

  The present invention can be used in a wide range of industrial fields. For example, electrical and electronic equipment and parts thereof, OA equipment, information terminal equipment, mechanical parts, home appliances, vehicle parts, building members, various containers, and leisure goods. -It is suitable for use in fields such as general merchandise and lighting equipment.

Claims (5)

Aromatic polycarbonate resin (A) having a mass average molecular weight of 15,000 to 40,000, 40 to 95% by mass,
The mass ratio (b1 / b2) of the aromatic (meth) acrylate unit (b1) to the methyl methacrylate unit (b2) is 5 to 80/20 to 95, and the mass average molecular weight is 5,000 to 30,000 (meta ) Acrylate copolymer (B) 5-60 mass%,
For a total of 100 parts by mass of the resin components (A) and (B) consisting of
Phosphorus stabilizer (C) 0.001 to 1 part by mass,
An aromatic polycarbonate resin composition comprising 0.001 to 1 part by mass of a full esterified product (D) of an aliphatic alcohol and an aliphatic carboxylic acid. A full esterified product (D) of an aliphatic alcohol and an aliphatic carboxylic acid is a full esterified product (D1) of a monoaliphatic alcohol and a monoaliphatic carboxylic acid, and a polyaliphatic alcohol and a monoaliphatic carboxylic acid. The aromatic polycarbonate resin composition according to claim 1, which comprises a fully esterified product (D2). A full esterified product (D1) of monoaliphatic alcohol and monoaliphatic carboxylic acid is a full esterified product of stearyl alcohol and stearic acid (stearyl stearate), and a full esterified product of behenyl alcohol and behenic acid (behenyl behenate). The aromatic polycarbonate resin composition according to claim 2, which is at least one selected from the group consisting of The full esterified product (D2) of a polyhydric aliphatic alcohol and a monoaliphatic carboxylic acid is a full esterified product (pentaerythritol tetrastearate) of pentaerythritol and stearic acid. Aromatic polycarbonate resin composition. A molded article comprising the resin composition according to any one of claims 1 to 4.