CN104066793A - Polycarbonate resin composition and molded article thereof - Google Patents

Abstract

A polycarbonate resin composition comprising 100 parts by mass of a resin component comprising 60 to 95% by mass of an aromatic polycarbonate resin, (B) 2 to 30% by mass of a polyolefin resin and/or a polyolefin elastomer containing an epoxy group or a glycidyl group, and (C) 1 to 38% by mass of a polyolefin resin other than the component (B); and (D) a phosphorus-containing compound, wherein the component (D) is (D1) and/or (D2) below. (D1) 0.01 to 0.5 parts by mass of at least 1 member selected from the group consisting of phosphite ester compounds and phosphate ester compounds having at least 1 alkoxy group bonded to a phosphorus atom, wherein the compound has an aryloxy group bonded to a phosphorus atom, and all ortho-positions of the aryloxy group are hydrogen atoms. (D2) 0.001 to 0.1 parts by mass of at least 1 member selected from phosphoric acid, phosphorous acid, phosphonic acid and phosphonous acid.

Description

Polycarbonate resin composition and molded article thereof

technical field

The present invention relates to a polycarbonate resin composition and its molded body. More specifically, it relates to a molded article having excellent impact resistance, no delamination and less uneven gloss, and a polycarbonate resin composition providing the molded article.

Background technique

Polycarbonate resin is used as an important raw material for electronic, information, electric parts, mechanical parts, etc. due to its excellent mechanical strength such as heat resistance and impact resistance, and transparency. However, since it also has disadvantages such as low fluidity and poor chemical resistance, alloying of polycarbonate with polyolefin is being studied in order to improve these characteristics.

For example, polycarbonate is alloyed with polyolefin-based resin and/or polyolefin-based elastomer having polycarbonate, an epoxy group, etc. (Patent Documents 1 to 4). Thereby, a polycarbonate resin having excellent fluidity and the like while maintaining mechanical strength such as heat resistance and impact resistance can be obtained.

Patent Document 3 describes that by mixing aromatic polycarbonate resins, polyethylene resins, polyolefin resins having epoxy groups or glycidyl groups, and amine compounds, polycarbonate resins excellent in fluidity and the like can be obtained. resin composition. In addition, Patent Document 4 discloses a resin composition containing an aromatic polycarbonate resin, a polyolefin resin, a polyolefin resin having an epoxy group or a glycidyl group, and a phosphorus-based flame retardant.

However, the resin compositions described in Patent Documents 1 to 4 may be peeled off due to the vicinity of the high-shear gate shape or molding conditions. Moreover, especially when an inorganic filler, a coloring material, etc. are mix|blended with this resin composition, the molded article may generate|occur|produce gloss unevenness, and further improvement is demanded.

prior art literature

patent documents

Patent Document 1: Japanese Patent Laid-Open No. 2009-275131

Patent Document 2: Japanese Patent Laid-Open No. 2009-298993

Patent Document 3: Japanese Patent Laid-Open No. 2010-24368

Patent Document 4: Japanese Patent Laid-Open No. 2011-132312

Contents of the invention

The problem to be solved by the invention

The object of the present invention is to provide a product that complements the disadvantages of aromatic polycarbonate resins, has excellent impact resistance, and does not exhibit delamination after molding even if it is a thin molded product, especially in the molding of film gates, pin gates, etc. A polycarbonate resin composition and a molded article thereof that do not cause peeling near the gate when the molded article is thin and have less uneven gloss.

means of solving problems

The inventors of the present invention have carried out extensive and intensive studies in order to achieve the above object, and found that by making polyolefin resins containing aromatic polycarbonate resins, epoxy groups or glycidyl groups in specific proportions, and/or A polyolefin-based elastomer and a polycarbonate resin composition in which a specific phosphorus-containing compound is added to the resin component of the polyolefin-based resin can achieve the above object, and the present invention has been accomplished.

That is, the present invention provides the following polycarbonate resin composition and its molded article.

1. A polycarbonate resin composition comprising (A) 60 to 95% by mass of an aromatic polycarbonate resin, (B) a polyolefin-based resin and/or a polyolefin-based resin containing an epoxy group or a glycidyl group 2 to 30% by mass of elastomer, and 100 parts by mass of resin components of 1 to 38% by mass of polyolefin resin other than (C) the above-mentioned (B) component; and (D) a phosphorus-containing compound, the (D) component being (D1) and/or (D2) below,

(D1) 0.01 to 0.5 parts by mass of at least one selected from phosphite compounds and phosphate compounds having at least one alkoxy group bonded to the phosphorus atom, wherein the compound has In the case of an aryloxy group, it is a compound in which all the ortho positions of the aryloxy group are hydrogen atoms;

(D2) 0.001 to 0.1 parts by mass of at least one selected from phosphoric acid, phosphorous acid, phosphonic acid, and phosphonous acid.

2. The polycarbonate resin composition according to the above 1, wherein (A) the aromatic polycarbonate resin comprises an aromatic polycarbonate resin having a hydroxyl group as a molecular chain terminal group, and the hydroxyl group is The content of clusters is 20-80 mol%.

3. The polycarbonate resin composition according to the above 1, wherein (A) the aromatic polycarbonate resin comprises an aromatic polycarbonate resin having a hydroxyl group as a molecular chain terminal group, and the hydroxyl group is The content of agglomerates is less than 20 mol%.

4. The polycarbonate resin composition according to the above 3, wherein, with respect to 100 parts by mass of the resin component, (E) is selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxide, and hydroxyl ammonium salts. and 0.0001 to 1 part by mass of at least one of quaternary phosphonium salts.

5. The polycarbonate resin composition as described in any one of said 1-4 which contains 3-20 mass parts of (F) phosphorus flame retardants with respect to 100 mass parts of said resin components.

6. The polycarbonate resin composition as described in any one of said 1-5 which contains 1-20 mass parts of (G) inorganic fillers with respect to 100 mass parts of said resin components.

7. The polycarbonate resin composition according to the above 6, wherein the (G) inorganic filler is an inorganic filler containing magnesium silicate.

8. The polycarbonate resin composition according to any one of 1 to 7 above, which contains 0.05 to 5 parts by mass of the (H) coloring material with respect to 100 parts by mass of the resin component.

9. The polycarbonate resin composition according to the above 8, wherein the (H) coloring material is a metal oxide.

10. The polycarbonate resin composition according to any one of 1 to 9 above, wherein the viscosity average molecular weight of the component (A) is 11,000 to 30,000.

11. A molded article obtained by injection molding the polycarbonate resin composition described in any one of 1 to 10 above.

Invention effect

According to the present invention, it is possible to provide a polycarbonate resin that can improve the compatibility between polycarbonate resin and polyolefin resin, has excellent impact resistance, does not exhibit delamination after molding even if it is a thin molded product, and has little gloss unevenness. Carbonate resin composition and its molded body.

Detailed ways

The polycarbonate resin composition of the present invention contains (A) 60 to 95% by mass of an aromatic polycarbonate resin, (B) a polyolefin-based resin and/or a polyolefin-based resin containing an epoxy group or a glycidyl group. 2 to 30% by mass of elastomer, and 100 parts by mass of resin components of 1 to 38% by mass of polyolefin resin other than (C) the above-mentioned (B) component; and (D) a phosphorus-containing compound, the (D) component being (D1) and/or (D2) below.

(D1) 0.01 to 0.5 parts by mass of at least one kind selected from phosphite compounds and phosphate compounds having at least one alkoxy group bonded to the phosphorus atom (wherein the compound has In the case of an aryloxy group, it is a compound in which all the ortho positions of the aryloxy group are hydrogen atoms).

(D2) 0.001 to 0.1 parts by mass of at least one selected from phosphoric acid, phosphorous acid, phosphonic acid, and phosphonous acid.

Each component used for the polycarbonate resin composition of this invention is demonstrated below.

[(A) Aromatic polycarbonate resin]

Various aromatic polycarbonate resins manufactured by reaction of a dihydric phenol and a carbonate precursor can be used as aromatic polycarbonate resin which is (A) component in this invention.

Examples of the dihydric phenol include various dihydric phenols, particularly 2,2-bis(4-hydroxyphenyl)propane [bisphenol A], bis(4-hydroxyphenyl)methane, 1 , 1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 4,4'-dihydroxydiphenyl, bis(4 -Hydroxyphenyl)cycloalkane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide and Bis(4-hydroxyphenyl)ketone, etc. These dihydric phenols may be used individually or in mixture of 2 or more types.

In particular, preferable dihydric phenols are bis(hydroxyphenyl)alkane-based, especially bisphenol A, or dihydric phenols containing bisphenol A as the main raw material.

Examples of carbonate precursors include carbonyl halides, carbonyl esters, and haloformic acid esters. Specifically, carbonyl chlorides, dihaloformic acid esters of dihydric phenols, diphenyl carbonate, carbonic acid Dimethyl ester, and diethyl carbonate, etc.

In addition, the aromatic polycarbonate may have a branched structure. Examples of branching agents include: 1,1,1-tris(4-hydroxyphenyl)ethane, α,α',α"-tris(4-hydroxyphenyl)-1,3,5- Triisopropylbenzene, phloroglucinol, trimellitic acid and isatin bis(o-cresol), etc.

The viscosity average molecular weight of the aromatic polycarbonate resin of (A) component in this invention becomes like this. Preferably it is 11,000-30,000, More preferably, it is 12,000-28,000, More preferably, it is 12,000-25,000. When the viscosity average molecular weight is 11000 or more, the impact resistance is sufficient, and when it is 30000 or less, the formability is good and delamination of the molded article does not occur.

It should be noted that the viscosity-average molecular weight of the component (A) in the present invention is obtained by substituting the specific viscosity (η _sp ) into the following formula. The specific viscosity (η _sp ) is measured at 20 It is obtained by dissolving about 0.7 g of aromatic polycarbonate resin in 100 cm ³ of dichloromethane at ℃.

(η _sp )/C=[η]+0.45×[η] ² C

[η]=1.23×10 ^-5 M ^0.83

(where [η] is the intrinsic viscosity, and C is the polymer concentration)

The compounding quantity of (A) component in this invention is 60-95 mass % in the total quantity of (A)-(C)component. If it is less than 60 mass %, impact resistance etc. will fall, and when it exceeds 95 mass %, the improvement effect of fluidity etc. may become insufficient. The compounding amount is preferably 65 to 92% by mass, more preferably 70 to 90% by mass.

The aromatic polycarbonate resin of (A) component used here contains the aromatic polycarbonate resin which has a hydroxyl group as its molecular chain terminal group, and it can determine whether to mix (E ) components are aliphatic amines, aromatic amines, ammonium hydroxide, hydroxyl ammonium salts, quaternary phosphonium salts, etc.

That is, when the content of the terminal hydroxyl group is 20 mol% or more relative to the total terminal groups of the aromatic polycarbonate resin, it is not necessary to add the above-mentioned (E) component, but the content of the terminal hydroxyl group of the aromatic polycarbonate resin is less than 20 mol% In this case, it is preferable to add the above-mentioned (E) component, that is, at least one compound selected from the group consisting of aliphatic amines, aromatic amines, ammonium hydroxide, hydroxyammonium salts, and quaternary phosphonium salts. Of course, even if the content of the terminal hydroxyl group is 20 mol% or more, the above-mentioned (E) component, etc. may be added, and conversely, even if the content of the terminal hydroxyl group is less than 20 mol%, the above-mentioned (E) component, etc. may not be added.

As the (A) component, when an aromatic polycarbonate resin having a terminal hydroxyl group content of 20 mol% or more is used with respect to all terminal groups of the aromatic polycarbonate resin, the content of the terminal hydroxyl group is changed from epoxy group or shrink From the viewpoint of the reactivity of the glyceryl group, it is preferably 20 to 80 mol%, more preferably 20 to 60 mol%, and still more preferably 20 to 50 mol%. If the content is 20 mol% or more, the reactivity with epoxy groups or glycidyl groups is good, and if it is 80 mol% or less, no crosslinking reaction occurs, and it is unlikely to cause a decrease in the fluidity of the resin composition obtained. Reduced impact resistance.

It should be noted that the content of terminal hydroxyl groups relative to the total terminal groups of the aromatic polycarbonate resin (hereinafter also referred to as "OH terminal fraction") can be determined by measuring ¹ H-NMR from the peak derived from terminal hydroxyl groups. integral value to determine.

[(B) Polyolefin-based resin and/or polyolefin-based elastomer containing epoxy group or glycidyl group]

The (B) component in the present invention, that is, the polyolefin-based resin can be, for example, a homopolymer of an olefin having an epoxy group or a glycidyl group, or a copolymer of an olefin and an unsaturated monomer having an epoxy group or a glycidyl group. A copolymer obtained by copolymerizing an olefin polymer, an olefin polymer and an unsaturated monomer having an epoxy group or a glycidyl group, such a copolymer may be a graft copolymer, a random copolymer or a block copolymer.

In addition, for example, hydrogen peroxide or an organic peracid such as perbenzoic acid may be used to replace unsaturated bonds present at the terminal of an olefin polymer, or a copolymer of an olefin and other unsaturated monomers, or their complexes. , performic acid, peracetic acid, etc., which are oxidized to introduce epoxy groups. That is, any polymer may be used as long as it has an epoxy group or a glycidyl group introduced into it.

In addition, the polyolefin-based elastomer in the (B) component refers to a low-crystalline or amorphous olefin-based elastomer containing an epoxy group or a glycidyl group and having a degree of crystallinity measured by X-ray diffraction method of 50% or less. copolymer.

Examples of olefins include ethylene, propylene, 1-butene, isobutene, 2-butene, cyclobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, and 3-methanol Base-1-butene, 4-methyl-1-butene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene, and 1-dodecene, etc. These may be used alone or in combination of two or more.

Examples of unsaturated monomers having an epoxy group or a glycidyl group include glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether, methacrylic Acyl glycidyl ether, 2-methacryl glycidyl ether, styrene p-glycidyl ether, glycidyl cinnamate, glycidyl itaconate, and N-[4-(2,3-cyclo Oxypropoxy)-3,5-dimethylbenzyl]methacrylamide, etc. These can be used alone or in combination of two or more. Furthermore, it is also possible to use these unsaturated monomers having epoxy groups or glycidyl groups and unsaturated monomers such as alkyl acrylates and methacrylates at the same time. Epoxy or glycidyl unsaturated monomers and their copolymerization are substances containing acrylate, methacrylate and other groups in addition to glycidyl.

In the olefins and monomers constituting the (B) component in the present invention, that is, the polyolefin resin and/or polyolefin elastomer, the content of the unsaturated monomer having an epoxy group or a glycidyl group is preferably 1 to 20 mass %. When the content is 1% by mass or more, the effect of improving the compatibility of the component (A) and the component (C) can be exhibited, the tensile elongation and impact resistance will not decrease, and the delamination of the molded product will not occur. . Moreover, if it is 20% by mass or less, self-crosslinking is unlikely to occur, the tensile elongation and impact resistance will not decrease, and delamination of the molded article will not occur. From such a viewpoint, content of the unsaturated monomer which has an epoxy group or a glycidyl group becomes like this. Preferably it is 2-18 mass %, More preferably, it is 4-15 mass %.

Moreover, it is preferable that the weight average molecular weight of (B) component is about 50,000-500,000. Within this range, while preventing delamination, good tensile elongation and high impact resistance can be obtained. In addition, the weight average molecular weight can be calculated|required using the gel permeation chromatography (GPC) method.

In the present invention, as the (B) component, one or more polyolefin resins having an epoxy group or a glycidyl group may be used, and one or more polyolefin resins having an epoxy group or a glycidyl group may be used. body, and one or more of the above-mentioned polyolefin-based resins and one or more of polyolefin-based elastomers may be used in combination.

The compounding quantity of (B) component in this invention is 2-30 mass % in the total quantity of (A)-(C)component. If it is less than 2 mass %, the improvement of the compatibility of (A) component and (C) component will be insufficient, impact resistance will fall, and the lamellar peeling of a molded object may generate|occur|produce. If it exceeds 30% by mass, self-crosslinking tends to occur, the impact resistance decreases, and layer peeling of the molded product may occur in some cases. From such a viewpoint, the blending amount is preferably 2 to 20% by mass, more preferably 3 to 10% by mass.

[(C) Polyolefin resin]

The (C)component in this invention is a polyolefin-type resin other than the polyolefin-type resin which has an epoxy group or a glycidyl group which is the said (B) component. Examples of polyolefin-based resins include homopolymers obtained by independently polymerizing the aforementioned olefins such as ethylene, propylene, and butene, and polymers obtained by copolymerizing them.

For example, polyethylene-based resins may be obtained by polymerizing ethylene alone, or may be obtained by copolymerizing mainly ethylene, and include high-density polyethylene, medium-density polyethylene, and low-density polyethylene. Polyethylene-based resins such as ethylene, linear low-density polyethylene, ethylene-α-olefin copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylate copolymer, and the like. In addition, examples of the ethylene-α-olefin copolymer include copolymers of propylene and ethylene, and may be any of graft copolymers, random copolymers, and block copolymers. Among them, high-density polyethylene is particularly preferable.

The melt index (MI) of these polyethylene-based resins is preferably about 0.01 to 50 g/10 minutes, more preferably 0.02 to 30 g/10 minutes. When MI is 0.01 g/10 minutes or more, the effect of improving fluidity can be sufficiently exhibited, and if it is 50 g/10 minutes or less, delamination of the molded article becomes less likely to occur.

In addition, MI in the case of a polyethylene-type resin can be calculated|required according to the measuring method of ASTM D1238, and is the value measured on the conditions of resin temperature 190 degreeC, and load 21.18N.

In addition, the polypropylene-based resin may be obtained by polymerizing propylene alone, or may be obtained by copolymerizing mainly propylene. Examples thereof include isotactic propylene homopolymers and syndiotactic propylene homopolymers. In addition, the copolymer includes, for example, a copolymer of propylene and ethylene, and may be any of a graft copolymer, a random copolymer, or a block copolymer.

The melt index (MI) of such a polypropylene resin is preferably about 0.1 to 60 g/10 minutes, and more preferably 0.1 to 50 g/10 minutes. If MI is 0.1 g/10 minutes or more, the effect of improving fluidity can be fully exhibited, and if it is 60 g/10 minutes or less, delamination of the molded article is less likely to occur. In addition, the MI of this polypropylene-type resin can be calculated|required according to the measuring method of ASTM D1238, and it is the value measured under the conditions of resin temperature 230 degreeC, and load 21.18N.

In addition, polyolefin-based resins having a melt index (MI) of about 0.01 to 60 g/10 min (230° C., 21.18 N) can be used similarly in addition to the above-mentioned polyethylene-based resins or polypropylene-based resins.

In the present invention, as the (C) component, one kind of the above-mentioned polyolefin-based resins may be used, or two or more kinds of the above-mentioned polyolefin-based resins may be used in combination.

The compounding quantity of (C)component in this invention is 1-38 mass % in the total amount of (A)-(C) component, Preferably it is 5-35 mass %, More preferably, it is 7-30 mass %. If it is less than 1% by mass, the effect of improving fluidity cannot be sufficiently exhibited, and if it exceeds 38% by mass, the impact resistance will decrease, and delamination of the molded article tends to easily occur in some cases.

[(D) Phosphorus-containing compound]

The phosphorus-containing compound used as (D)component of this invention is following (D1) and/or (D2).

(D1) 0.01 to 0.5 parts by mass of at least one kind selected from phosphite compounds and phosphate compounds having at least one alkoxy group bonded to the phosphorus atom (wherein the compound has In the case of an aryloxy group, it is a compound in which all the ortho positions of the aryloxy group are hydrogen atoms).

(D2) 0.001 to 0.1 parts by mass of at least one selected from phosphoric acid, phosphorous acid, phosphonic acid, and phosphonous acid.

The component (D) of the present invention can play the role of activating the epoxy group or glycidyl group of the epoxy group or glycidyl group-containing polyolefin-based resin and/or polyolefin-based elastomer of the (B) component. , improve the generation efficiency of the reaction product of (A) component and (B) component that acts as a compatibilizing component, improve the compatibility of the resin of the (A) and (C) component at the same time, improve the (A) component The dispersibility of the (C) component in the film suppresses the orientation of the (C) component, and suppresses delamination and uneven gloss. The above effect is remarkable when the (G) inorganic filler and (H) coloring material described later are used in combination, and is particularly remarkable when magnesium silicate is used as the (G) inorganic filler and a metal oxide is used as the (H) coloring material.

<(D1) Components>

The (D1) component in this invention is at least 1 sort(s) chosen from the phosphite compound and the phosphoric acid ester compound which couple|bonded at least 1 alkoxy group to a phosphorus atom. However, when the compound has an aryloxy group bonded to a phosphorus atom, all the ortho-positions of the aryloxy group are hydrogen atoms.

Examples of the phosphite compound and the phosphoric acid ester compound in which at least one alkoxy group is bonded to the phosphorus atom include phosphoric acid, phosphorous acid, phosphonic acid, and esters of phosphonous acid.

Examples of the phosphite compound include: tridecyl phosphite, trioctyl phosphite, trioctadecyl phosphite, didecyl monophenyl phosphite, dioctyl Monophenyl phosphite, diisopropyl monophenyl phosphite, monobutyl diphenyl phosphite, monodecyl diphenyl phosphite, monooctyl diphenyl phosphite, dihard Aliphatic pentaerythritol diphosphite, etc.

Examples of the phosphate ester compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, dibutylphenyl phosphate, dioctyl phenyl phosphate, and tributyl phosphate. base phosphate, diisopropylphenyl phosphate, etc.

Among the above-mentioned compounds, from the viewpoint of improving compatibility, tridecyl phosphite, monooctyl diphenyl phosphite, and distearyl pentaerythritol diphosphite are preferable. These compounds may be used alone or in combination of two or more.

The compounding quantity of (D1) component in this invention is 0.01-0.5 mass parts with respect to 100 mass parts of resin components containing said (A)-(C), Preferably it is 0.03-0.4 mass parts. If it is less than 0.01 parts by mass, the effect of improving the production efficiency of the above-mentioned compatibilizing components becomes insufficient, and if it exceeds 0.5 parts by mass, the production efficiency of the compatibilizing components becomes too high, the number of crosslinking components increases, and the impact resistance sex decline.

<(D2) Components>

The (D2) component in this invention is at least 1 sort(s) chosen from phosphoric acid, phosphorous acid, a phosphonic acid, and a phosphonous acid. Among the above, phosphoric acid and phosphorous acid are preferable. These compounds may be used alone or in combination of two or more.

Component (D2) is a substance that activates the epoxy group or glycidyl group in component (B) to promote self-crosslinking reaction, thereby increasing the strength of the compatibilizing component and suppressing the interaction between component (A) and (C) Suppresses delamination and delamination due to deformation and orientation due to viscosity difference of component.

The compounding quantity of (D2) component in this invention is 0.001-0.1 mass part with respect to 100 mass parts of resin components containing said (A)-(C), Preferably it is 0.002-0.05 mass part. If it is less than 0.001 parts by mass, the effect of promoting the above-mentioned self-crosslinking reaction becomes insufficient. If it exceeds 0.1 parts by mass, the above-mentioned self-crosslinking becomes too much, and the impact resistance decreases. ) The reaction amount of the component is relatively reduced, and the function as a compatibilizing component is reduced.

As (D)component in this invention, either one of the said (D1) or (D2) component may be used alone, and may be used together. When the above-mentioned (D1) and (D2) components are used together, it is preferable to use 0.01 to 0.5 parts by mass of the (D1) component and 0.001 to 0.001 to The range of 0.1 mass part is compounded.

In addition, in the polycarbonate resin composition of the present invention, in addition to the above (A) to (D) components, (E) can also be mixed with (E) selected from aliphatic amine salts, aromatic amine salts, ammonium hydroxide, hydroxyl ammonium salts , and at least one of quaternary phosphonium salts, (F) phosphorus-based flame retardants for improving flame retardancy, (G) inorganic fillers for improving flame retardancy and rigidity, or for improving appearance (H) Coloring material.

[(E) Aliphatic amine salts, aromatic amine salts, ammonium hydroxide, hydroxyl ammonium salts, and quaternary phosphonium salts]

The (E) component in this invention is at least 1 sort(s) chosen from an aliphatic amine salt, an aromatic amine salt, ammonium hydroxide, a hydroxyl ammonium salt, and a quaternary phosphonium salt, and can use it as needed.

Aliphatic amine salts and aromatic amine salts, for example, can be represented by the general formula R ¹ R ² R ³ N·1/nA ^1. When they are aliphatic amine salts, R ¹ to R ³ independently represent a hydrogen atom or an aliphatic group ( Among them, not all of them are hydrogen atoms at the same time). In the case of an aromatic amine salt, R ¹ to R ³ independently represent a hydrogen atom or an aromatic group (however, not all of them are hydrogen atoms at the same time). ^A1 represents an acid, for example: hydrochloric acid, sulfuric acid, nitric acid, chloric acid, perchloric acid, acetic acid, monoalkyl sulfuric acid, sulfonic acid compound, etc. n is the valence of the anion of acid ^A1 , for example, n=1 in the case of hydrochloric acid and n=2 in the case of sulfuric acid.

Ammonium hydroxide can be represented by, for example, the general formula R ⁴ R ⁵ R ⁶ R ⁷ N ⁺ ·OH ^- . R ⁴ to R ⁷ independently represent, for example, a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms (however, not all of them are hydrogen atoms at the same time).

Specific examples of the ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetraisopropylammonium hydroxide, and the like.

On the other hand, as a hydroxyammonium salt, for example, it can be represented by the general formula R ⁸ R ⁹ NOH·1/mA ² , where R ⁸ and R ⁹ independently represent a hydrogen atom or a linear or branched chain having 1 to 5 carbon atoms. Chain-like alkyl groups (however, not all of them are hydrogen atoms at the same time). A ² represents an acid, and m is the valence number of the anion of the acid A ² .

Examples of the hydroxyammonium salt include methylhydroxylamine hydrochloride, ethylhydroxylamine hydrochloride, n-propylhydroxylamine hydrochloride, isopropylhydroxylamine hydrochloride, dimethylhydroxylamine hydrochloride, and dimethylhydroxylamine hydrochloride. Amine hydrochloride, diethylhydroxylamine hydrochloride, and hydroxylamines obtained by substituting hydrochloric acid in these hydroxylamines with other acids such as sulfuric acid, nitric acid, acetic acid, monoalkylsulfuric acid, sulfonic acid compounds, etc. .

In addition, the quaternary phosphonium salt is not particularly limited, and for example, a compound represented by any one of the following general formulas (I) to (III) can be used.

(PR ₄ ) ⁺ ·(X ² ) ^- ···(I)

(PR ₄ ) ⁺ ₂ ·(Y ² ) ^2- ···(II)

[(PR ₄ ) ⁺ O ^- ] _n -P(=O)R” _3-n ···(III)

In the above general formulas (I) to (III), R represents an organic group, such as: methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, cyclohexyl and other alkyl groups; cycloalkyl , phenyl, tolyl, xylyl, naphthyl, biphenyl and other aryl groups; benzyl and other aralkyl groups, etc. At least one of the 4 R's bonded to the phosphorus atom must be an aryl group. In addition, four Rs may be the same or different from each other, and two Rs may be bonded to form a ring structure.

In the above general formula (I), X ² represents a monovalent counter anion such as a halogen atom, hydroxyl, alkoxy, aryloxy, alkylcarbonyloxy, arylcarbonyloxy, HCO ₃ or BR′ ₄ . Here, R' represents a hydrogen atom or a hydrocarbon group such as an alkyl group or an aryl group, and four R's may be the same or different from each other.

In the above general formula (II), Y ² represents a divalent counter anion such as CO ₃ (including two monovalent counter anions).

In the above general formula (III), R" represents a hydrocarbon group, an alkoxy group, an aryloxy group or a hydroxyl group, R" may be the same or different from each other, and n represents an integer of 1-3.

Specific examples of the quaternary phosphonium salt compound represented by the above general formula (I) include, for example: tetraphenylphosphonium hydroxide, biphenyltriphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide Phosphonium, phenoxyphenyltriphenylphosphonium hydroxide, naphthylphenyltriphenylphosphonium hydroxide, tetraphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, Methoxyphenyltriphenylphosphonium tetraphenylborate, phenoxyphenyltriphenylphosphonium tetraphenylborate, naphthylphenyltriphenylphosphonium tetraphenylborate, tetraphenyl Phosphonium phenoxide, biphenyl triphenyl phosphonium phenoxide, methoxyphenyl triphenyl phosphonium phenoxide, phenoxyphenyl triphenyl phosphonium phenoxide, naphthylphenyl triphenyl phosphonium phenoxide, four Phenylphosphonium chloride, biphenyltriphenylphosphonium chloride, methoxyphenyltriphenylphosphonium chloride, phenoxyphenyltriphenylphosphonium chloride, or naphthylphenyltriphenylphosphonium chloride , cyclohexyltriphenylphosphonium tetraphenylborate, etc.

Specific examples of quaternary phosphonium salt compounds having a divalent counter anion represented by the above general formula (II) include bis(tetraphenylphosphonium) carbonate, bis(biphenyltriphenylphosphonium) ) carbonate, bis(naphthalene triphenylphosphonium) carbonate and other quaternary phosphonium salts, other examples: bis-tetraphenylphosphonium salt of 2,2-bis(4-hydroxyphenyl)propane, ethylene bis (triphenylphosphonium) dibromide, trimethylenebis(triphenylphosphonium)-bis(tetraphenylborate) and the like.

Specific examples of the quaternary phosphonium salt compound having a phosphate represented by the above general formula (III) include, for example, tetraphenylphosphonium phosphate, tetraphenylphosphonium phenylphosphonium, tetraphenylphosphonium diphenylphosphonium, etc. .

Among these quaternary phosphonium salts, the above-mentioned general formula (I) is preferable from the viewpoint of improving the compatibility between the (A) component, that is, the aromatic polycarbonate resin, and the above-mentioned (C) component, that is, the polyolefin resin, and improving the peeling. The one shown having one or more aryl groups bonded to a phosphorus atom is more preferably a substance having three or more aryl groups bonded to a phosphorus atom. A quaternary phosphonium salt may be used individually or in combination of 2 or more types.

In the present invention, as described above, it is particularly preferable to mix ( E) component can further improve mechanical strength, peeling strength, etc. by mix|blending (E) component. When compounding, it is preferable that the compounding quantity of (E) component is 0.0001-1 mass part with respect to 100 mass parts of resin components containing (A)-(C). If it is 1 part by mass or less, the molecular weight of the polycarbonate in a polycarbonate resin composition will not fall, and impact resistance will not fall. From such a viewpoint, the compounding quantity becomes like this. More preferably, it is 0.0002-0.5 mass part, More preferably, it is 0.0004-0.1 mass part.

When compounding the (E) component, the (E) component, that is, aliphatic amine salts, aromatic amine salts, ammonium hydroxide, hydroxyl ammonium salts, and quaternary phosphonium salts, can be used in combination of two or more. From the viewpoint of exfoliation, quaternary ammonium salts such as tetraalkylammonium hydroxide and quaternary phosphonium salts can be used in combination. When used in combination, from the viewpoint of controlling the molecular weight of the finished polycarbonate and expressing mechanical strength, it is preferable to use amines The compounding quantity of is set to 0.1-50 times the compounding quantity with respect to a quaternary phosphonium salt.

[(F) Phosphorous flame retardant]

As (F)component in this invention, red phosphorus and a phosphoric acid ester type flame retardant are mentioned.

The phosphoric acid ester-based flame retardant may contain phosphoric acid ester monomers, oligomers, polymers, or mixtures thereof, and examples thereof include compounds other than the above-mentioned (D1) component. Specifically, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tris(xylyl) phosphate, tris(isopropylphenyl) phosphate, trinaphthyl phosphate, Bisphenol A bisphosphate, hydroquinone diphosphate, resorcinol diphosphate, resorcinol-diphenylphosphate, trioxybenzene triphosphate, etc., or their substitutes, condensation things etc.

Examples of commercially available phosphate compounds that can be preferably used as phosphate-based flame retardants include: TPP [triphenyl phosphate] manufactured by Daihachi Chemical Industry Co., Ltd., TXP [tris(xylyl) phosphate] ], CR733S [resorcinol bis (diphenyl phosphate)], CR741 [bisphenol A bis (diphenyl phosphate)], PX200 [1,3-phenylene-tetrakis (2,6-di Methylphenyl) phosphate, PX201L [1,4-phenylene-tetrakis (2,6-dimethylphenyl) phosphate, PX202 [4,4'-biphenylene-tetrakis (2,6 - dimethylphenyl) phosphate and the like.

The above-mentioned phosphate-based flame retardant can be obtained by reacting divalent phenols and monovalent phenols represented by Ar·OH with phosphorus oxychloride.

The phosphorus-based flame retardants of these (F)components can be used individually or in combination of 2 or more types, respectively. The content of these components (F) is preferably 3 to 20 parts by mass, more preferably 5 to 20 parts by mass, and even more preferably 8 to 20 parts by mass with respect to 100 parts by mass of the resin component containing the aforementioned (A) to (C). .

By blending 3 parts by mass or more, desired flame retardancy can be obtained, and by blending 20 parts by mass or less, it is possible to avoid a fall in impact resistance or the like.

[(G) Inorganic Filler]

In the present invention, in order to further improve the rigidity and flame retardancy of the molded article, an inorganic filler that is the component (G) may be contained as needed.

Here, examples of the inorganic filler include talc, mica, kaolin, diatomaceous earth, and calcium carbonate. Among them, fillers such as platy talc and mica are preferable, and talc which is magnesium silicate is more preferable. These inorganic fillers may be used alone or in combination of two or more.

The average particle diameter of the inorganic filler is preferably 0.1 to 50 μm, more preferably 0.2 to 20 μm.

Here, the content of the (G) inorganic filler is preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the resin component containing the aforementioned (A) to (C). When content of (G) component is 1 mass part or more, the improvement effect of target rigidity and flame retardancy is sufficient, and when it is 20 mass parts or less, fall of impact resistance etc. does not generate|occur|produce. The content of the component (G) can be appropriately determined in consideration of the required properties and formability of the molded product, such as the thickness of the molded product and the flow length of the resin.

[(H) coloring material]

In the present invention, in order to improve the appearance of the molded article of the polycarbonate resin composition of the present invention, a coloring material that is the component (H) may be used as needed.

As the coloring material, any of organic or inorganic coloring materials can be used. Examples of organic coloring materials include carbon black and the like, and examples of inorganic coloring materials include metal oxide coloring materials such as titanium oxide, zinc oxide, and iron oxide. Among these coloring materials, inorganic coloring materials are preferably used, and metal oxides are more preferably used. In addition, these coloring materials may be used individually or in combination of 2 or more types.

The compounding quantity of these (H)components is preferably the range of 0.05-5 mass parts with respect to 100 mass parts of resin components containing said (A)-(C), More preferably, it is the range of 0.1-3 mass parts.

[additive]

Moreover, in the polycarbonate resin composition of this invention, various additives can be mix|blend other than said (A)-(H) component in the range which does not impair the object of this invention. Examples of additives include ultraviolet absorbers, light stabilizers, flame retardant aids, antistatic agents, antiblocking agents, mold release agents, and lubricants.

[Polycarbonate resin composition and molded article]

The polycarbonate resin composition of the present invention can be obtained by blending the above-mentioned components (A) to (D), components (E) to (H) and various additives as needed, and melt-kneading them by a conventional method. The order of compounding the components is not particularly limited. Specifically, when compounding (E) an amine salt of the component, etc., it is preferable to combine (A) an aromatic polycarbonate resin, (B) an epoxy group-containing or glycidol (D) phosphorus-containing compound and (F) phosphorus-based flame retardant after mixing polyolefin or polyolefin elastomer and (E) component amine salt, (C) polyolefin-based resin can be combined with (A) component It is preferable to combine (A) component and ( B) Compounding is performed after mixing the components.

Examples of the melt-kneading machine used for melt-kneading include a Banbury mixer, a single-screw extruder, a twin-screw extruder, a co-kneader, and a multi-screw extruder. The heating temperature in melt-kneading is usually 220 to 300°C, particularly suitably about 250°C.

If melt kneading is carried out under the above-mentioned conditions, the phosphorus-containing compound of (D) component can make the epoxy group or glycidyl group of the epoxy group or glycidyl group-containing polyolefin or polyolefin elastomer of (B) component Activation, thereby promoting the formation of compatibilizing components. Thus, in the polycarbonate resin composition obtained in the present invention, the aromatic polycarbonate resin of the (A) component exists in the matrix phase, the polyolefin resin of the (C) component exists regionally, and the polyolefin resin exists at the interface. A compatibilizing component derived from the reaction product of carbonates and polyolefins containing epoxy or glycidyl groups. The presence of an appropriate amount of compatibilizing components can stabilize the interface, thereby obtaining a polycarbonate resin that has improved compatibility between polycarbonate and polyolefin, excellent mechanical properties such as impact resistance, and bending strength, and is not easily peeled off. combination.

The polycarbonate resin composition of the present invention can be produced by applying known molding methods such as hollow molding, injection molding, extrusion molding, vacuum molding, pressure molding, thermal bending molding, compression molding, tape casting, and rotational molding. Forming a shaped body, particularly preferably a molding method based on injection molding.

In addition, since the polycarbonate resin composition of the present invention is excellent in impact resistance and appearance, it can be used as automobile parts, electronic equipment, housings of information equipment, etc. requiring these properties by injection molding.

The present invention will be described in more detail by way of examples, but the present invention is not limited by these examples. In the following, GMA represents glycidyl methacrylate, and MI represents melt index.

Example

The components (A) to (H) used in Examples and Comparative Examples are as follows.

(A) Aromatic polycarbonate resin

A-1: Tarflon FN2600A [manufactured by Idemitsu Kosan Co., Ltd., molecular weight 25400] OH terminal fraction: 4 mol %

A-2: PC produced by melting method [molecular weight 21200] OH terminal fraction: 30 mol%

Add 4560g (20 moles) of bisphenol A and 4418g (20.65 moles) of diphenyl carbonate to a SUS316 autoclave with an inner volume of 30 liters, and add tetramethylammonium hydroxide (TMAH) as a catalyst to bisphenol A 2.5×10 ^-4 mol, tetraphenylphosphonium tetraphenylborate (TPPK manufactured by Hokko Chemical Co., Ltd.) 1×10 ^-5 mol, after heating at 210°C for 30 minutes, at 240°C, 270°C, 290°C The temperature was raised step by step, and then the degree of vacuum was slowly increased, and finally the mixture was stirred and mixed at 0.4 mmHg for 2 hours to obtain the polycarbonate shown in A-2 above.

It should be noted that, after dissolving 70 mg of polycarbonate resin in 0.6 mL of deuterated chloroform at room temperature, ¹ H-NMR was measured ( ¹ H nuclear magnetic resonance frequency: 500 MHz, observation frequency range: 10000 Hz, accumulation number: 256 times), Based on the peak a (7.06, 7.05ppm) derived from the terminal hydroxyl group, the peak (6.67, 6.65ppm) and c (4.87ppm) of the phenyl hydrogen of the terminal bisphenol A, the content of the terminal hydroxyl group (OH terminal fraction) is calculated ).

(B) Polyolefin-based resin and/or polyolefin-based elastomer containing epoxy group or glycidyl group

B-1: Ethylene-GMA copolymer [manufactured by Sumitomo Chemical Co., Ltd., Bondfast E, GMA content 12% by mass]

B-2: Polypropylene-GMA graft copolymer [manufactured by blending polypropylene, GMA, and organic peroxide, followed by melt-kneading by batch kneading], GMA content 9% by mass]

(C) Polyolefin resin

C-1: Polypropylene block polymer [manufactured by Prime Polymer Co., Ltd., J-785H, MI=15 g/10 minutes]

C-2: Polypropylene block polymer [manufactured by Prime Polymer Co., Ltd., E-185G, MI=0.35 g/10 minutes]

C-3: polyethylene [manufactured by Prime Polymer Co., Ltd., 64OUF, MI=0.21 g/10 minutes]

(D1) Components

D-1: Monooctyl diphenyl phosphite [manufactured by ADEKA Corporation, Adekastab C]

D-2: Distearyl pentaerythritol diphosphite [manufactured by ADEKA, PEP-8]

D-3: Tridecyl phosphite [manufactured by ADEKA, 3010]

(D2) Components

D-4: 1% phosphoric acid aqueous solution

(D) Phosphorus-containing compounds other than components

d-1: Tris(2,4-di-tert-butylphenyl)phosphite [manufactured by BASF, Irgafos168]

d-2: Triphenyl phosphite [manufactured by ADEKA, TPP]

d-3: 2,2'-methylenebis(4,6-dibutylphenyl)octyl phosphite [manufactured by ADEKA Corporation, HP-10]

d-4: Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite [manufactured by ADEKA Corporation, PEP-36]

(E) Ammonium hydroxide

E-1: Tetramethylammonium hydroxide [manufactured by Wako Pure Chemical Industries, Ltd., 3% aqueous solution]

(F) Phosphorous flame retardant

F-1: Aromatic condensed phosphoric acid ester-based flame retardant [manufactured by Daihachi Chemical Industry Co., Ltd., CR-741]

(G) Inorganic filler material

G-1: Talc [manufactured by Fuji Talc Industry Co., Ltd., TPA-25]

(H) Coloring material

H-1: Titanium oxide [manufactured by Ishihara Sangyo Co., Ltd., CR63]

H-2: Carbon black [manufactured by Mitsubishi Chemical Corporation, MA-100]

H-3: Iron oxide [manufactured by Lanxess, 180M]

<Manufacturing method of resin composition (pellets)>

A two-screw extruder [manufactured by Nippon Steel Works Co., Ltd., TEX44] with two supply ports and an exhaust port was used as the extruder, and the set temperature was 250° C., the screw speed was 300 rpm, and the discharge rate was 100 kg/ The components (A) to (H) shown in Table 1 were melt-kneaded under the condition of 1 hour to obtain the target pellets.

<Evaluation method>

(1) Viscosity average molecular weight (Mv) of polycarbonate resin after mixing

Add dichloromethane to the mixed polycarbonate resin, absorb the insoluble components with bentonite, filter out the soluble components, dry them to form a film, weigh the obtained film, and measure the viscosity-average molecular weight.

In the measurement of the viscosity-average molecular weight, about 0.7 g of the above-mentioned film was dissolved in 100 ^cm of methylene chloride at 20° C., and the specific viscosity (η _sp ) of the solution was measured with an Ubbelohde viscometer, and the specific viscosity (η _sp ) was brought into The viscosity average molecular weight was calculated|required by the following formula.

(η _sp )/C=[η]+0.45×[η] ² C

[η]=1.23×10 ^-5 M ^0.83

(where [η] is the intrinsic viscosity, and C is the polymer concentration)

(2) Impact resistance (Izod impact resistance)

Measured based on JIS K7110 (cantilever beam, thickness of test piece: 3.0 mm).

(3) Peel resistance (evaluation of peeling by bending test)

The pellets obtained above were dried at 110° C. for 6 hours or more, and then molded into a test piece with a thickness of 3.2 mm in the shape of test piece 1B according to JIS K7162 at a molding temperature of 260° C. and a mold temperature of 60° C.

The above-mentioned test piece was bent from the center until both ends touched, and then bent in the same manner in the opposite direction. The detachability was evaluated by the number of times wrinkles were generated on the surface. In addition, in Table 1, the case which did not peel off after bending 10 times or more was set as "10<".

(4) Uneven gloss (measurement of Δ gloss)

The particles obtained above were molded under the conditions of cylinder temperature 260°C, mold temperature 60°C, and film gate (width 50mm, thickness 1mm) with a filling time of 1.0 second to obtain a test with a thickness of 1.5mm and a square of 150×150mm piece.

Using a gloss meter [manufactured by Nippon Denshoku Industries Co., Ltd., Gloss Meter VG2000], the gloss values of the portion from the gate to 2 cm and the portion from the end to 2 cm in the above-mentioned test piece were measured at a reflection angle of 60°, The difference between these values (Δgloss) was expressed as gloss unevenness. The greater the Δ gloss value, the greater the unevenness in gloss.

[Examples 1-5, Comparative Examples 1-5]

The resin composition was blended in the blending ratio shown in Table 1 to produce pellets, and the preparation of test pieces and evaluation of physical properties were performed by the above-mentioned method. Table 1 shows the obtained results.

[Table 1]

Table 1

(mass%) ^*1 : Mass% of the total amount of (A), (B) and (C) components

(Parts by mass) ^*2 : Parts by mass relative to 100 parts by mass of the total amount of components (A), (B) and (C)

(Parts by mass) ^*3 : Parts by mass of the active ingredient relative to 100 parts by mass of the total of components (A), (B) and (C)

As can be seen from Table 1, molded articles obtained from the polycarbonate resin composition of the present invention are superior in impact resistance compared to respective corresponding comparative examples, and even in the case of thin molded articles having film gates, they are There was no layered peeling within 10 times of peeling, and there was little unevenness in gloss.

In addition, as can be seen from Comparative Example 5, although a phosphite compound having one alkoxy group (octyloxy group) bonded to the phosphorus atom was used as the (D) component, the phosphite compound has A bonded aryloxy group has a substituent at the ortho-position of the aryloxy group, so the effect of the present invention cannot be obtained.

Industrial availability

The polycarbonate resin composition of the present invention is excellent in impact resistance, does not exhibit lamellar peeling even in the case of thin molded products, and has little gloss unevenness, so it is used for automobile parts, electronic equipment, and casings of information equipment. Body etc. are useful.

Claims (11)

1. A polycarbonate resin composition comprising 100 parts by mass of a resin component and (D) a phosphorus-containing compound, wherein the resin component comprises (A) 60 to 95 mass % of an aromatic polycarbonate resin, (B ) 2-30% by mass of polyolefin-based resin and/or polyolefin-based elastomer containing epoxy group or glycidyl group, and 1-38% by mass of polyolefin-based resin other than component (B) described in (C), This (D) component is following (D1) and/or (D2), (D1) 0.01 to 0.5 parts by mass of at least one selected from phosphite compounds and phosphate compounds having at least one alkoxy group bonded to the phosphorus atom, wherein the compound has When an aryloxy group is present, all the ortho positions of the aryloxy group are hydrogen atoms; (D2) 0.001 to 0.1 parts by mass of at least one selected from phosphoric acid, phosphorous acid, phosphonic acid, and phosphonous acid. 2. polycarbonate resin composition according to claim 1, wherein, (A) The aromatic polycarbonate resin contains the aromatic polycarbonate resin which has a hydroxyl group as a molecular chain terminal group, and the content of this hydroxyl group with respect to all terminal groups is 20-80 mol%. 3. polycarbonate resin composition according to claim 1, wherein, (A) The aromatic polycarbonate resin contains the aromatic polycarbonate resin which has a hydroxyl group as a molecular chain terminal group, and the content of this hydroxyl group with respect to all terminal groups is less than 20 mol%. 4. polycarbonate resin composition according to claim 3, wherein, 0.0001 to 1 part by mass of (E) at least one selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxide, hydroxylammonium salts, and quaternary phosphonium salts is contained with respect to 100 parts by mass of the resin component. 5. The polycarbonate resin composition according to any one of claims 1 to 4, wherein, 3-20 mass parts of (F) phosphorus flame retardants are contained with respect to 100 mass parts of said resin components. 6. The polycarbonate resin composition according to any one of claims 1 to 5, wherein, 1-20 mass parts of (G) inorganic fillers are contained with respect to 100 mass parts of said resin components. 7. polycarbonate resin composition according to claim 6, wherein, The (G) inorganic filler is an inorganic filler containing magnesium silicate. 8. The polycarbonate resin composition according to any one of claims 1 to 7, wherein, 0.05-5 mass parts of (H) coloring materials are contained with respect to 100 mass parts of said resin components. 9. polycarbonate resin composition according to claim 8, wherein, The (H) coloring material is a metal oxide. 10. The polycarbonate resin composition according to any one of claims 1 to 9, wherein, The viscosity average molecular weight of the said (A) component is 11000-30000. 11. A molded article obtained by injection molding the polycarbonate resin composition according to any one of claims 1 to 10.