JP2013163768A - Polycarbonate resin composition and molded form thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition excellent in balance among fluidity, chemical resistance and flame retardancy, presenting no laminar debonding after molded even in the case of a thin-wall molded product thereof, and to provide a molded form thereof.SOLUTION: A polycarbonate resin composition comprises: 100 pts.mass of a resin component including (A) 60-95 mass% of an aromatic polycarbonate resin, (B) 2-10 mass% of an epoxy or glycidyl group-containing polyolefin resin and/or polyolefin elastomer, (C) 2-15 mass% of a polyolefin resin other than the B component and (D) 0-20 mass% of a styrenic resin; (E) 5-20 pts.mass of a phosphorus-based flame retardant; (F) 3-20 pts.mass of an inorganic filler; and (G) an activating agent, wherein the G component is G1 and/or G2 compound described below: (G1) 0.001-1 pt.mass of at least one compound selected from the group consisting of phosphite and phosphate compounds each with at least one alkoxy group bound to the phosphorus atom (wherein, the compound is such that: if having aryloxy group bound to the phosphorus atom, all the ortho positions of the aryloxy group have hydrogen atoms), and (G2) 0.000001-0.01 pt.mass of at least one compound selected from the group consisting of phosphoric acid, phosphorous acid and organic sulphonic acid-based compounds.

Description

  The present invention relates to a polycarbonate resin composition and a molded body thereof. More specifically, the present invention relates to a molded article that has an excellent balance of fluidity, chemical resistance, and flame retardancy and does not exhibit delamination, and a polycarbonate resin composition that provides the molded article.

  Polycarbonate resins are excellent in mechanical strength such as heat resistance and impact resistance, transparency, and the like, and are therefore used as important materials such as electronic, information, electrical parts and mechanical parts. However, since it has weak points such as low fluidity and poor chemical resistance, the alloying of polycarbonate with polyolefin has been studied in order to improve these characteristics.

For example, polycarbonate is alloyed with a polycarbonate, a polyolefin resin having an epoxy group or the like and / or a polyolefin elastomer, and a polyolefin (Patent Documents 1 to 4). As a result, a polycarbonate resin that maintains mechanical strength such as heat resistance and impact resistance and is excellent in chemical resistance and fluidity is obtained.
Patent Document 3 discloses a polycarbonate resin composition excellent in fluidity and chemical resistance by mixing an aromatic polycarbonate resin, a polyolefin resin, a polyolefin resin having an epoxy group or a glycidyl group, and an amine compound. It is disclosed that it can be obtained. Patent Document 4 discloses a resin composition that contains an aromatic polycarbonate resin, a polyolefin resin, a polyolefin resin having an epoxy group or a glycidyl group, and a phosphorus flame retardant, and is excellent in chemical resistance and flame retardancy. It is disclosed.

JP 2009-275131 A JP 2009-298993 A JP 2010-24368 A JP 2011-131321 A

However, with respect to flame retardancy, higher performance is required, and a material having a good balance of fluidity, chemical resistance, and flame retardancy is required.
If a large amount of an inorganic filler such as talc is added to improve the flame retardancy, peeling may occur depending on the vicinity of the gate shape where high shear is applied or molding conditions. descend. On the other hand, in order to improve flame retardancy, when a large amount of phosphorus flame retardant is added, the chemical resistance is lowered, and when the addition amount of polyolefin resin is reduced, both the fluidity and the chemical resistance are lowered.
The present invention compensates for the drawbacks of aromatic polycarbonate resin, has an excellent balance of fluidity, chemical resistance, and flame retardancy, and does not exhibit delamination after molding, even for thin molded products. It is an object of the present invention to provide a polycarbonate resin composition that does not cause peeling in the vicinity of the gate when a thin molded product is molded with a pin gate or the like, and a molded product thereof.

  As a result of diligent research to achieve the above object, the present inventors have found that an aromatic polycarbonate resin, a polyolefin resin and / or polyolefin elastomer containing an epoxy group or a glycidyl group, a polyolefin resin, and a styrene resin It was found that the above-mentioned object was achieved by using a polycarbonate resin composition in which specific additive components were added to resin components each containing a specific ratio, and the present invention was completed.

That is, the present invention provides the following polycarbonate resin composition and molded article.
1. (A) Aromatic polycarbonate resin 60-95 mass%, (B) Polyolefin resin and / or polyolefin elastomer 2-10 mass% containing epoxy group or glycidyl group, (C) Polyolefin other than the component (B) (E) phosphorus flame retardant 5 to 20 parts by mass, (F) inorganic filler 3 with respect to 100 parts by mass of resin component consisting of 2 to 15% by mass of resin and (D) styrene resin 0 to 20% by mass A polycarbonate resin composition containing ˜20 parts by mass and (G) an activator, wherein the component (G) is the following (G1) and / or (G2).
(G1) At least one selected from the group consisting of a phosphite compound and a phosphate compound in which at least one alkoxy group is bonded to a phosphorus atom (provided that the compound has an aryloxy group bonded to a phosphorus atom; Compound in which all ortho positions of the aryloxy group are hydrogen atoms) 0.001 to 1 part by mass (G2) At least one selected from the group consisting of phosphoric acid, phosphorous acid, and organic sulfonic acid compounds. 000001-0.01 parts by mass (A) The polycarbonate resin composition according to 1 above, wherein the aromatic polycarbonate resin includes a hydroxyl group as a molecular chain terminal group, and the content of the hydroxyl group with respect to all terminal groups is 20 to 80 mol%. .
3. (A) The polycarbonate resin composition according to 1 above, wherein the aromatic polycarbonate resin contains a hydroxyl group as a molecular chain terminal group, and the content of the hydroxyl group with respect to all terminal groups is less than 20 mol%.
4). 0.0001 to 1 at least one selected from the group consisting of (H) aliphatic amine salt, aromatic amine salt, ammonium hydroxide, hydroxyammonium salt, and quaternary phosphonium salt with respect to 100 parts by mass of the resin component. 4. The polycarbonate resin composition according to 3 above, which is blended in parts by mass.
5. The polycarbonate resin composition according to any one of 1 to 4 above, comprising 0.1 to 1 part by mass of (I) a fluorine-containing polymer with respect to 100 parts by mass of the resin component.
6). (D) The group in which the styrene resin is composed of acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and methyl methacrylate-butadiene rubber-styrene copolymer (MBS resin). The polycarbonate resin composition according to any one of 1 to 5, which is at least one selected from the group consisting of:
7). (G2) The polycarbonate resin composition in any one of said 1-6 whose organic sulfonic acid type compound of a component is an aryl sulfonic acid ester.
8). (F) The polycarbonate resin composition according to any one of 1 to 7 above, wherein the inorganic filler is talc and / or mica.
9. The polycarbonate resin composition according to any one of 1 to 8 above, wherein a melt volume flow rate (MVR) measured at a temperature of 280 ° C. and a load of 2.16 kg is 2 to 30 ml / 10 minutes.
10. The molded object which consists of a polycarbonate resin composition in any one of said 1-9.

  According to the present invention, the compatibility between the polycarbonate resin and the polyolefin resin can be enhanced, and the balance between fluidity, chemical resistance, and flame retardancy is excellent, and even if it is a thin-walled molded product, delamination is performed after molding. It is possible to provide a polycarbonate resin composition that is not exhibited and a molded body thereof.

The polycarbonate resin composition of the present invention comprises (A) 60 to 95% by mass of an aromatic polycarbonate resin, (B) 2 to 10% by mass of a polyolefin resin and / or polyolefin elastomer containing an epoxy group or glycidyl group, (C ) 2E to 15% by mass of a polyolefin resin other than the component (B), and (D) 100 parts by mass of a resin component consisting of 0 to 20% by mass of a styrene resin. Part (F) 3-20 parts by mass of an inorganic filler, and (G) an activator, wherein the component (G) is a polycarbonate resin composition (G1) and / or (G2) below. .
(G1) At least one selected from the group consisting of a phosphite compound and a phosphate compound in which at least one alkoxy group is bonded to a phosphorus atom (provided that when the compound has an aryloxy group bonded to a phosphorus atom, Compound in which all ortho positions of aryloxy group are hydrogen atoms) 0.001 to 1 part by mass (G2) At least one selected from the group consisting of phosphoric acid, phosphorous acid, and organic sulfonic acid compounds 0.000001 -0.01 mass part Hereinafter, each component used for the polycarbonate resin composition of this invention is demonstrated.

[(A) Aromatic polycarbonate resin]
As the aromatic polycarbonate resin as the component (A) in the present invention, various aromatic polycarbonates produced by the reaction of a dihydric phenol and a carbonate precursor can be used.

Various divalent phenols may be mentioned, and in particular, 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. These dihydric phenols may be used alone or in combination of two or more.
Particularly preferred dihydric phenols are those based on bis (hydroxyphenyl) alkanes, especially bisphenol A or bisphenol A.

  Examples of the carbonate precursor include carbonyl halide, carbonyl ester and haloformate, specifically phosgene, dihaloformate of dihydric phenol, diphenyl carbonate, dimethyl carbonate and diethyl carbonate.

  The aromatic polycarbonate may have a branched structure, and examples of the branching agent include 1,1,1-tris (4-hydroxyphenyl) ethane, α, α ′, α ″ -tris (4- (Bitroxyphenyl) -1,3,5-triisopropylbenzene, phloroglysin, trimellitic acid, and isatin bis (o-cresol).

  The viscosity average molecular weight of the aromatic polycarbonate resin as the component (A) in the present invention is preferably 11000 to 35000, more preferably 12000 to 30000, and further preferably 15000 to 30000. If the viscosity average molecular weight is 11000 or more, chemical resistance, impact resistance and tensile strength are sufficient, and if it is 35000 or less, moldability and tensile strength are good and delamination of the molded article does not occur. .

The viscosity average molecular weight of the component (A) in the present invention is a specific viscosity (η _sp ) measured by using an Ubbelohde viscometer with a solution obtained by dissolving about 0.7 g of an aromatic polycarbonate resin in 100 cm ³ of methylene chloride at 20 ° C. Is obtained by inserting into the following equation.
(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 amount of (A)-(D) component. If it is less than 60% by mass, the tensile strength, elastic modulus and the like are lowered, and if it exceeds 95% by mass, improvement effects such as fluidity and chemical resistance may be insufficient. A compounding quantity becomes like this. Preferably it is 65-92 mass%, More preferably, it is 70-90 mass%.

  The aromatic polycarbonate resin of the component (A) used here includes those having a hydroxyl group as a molecular chain end group. The amount of this hydroxyl group (hereinafter also referred to as “terminal hydroxyl group”) is increased, For the purpose of improving peeling, aliphatic amines, aromatic amines, ammonium hydroxide, hydroxylamine salt, quaternary phosphonium salt, etc., which are components (H) described later, can be blended.

  That is, when the content of terminal hydroxyl groups with respect to all terminal groups of the aromatic polycarbonate resin is 20 mol% or more, it is not necessary to add the component (H). When the content is less than 20 mol%, at least one selected from the group consisting of aliphatic amines, aromatic amines, ammonium hydroxides, hydroxylamine salts, and quaternary phosphonium salts as the component (H). It is preferable to mix seed compounds. Of course, even if the content of the terminal hydroxyl group is 20 mol% or more, the above component (H) may be blended, and conversely, the content of the terminal hydroxyl group is less than 20 mol%. However, there is no problem even if the component (H) is not blended.

In the case where an aromatic polycarbonate resin having a terminal hydroxyl group content of 20 mol% or more with respect to all terminal groups of the aromatic polycarbonate resin is used as the component (A), the hydroxyl group content is From a reactive viewpoint with an epoxy group or a glycidyl group, Preferably it is 20-80 mol%, More preferably, it is 20-60 mol%, More preferably, it is 20-50 mol%. If the content is 20 mol% or more, the reactivity with the epoxy group or the clicidyl group is good, and if it is 80 mol% or less, the crosslinking reaction does not occur, and the resulting resin composition has reduced fluidity and resistance. There is no risk of a drop in impact.
The amount of terminal hydroxyl groups relative to all terminal groups of the aromatic polycarbonate resin (hereinafter also referred to as “OH terminal fraction”) is determined from the integrated value of the peak derived from the terminal hydroxyl groups by measuring ¹ H-NMR. it can.

[(B) Polyolefin resin and / or polyolefin elastomer containing epoxy group or glycidyl group]
The polyolefin resin which is the component (B) in the present invention is used for the purpose of compatibilizing the component (A) and the component (C). For example, an olefin homopolymer having an epoxy group or a glycidyl group, Alternatively, it may be a copolymer of an olefin and an unsaturated monomer having an epoxy group or a glycidyl group, or an olefin polymer obtained by copolymerizing 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.

  Further, for example, the terminal of the olefin polymer, or the unsaturated bond existing in the copolymer of olefin and other unsaturated monomer and the composite thereof, hydrogen peroxide, organic peracid, etc. An epoxy group may be introduced by oxidation with benzoic acid, performic acid, peracetic acid, or the like. That is, any olefin polymer may be used as long as an epoxy group or a glycidyl group is introduced.

  The polyolefin elastomer in the component (B) is an epoxy or glycidyl group and has a low crystallinity or an amorphous olefin copolymer having a crystallinity of 50% or less as measured by an X-ray diffraction method. It is a coalescence.

  As the olefin, ethylene, propylene, 1-butene, isobutylene, 2-butene, cyclobutene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-butene, 4-methyl-1- Examples include butene, cyclopentene, 1-hexene, cyclohexene, 1-octene, 1-decene, and 1-dodecene. These may be used alone or in combination of two or more.

  Examples of the unsaturated monomer having an epoxy group or glycidyl group include glycidyl acrylate, glycidyl methacrylate, vinyl glycidyl ether, allyl glycidyl ether, methacryl glycidyl ether, 2-methylpropenyl glycidyl ether, styrene-p-glycidyl ether, glycidyl cinna Mate, glycidyl itaconate, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] methacrylamide and the like. These may be used alone or in combination of two or more, and together with these unsaturated monomers having an epoxy group or glycidyl group, for example, alkyl acrylate, alkyl methacrylate, etc. In addition to a glycidyl group, a group such as an acrylic ester or a methacrylic ester is included, such as a copolymerization of these using an unsaturated monomer having no epoxy group or glycidyl group. Also good.

  Of the olefin and monomer constituting the polyolefin resin and / or polyolefin elastomer that is the component (B) in the present invention, the content of the unsaturated monomer having an epoxy group or glycidyl group is 1 to 20 mass. % Is preferred. When the content is 1% by mass or more, the effect of improving the compatibility between the component (A) and the component (C) is exhibited, the tensile elongation and the impact resistance are not lowered, and the layered peeling of the molded body occurs. There is nothing. On the other hand, if it is 20% by mass or less, self-crosslinking does not occur, tensile elongation and impact resistance do not decrease, and further, no layered peeling of the molded product occurs. From such points, the content of the unsaturated monomer having an epoxy group or a glycidyl group is more preferably 2 to 18% by mass, and further preferably 4 to 15% by mass.

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

  In the present invention, as the component (B), one or more polyolefin resins having an epoxy group or glycidyl group may be used, or one or more polyolefin elastomers having an epoxy group or glycidyl group may be used, Moreover, you may use together 1 or more types of the said polyolefin-type resin, and 1 or more types of polyolefin-type elastomer.

  The compounding quantity of (B) component in this invention is 2-10 mass% in the total amount of (A)-(D) component. If the content is less than 2% by mass, the compatibility between the component (A) and the component (C) cannot be improved sufficiently, the tensile elongation and the impact resistance are lowered, and further, delamination of the molded product occurs. There is. If it exceeds 10% by mass, self-crosslinking tends to occur, the fluidity is lowered, and the tensile elongation and impact resistance are lowered. From such a point, the blending amount is preferably 2 to 8% by mass.

[(C) Polyolefin resin]
The polyolefin resin as the component (C) in the present invention is used for the purpose of improving the chemical resistance and fluidity of the component (A) as the main component, and the epoxy group or the component (B). A polyolefin resin other than a polyolefin resin having a glycidyl group. Examples of the polyolefin-based resin include those obtained by polymerizing olefins such as ethylene, propylene, and butene alone, and polymers obtained by copolymerizing these.

  For example, the polyethylene resin may be one obtained by polymerizing ethylene alone, or may be one obtained by copolymerizing mainly ethylene, high density polyethylene, medium density polyethylene, low density polyethylene, linear Examples thereof include polyethylene resins such as low density polyethylene, ethylene-α-olefin copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methacrylate copolymer. Examples of the ethylene-α-olefin copolymer include a copolymer of propylene and ethylene, and any of a graft copolymer, a random copolymer, and a block copolymer may be used.

The melt flow rate (MFR) of these polyethylene resins is preferably about 0.01 to 50 g / 10 minutes, and more preferably 0.02 to 30 g / 10 minutes. When the MFR is 0.01 g / 10 min or more, the effect of improving the fluidity can be sufficiently exerted, and when the MFR is 50 g / 10 min or less, delamination of the molded body hardly occurs.
In addition, MFR in the case of a polyethylene-type resin is calculated | required by the measuring method based on ASTMD1238, and is measured in resin temperature 190 degreeC and load 21.18N.

  In addition, the polypropylene resin may be one obtained by polymerizing propylene alone, or may be one obtained by copolymerizing mainly propylene. For example, it may be an isotactic propylene homopolymer or a syndiotactic propylene homopolymer. Examples of the copolymer include a copolymer of propylene and ethylene, and may be any of a graft copolymer, a random copolymer, and a block copolymer.

  Such a polypropylene resin has a melt flow rate (MFR) of preferably about 0.1 to 60 g / 10 minutes, more preferably 0.1 to 50 g / 10 minutes. When the MFR is 0.1 g / 10 min or more, the effect of improving the fluidity can be sufficiently exerted, and when the MFR is 60 g / 10 min or less, delamination of the molded body hardly occurs. In addition, MFR of this polypropylene resin was calculated | required by the measuring method based on ASTMD1238, and was measured in resin temperature 230 degreeC and the load 21.18N.

  In addition to the above polyethylene resin or polypropylene resin, any polyolefin resin having a melt flow rate (MFR) of about 0.01 to 60 g / 10 min (230 ° C., load 21.18 N) is used in the same manner. can do.

In the present invention, as the component (C), one type of the polyolefin resin may be used, or two or more types may be used in combination.
The compounding quantity of (C) component in this invention is 2-15 mass% in the total amount of (A)-(D) component, and it is preferable that it is 3-14 mass%. If it is less than 2% by mass, the effect of improving the fluidity and chemical resistance cannot be sufficiently exhibited. If it exceeds 15% by mass, the tensile elongation, elastic modulus and impact resistance are lowered, and in some cases, delamination of the molded product occurs. It tends to be easier.

[(D) Styrenic resin]
The styrenic resin used as the component (D) of the present invention is used for the purpose of improving the molding processability of the polycarbonate resin, particularly the fluidity, and uses an amorphous styrenic resin and a crystalline styrenic resin. be able to.
As an amorphous styrenic resin, 20 to 100% by mass of a monovinyl aromatic monomer such as styrene or α-methylstyrene, 0 to 60% by mass of a vinyl cyanide monomer such as acrylonitrile or methacrylonitrile, And a crystal structure obtained by polymerizing a monomer or a monomer mixture composed of 0 to 50% by mass of other vinyl monomers such as maleimide, methyl (meth) acrylate and the like which can be copolymerized therewith. Polymers that do not.
These polymers include general-purpose polystyrene (GPPS), acrylonitrile-styrene copolymer (AS resin), and the like.

  As the amorphous styrenic resin, a rubber-modified styrenic resin reinforced with a rubbery polymer can be preferably used. Examples of the rubber-modified styrene-based resin include impact-resistant polystyrene (HIPS) in which styrene is polymerized on rubber such as polybutadiene, acrylonitrile-butadiene-styrene copolymer (ABS resin) in which acrylonitrile and styrene are polymerized on polybutadiene, There is a methyl methacrylate-butadiene-styrene copolymer (MBS resin) obtained by polymerizing methyl methacrylate and styrene on polybutadiene, and two or more rubber-modified styrene resins can be used together. It can also be used as a mixture with a modified amorphous styrenic resin.

The rubber content in the rubber-modified styrenic resin is preferably 2 to 50% by mass, more preferably 5 to 30% by mass, and still more preferably 5 to 15% by mass. If the ratio of rubber is 2% by mass or more, impact resistance is sufficient, and if it is 50% by mass or less, problems such as deterioration of thermal stability, deterioration of melt fluidity, generation of gel, coloring, etc. Does not occur.
Specific examples of the rubber include a rubbery polymer containing polybutadiene, acrylate and / or methacrylate, styrene-butadiene-styrene rubber (SBS), styrene-butadiene rubber (SBR), butadiene-acrylic rubber, isoprene rubber, isoprene. -Styrene rubber, isoprene-acrylic rubber, ethylene-propylene rubber and the like. Of these, polybutadiene is particularly preferable. The polybutadiene used here is a low cis polybutadiene (for example, one containing 1 to 30 mol% of 1,2-vinyl bond and 30 to 42 mol% of 1,4-cis bond), or high cis polybutadiene (for example, 1, Any of those containing 20 mol% or less of 2-vinyl bond and 78 mol% or more of 1,4-cis bond) may be used, or a mixture thereof may be used.

  In addition, examples of the crystalline styrene resin include styrene (co) polymers having a syndiotactic structure and an isotactic structure. In the present invention, an amorphous styrene resin is used for the purpose of further improving fluidity. It is preferable to use a resin. Further, among amorphous styrenic resins, the melt flow rate (MFR) at 200 ° C. and 5 kg load is preferably 0.5 to 100 g / 10 minutes, more preferably 2 to 80 g / 10 minutes, still more preferably 2 to 2. The one with 50 g / 10 min is used. When the melt flow rate (MFR) is 5 g / 10 minutes or more, sufficient fluidity is obtained, and when the melt flow rate (MFR) is 100 g / 10 minutes or less, the impact resistance of the flame-retardant polycarbonate resin composition is improved.

Among amorphous styrene resins, high impact polystyrene resin (HIPS), acrylonitrile-styrene copolymer (AS resin) and acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-styrene copolymer Copolymer (MS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), acrylonitrile-methyl acrylate-styrene copolymer (AAS resin), acrylonitrile- (ethylene / propylene / diene copolymer) -styrene A copolymer (AES resin) is preferred, and acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and methyl methacrylate-butadiene-styrene copolymer (MBS resin). Particularly preferred.
Examples of these particularly preferred resins include 290FF (manufactured by Techno Polymer Co., Ltd.), S100N, S200N, S101 (manufactured by UMG ABS Co., Ltd.), and PN-117C (manufactured by Kitami Jitsugyo Co., Ltd.). Examples of ABS resin include Santac AT-05, SXH-330 (manufactured by Nippon A & L Co., Ltd.), Toyolac 500 and 700 (manufactured by Toray Industries, Inc.), and PA-756 (manufactured by Kitami Jitsugyo Co., Ltd.). it can. Examples of the MBS resin include C223A (manufactured by Mitsubishi Rayon Co., Ltd.).

In the present invention, as the component (D), one type of the styrene resin may be used, or two or more types may be used in combination.
The compounding quantity of (D) component in this invention is 0-20 mass% in the total amount of (A)-(D) component, It is preferable that it is 0-15 mass%, It is 1-10 mass%. More preferably. If the blending amount exceeds 20% by mass, the flame retardancy is lowered.

[(E) Phosphorus flame retardant]
Examples of the component (E) in the present invention include red phosphorus and phosphate ester flame retardants.
As the phosphoric ester-based flame retardant, those not containing halogen are particularly preferable, which are composed of phosphate ester monomers, oligomers, polymers or mixtures thereof, and include compounds other than the component (G1) described later. It is done. Specifically, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, trinaphthyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, resorcinol- Examples thereof include diphenyl phosphate, trioxybenzene triphosphate and the like, or substituted products and condensates thereof.

Examples of commercially available phosphate ester compounds that can be suitably used as a phosphate ester flame retardant include, for example, TPP [triphenyl phosphate], TXP [trixylenyl phosphate], and CR733S [manufactured by Daihachi Chemical Industry Co., Ltd. Resorcinol bis (diphenyl phosphate)], CR741 [bisphenol A bis (diphenyl phosphate)], PX200 [1,3-phenylene-tetrakis (2,6-dimethylphenyl) phosphate, PX201L [1,4-phenylene-tetrakis (2, 6-dimethylphenyl) phosphate, PX202 [4,4′-biphenylene-tetrakis) 2,6-dimethylphenyl) phosphate, and the like.
The phosphate ester flame retardant can be obtained by reacting divalent phenols and monovalent phenols represented by Ar.OH with phosphorus oxychloride.

These phosphorus flame retardants of component (E) can be used alone or in combination of two or more. Content of these components (E) is 5-20 mass parts with respect to 100 mass parts of resin components which consist of said (A)-(D), Preferably it is 8-20 mass parts, More preferably, it is 10 ˜20 parts by mass.
If the blending amount is less than 5 parts by mass, the desired flame retardancy cannot be obtained, and if it exceeds 20 parts by mass, the chemical resistance, heat resistance, tensile elongation and impact resistance are lowered.

[(F) Inorganic filler]
The inorganic filler which is the component (F) in the present invention is used for further improving the rigidity and flame retardancy of the molded product.
Here, examples of the inorganic filler include talc, mica, kaolin, diatomaceous earth, and calcium carbonate. Of these, plate-like talc and mica, and fibrous fillers such as glass fiber and carbon fiber are preferable, and plate-like talc and / or mica are more preferable. These inorganic fillers may be used alone or in combination of two or more.
The average particle size of the inorganic filler is preferably 0.1 to 50 μm, more preferably 0.2 to 20 μm.

  Here, content of (F) inorganic filler is 3-20 mass parts with respect to 100 mass parts of resin components which consist of said (A)-(D), Preferably it is 5-15 mass parts. Preferably it is 7-15 mass parts. When the content of the component (F) is less than 3 parts by mass, the intended rigidity and flame retardancy improvement effect is insufficient, and when it exceeds 20 parts by mass, peeling tends to occur near the gate of the molded product. Moreover, fluidity | liquidity falls.

[(G) Activator]
The activator used as the component (G) of the present invention is the following (G1) and / or (G2). As used herein, the term “activator” means that the epoxy resin or glycidyl group of the polyolefin resin and / or polyolefin elastomer containing the epoxy group or glycidyl group of the component (B) is activated. The component which has the function which can improve the reactivity is said.
(G1) At least one selected from the group consisting of a phosphite compound and a phosphate compound in which at least one alkoxy group is bonded to a phosphorus atom (provided that the compound has an aryloxy group bonded to a phosphorus atom; Compound in which all ortho positions of the aryloxy group are hydrogen atoms) 0.001 to 1 part by mass (G2) At least one selected from the group consisting of phosphoric acid, phosphorous acid, and organic sulfonic acid compounds. The component (G) of the present invention activates the epoxy group or glycidyl group of the polyolefin resin and / or polyolefin elastomer containing the epoxy group or glycidyl group of the component (B), While improving the production | generation efficiency of the reaction product of (A) component and (B) component, said (A) component thru | or ( It improves the compatibility of the component C) resin, improves the dispersibility of the component (C) in the component (A), suppresses the orientation of the component (C), and functions to suppress delamination. .

<(G1) component>
The component (G1) in the present invention is at least one selected from the group consisting of a phosphite compound and a phosphate compound in which at least one alkoxy group is bonded to a phosphorus atom. However, when the compound has an aryloxy group bonded to a phosphorus atom, the compound is characterized in that all the ortho positions of the aryloxy group are hydrogen atoms.
Examples of phosphite compounds and phosphate compounds in which at least one alkoxy group is bonded to a 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 Examples thereof include phosphite, monooctyl diphenyl phosphite, distearyl pentaerythritol diphosphite and the like.
Examples of the phosphate compound include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, dibutylphenyl phosphate, dioctylphenyl phosphate, diisopropylphenyl phosphate, and the like.
Among the above compounds, tridecyl phosphite, monooctyl diphenyl phosphite, and distearyl pentaerythritol diphosphite are preferable in terms of enhancing the compatibility. The said compound may be used independently and may be used in combination of 2 or more type.

  The compounding quantity of the (G1) component in this invention is 0.001-1 mass part with respect to 100 mass parts of resin components which consist of said (A)-(D), Preferably it is 0.01-0.5. It is 0.05 mass part, More preferably, it is 0.05-0.5 mass part. If the amount is less than 0.001 part by mass, the effect of increasing the generation efficiency of the above-described compatibilizing component is insufficient. Impact properties will be reduced.

<(G2) component>
The component (G2) in the present invention is at least one selected from the group consisting of phosphoric acid, phosphorous acid, and organic sulfonic acid compounds, and is preferably an organic sulfonic acid compound. Of the organic sulfonic acid compounds, aryl sulfonic acid esters are preferred from the viewpoint that they are less likely to volatilize even at the temperature of the extruder when molding a molded body. The aryl sulfonic acid ester is decomposed in the extruder at the time of molding to become a small amount of acid as the aryl sulfonic acid, and this acid activates the epoxy group or glycidyl group, and (C) in the component (A) in the extruder. The dispersibility of the component can be improved, and the peelability of the molded product can be improved.
Examples of the aryl sulfonate esters include p-toluene butyl butyl, p-toluene sulfonate ethyl, p-toluene sulfonate methyl, p-toluene sulfonate isobutyl, naphthalene sulfonate ethyl, naphthalene sulfonate ethyl naphthalene sulfonate. Arylsulfonic acid alkyl esters such as Of these, butyl p-toluenesulfonate is particularly preferred from the standpoint of acid generation and stability.
The above component (G2) may be used alone or in combination of two or more.

  The compounding quantity of the (G2) component in this invention is 0.000001-0.01 mass part with respect to 100 mass parts of resin components which consist of said (A)-(D), Preferably it is 0.0001-0. 0.01 parts by mass, more preferably 0.001 to 0.01 parts by mass. If the amount is less than 0.000001 part by mass, the effect of increasing the generation efficiency of the above-described compatibilizing component is insufficient. If the amount exceeds 0.01 part by mass, the production apparatus may be corroded. The wet heat stability and the heat stability of the resin deteriorate.

  As the component (G) in the present invention, only one of the components (G1) and (G2) may be used, or a combination thereof may be used. When the components (G1) and (G2) are used in combination, the component (G1) is added in an amount of 0.001 to 0.5 parts by mass with respect to 100 parts by mass of the resin component consisting of the components (A) to (D). (G2) It is preferable to mix | blend component in 0.000001-0.01 mass part.

  In addition to the above components (A) to (G), the polycarbonate resin composition of the present invention includes (H) an aliphatic amine salt, aromatic amine salt, ammonium hydroxide, hydroxylamine salt as required. And at least one selected from the group consisting of quaternary phosphonium salts may be added, or (I) a fluorine-containing polymer may be added.

[(H) Aliphatic amine salt, aromatic amine salt, ammonium hydroxide, hydroxylamine salt, and quaternary phosphonium salt]
The component (H) in the present invention is at least one selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxide, hydroxylamine salts, and quaternary phosphonium salts, and is used as necessary. .
The aliphatic amine salt and the aromatic amine salt can be represented by, for example, the general formula R ¹ R ² R ³ N · 1 / nA ¹ , and in the case of the aliphatic amine salt, R ^{1 to} R ³ are independently hydrogen atoms. Or an aliphatic group (but not all 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 are hydrogen atoms at the same time). A ¹ represents an acid, and examples thereof include hydrochloric acid, sulfuric acid, nitric acid, chloric acid, perchloric acid, acetic acid, monoalkyl sulfuric acid, and sulfonic acid compounds. n is the valence of the anion acid A ^1, for example, in the case of hydrochloric acid n = 1, in the case of sulfuric acid it is n = 2.

Ammonium hydroxide, for example the general formula ^{R 4 R 5 R 6 R 7} N + · OH - can be represented by. 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 are hydrogen atoms at the same time).

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

On the other hand, the hydroxylamine salt can be represented by, for example, the general formula R ⁸ R ⁹ NOH · 1 / mA ² , and R ⁸ and R ⁹ are independently, for example, a hydrogen atom or a straight chain having 1 to 5 carbon atoms or Indicates a branched alkyl group (but not all hydrogen atoms at the same time). A ² represents an acid, and m is the valence of the anion of acid A ² .

  Examples of this hydroxylamine salt include methylhydroxylamine hydrochloride, ethylhydroxylamine hydrochloride, n-propylhydroxylamine hydrochloride, isopropylhydroxylamine hydrochloride, dimethylhydroxylamine hydrochloride, diethylhydroxylamine hydrochloride, and hydrochloric acid in these hydroxylamines. Examples include hydroxylamines substituted with other acids such as sulfuric acid, nitric acid, acetic acid, monoalkyl sulfuric acid, and sulfonic acid compounds.

Moreover, although a quaternary phosphonium salt is not specifically limited, For example, the compound represented by either of the following general formula (I)-(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, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an octyl group, a cyclohexyl group, or a cycloalkyl group. Group, phenyl group, tolyl group, xylyl group, naphthyl group, aryl group such as biphenyl group, arylalkyl group such as benzyl group, and the like. At least one of the four R bonded to the phosphorus atom needs to be an aryl group. The four Rs may be the same or different from each other, and two Rs may be bonded to form a ring structure.

In the general formula (I), X ² represents a monovalent counter anion such as a halogen atom, a hydroxyl group, an alkyloxy group, an aryloxy group, an alkylcarbonyloxy group, an arylcarbonyloxy group, 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 the four R ′ 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 the case of two monovalent counter anions).
In the general formula (III), R ″ represents a hydrocarbon group, an alkyloxy group, an aryloxy group or a hydroxyl group, R ″ may be the same as or different from each other, and n represents an integer of 1 to 3.

  Specific examples of the quaternary phosphonium compound represented by the general formula (I) include, for example, tetraphenylphosphonium hydroxide, biphenyltriphenylphosphonium hydroxide, methoxyphenyltriphenylphosphonium hydroxide, phenoxyphenyltriphenylphosphonium hydroxide. , Naphthylphenyltriphenylphosphonium hydroxide, tetraphenylphosphonium tetraphenylborate, biphenyltriphenylphosphonium tetraphenylborate, methoxyphenyltriphenylphosphonium tetraphenylborate, phenoxyphenyltriphenylphosphonium tetraphenylborate, naphthylphenyltriphenylphosphonium tetraphenylborate Tetraphenylphosphonium phenoxide Biphenyltriphenylphosphonium phenoxide, methoxyphenyltriphenylphosphonium phenoxide, phenoxyphenyltriphenylphosphonium phenoxide, naphthylphenyltriphenylphosphonium phenoxide, tetraphenylphosphonium chloride, biphenyltriphenylphosphonium chloride, methoxyphenyltriphenylphosphonium chloride, phenoxyphenyltriphenylphosphonium Examples include chloride, naphthylphenyltriphenylphosphonium chloride, cyclohexyltriphenylphosphonium tetraphenylborate, and the like.

  Specific examples of the quaternary phosphonium compound having a divalent counter anion represented by the above general formula (II) include, for example, bis (tetraphenylphosphonium) carbonate, bis (biphenyltriphenylphosphonium) carbonate, bis (naphthyl). Quaternary phosphonium salts such as triphenylphosphonium) carbonate, and further, for example, bis-tetraphenylphosphonium salt of 2,2-bis (4-hydroxyphenyl) propane, ethylenebis (triphenylphosphonium) dibromide, trimethylenebis (tri Phenylphosphonium) -bis (tetraphenylborate) and the like can also be mentioned.

  Specific examples of the quaternary phosphonium compound having a phosphate represented by the general formula (III) include, for example, tetraphenylphosphonium phosphate, tetraphenylphosphonium phenylphosphate, tetraphenylphosphonium diphenylphosphate, and the like. Can be mentioned.

  From the viewpoint of improving the compatibility between the aromatic polycarbonate resin as the component (A) and the polyolefin resin as the component (C) and improving the peeling, among these quaternary phosphonium salts, the above general A compound represented by the formula (I) having at least one aryl group bonded to a phosphorus atom is preferable, and a compound having three or more aryl groups is more preferable. Quaternary phosphonium salts may be used alone or in combination of two or more.

  In the present invention, as described above, the component (H) is used in accordance with the ratio of the terminal hydroxyl groups to the total terminal groups of the aromatic polycarbonate resin of the component (A), that is, the terminal hydroxyl groups with respect to the total terminal groups. When the group is less than 20 mol%, it is particularly preferable to add it. By adding it, mechanical strength, peel strength, etc. can be further improved. When mix | blending, the compounding quantity of (H) component becomes like this. Preferably it is 0.0001-1 mass part with respect to 100 mass parts of resin components which consist of (A)-(D). If it is 1 part by mass or less, the molecular weight of the polycarbonate in the polycarbonate resin composition does not decrease, and the chemical resistance, tensile elongation, and impact resistance do not decrease. From such points, the blending amount is more preferably 0.0002 to 0.5 parts by mass, and 0.0004 to 0.1 parts by mass with respect to 100 parts by mass of the resin component consisting of (A) to (D). More preferably, it is a part.

  When the component (H) is blended, the component (H) aliphatic amine salt, aromatic amine salt, ammonium hydroxide, hydroxylamine salt, and quaternary phosphonium salt may be used in combination of two or more. However, from the viewpoint of improving compatibility and improving exfoliation, a quaternary ammonium salt such as a tetraalkylammonium hydroxide may be used in combination with a quaternary phosphonium salt. Is preferably 0.1 to 50 times the amount of the quaternary phosphonium salt in terms of controlling the molecular weight of the finished polycarbonate and expressing mechanical strength and the like.

[(I) Fluorine-containing polymer]
In the polycarbonate resin composition of the present invention, a fluorine-containing polymer as component (I) may be used as necessary for further improvement of flame retardancy (5 VB in UL94 5V test).
The fluorine-containing polymer as component (I) is usually a polymer or copolymer having a fluoroethylene structure, such as a difluoroethylene polymer, a tetrafluoroethylene polymer, or a tetrafluoroethylene-hexafluoropropylene copolymer. And a copolymer of tetrafluoroethylene and an ethylene monomer not containing fluorine. Polytetrafluoroethylene (PTFE) is preferable, and the average molecular weight is preferably 500,000 or more, and more preferably 500,000 to 10,000,000.

As polytetrafluoroethylene that can be used in the present invention, all of the currently known types can be used. Of polytetrafluoroethylene, those having a fibril-forming ability are preferred.
Although there is no restriction | limiting in particular in the polytetrafluoroethylene (PTFE) which has a fibril formation ability, For example, what is classified into the type 3 in ASTM standard is mentioned.
Specific examples thereof include, for example, Teflon 6-J (Mitsui / DuPont Fluorochemical Co., Ltd.), Polyflon D-1, Polyflon F-103, Polyflon F201 (Daikin Industries Co., Ltd.), CD076, CD097E (Asahi Glass Co., Ltd.) Manufactured) and the like.
Other than those classified as type 3 above, for example, Algoflon F5 (manufactured by Montefluos Co., Ltd.), polyflon MPA, polyflon FA-100 (manufactured by Daikin Industries, Ltd.) and the like can be mentioned.
These polytetrafluoroethylene (PTFE) may be used independently and may combine 2 or more types.
The polytetrafluoroethylene (PTFE) having the fibril-forming ability as described above is obtained by, for example, using tetrafluoroethylene in an aqueous solvent in the presence of sodium, potassium, ammonium peroxydisulfide, at a pressure of 7 to 700 kPa, and at a temperature. It can be obtained by polymerizing at 0 to 200 ° C, preferably 20 to 100 ° C.

  (I) The compounding quantity of a fluorine-containing polymer becomes like this. Preferably it is 0.1-1 mass part with respect to 100 mass parts of resin components which consist of said (A)-(D), More preferably, it is 0.2-0.8. Part by mass. If the blending amount is 0.1 parts by mass or more, the dripping prevention property is improved, and if it is 1 part by mass or less, the surface appearance and mechanical properties (impact resistance) are not affected.

[Additive]
Moreover, in the polycarbonate resin composition of this invention, various additives can be mix | blended in the range which does not impair the objective of this invention other than said (A)-(I) component. Examples of the additive include an ultraviolet absorber, a light stabilizer, a flame retardant aid, an antistatic agent, a colorant, an antiblocking agent, a release agent, and a lubricant.

Among these, the colorant is used for improving the appearance of the molded product, and any organic or inorganic colorant can be used. Examples of the organic colorant include carbon black, and examples of the inorganic colorant include metal oxide colorants such as titanium oxide, zinc oxide, and iron oxide. Moreover, these coloring materials may be used independently and may combine 2 or more types.
When blending the colorant, the blending amount is preferably in the range of 0.003 to 5 parts by mass, more preferably 100 parts by mass of the resin component consisting of (A) to (D). Is in the range of 0.005 to 3 parts by mass.

[Polycarbonate resin composition and molded body]
The polycarbonate resin composition of the present invention is prepared by blending the above components (A) to (G), the components (H) to (I) and various additives, which are used as necessary, by a conventional method, and melt-kneading. Can be obtained. More preferably, when the amine salt of component (H) is blended, (A) aromatic polycarbonate resin, (B) epoxy group or glycidyl group-containing polyolefin or polyolefin elastomer, and (H) component amine salt, etc. are mixed. (D) Styrenic resin, (E) phosphorus flame retardant, and (G) activator are preferably blended, and (C) polyolefin resin is a mixture of components (A) and (B). It may be blended at the same time or after mixing them, and (F) inorganic filler is blended after mixing (A) component and (B) component regardless of whether or not (H) component is blended. It is preferable. Examples of the melt kneader for melting and kneading include a Banbury mixer, a single screw extruder, a twin screw extruder, a kneader, and a multi screw extruder. The heating temperature in melt kneading is usually 220 to 300 ° C, particularly about 250 ° C.

  When melt kneaded under the above conditions, the (G) component activates the epoxy group or glycidyl group-containing polyolefin or polyolefin elastomer of the component (B) and promotes the reaction with the component (A). As a result, the polycarbonate resin composition obtained in the present invention has (A) component aromatic polycarbonate resin in the matrix phase and (C) component polyolefin resin in the domain, and the polycarbonate and epoxy groups or A compatibilizing component due to a reaction product with a polyolefin containing a glycidyl group is present. The moderate amount of the compatibilizing component stabilizes the interface, improves the compatibility between polycarbonate and polyolefin, has excellent mechanical properties such as impact resistance and bending strength, fluidity and chemical resistance, and is difficult to peel off. A polycarbonate resin composition can be obtained.

  From the viewpoint of moldability, the polycarbonate resin composition of the present invention preferably has a melt volume flow rate (MVR) measured at a temperature of 280 ° C. and a load of 2.16 kg of 2 to 30 ml / 10 minutes, preferably 5 to 25 ml / More preferably, it is 10 minutes. If the MVR is 2 ml / 10 minutes or more, the fluidity is good, and if it is 30 ml / 10 minutes or less, the chemical resistance and impact resistance are good.

The polycarbonate resin composition of the present invention is molded by applying known molding methods such as hollow molding, injection molding, extrusion molding, vacuum molding, pressure molding, hot bending molding, compression molding, calender molding, and rotational molding. A molding method by injection molding is particularly preferable.
In addition, the polycarbonate resin composition of the present invention has an excellent balance of fluidity, chemical resistance, and flame retardancy, and does not exhibit delamination, so automobile parts and electronic devices that require these characteristics by injection molding. It can be used as a housing for devices and information devices.

  The present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, GMA represents glycidyl methacrylate, MFR represents a melt flow rate, and MVR represents a melt volume flow rate.

Components (A) to (I) used in Examples and Comparative Examples are shown below.
(A) Aromatic polycarbonate resin A-1: Taflon FN3000A [manufactured by Idemitsu Kosan Co., Ltd., molecular weight 29,300] OH terminal fraction: 5 mol%
A-2: Taflon FN2600A [manufactured by Idemitsu Kosan Co., Ltd., molecular weight 25,400] OH terminal fraction: 4 mol%
A-3: PC produced by a melting method [molecular weight 21,200] OH terminal fraction: 30 mol%
A SUS316 autoclave with an internal volume of 30 liters was charged with 4560 g (20 mol) of bisphenol A and 4418 g (20.65 mol) of diphenyl carbonate, and tetramethylammonium hydroxide (TMAH) as a catalyst was 2.5 × with respect to bisphenol A. 10 ^-4 mol, 1 × 10 ^-5 mol of tetraphenylphosphonium tetraphenylborate (manufactured by Hokuko Chemical Co., Ltd., TPPK) was added and heated at 210 ° C for 30 minutes, then 240 ° C, 270 ° C and 290 ° C stepwise. The temperature was raised, the degree of vacuum was gradually increased, and the mixture was finally stirred and mixed at 0.4 mmHg for 2 hours to obtain the polycarbonate shown in A-3 above.
The amount of terminal hydroxyl groups (OH terminal fraction) was determined by dissolving ¹ mg of polycarbonate resin in 0.6 mL of deuterated chloroform at room temperature and then measuring ¹ H-NMR ( ¹ H nuclear resonance frequency: 500 MHz, observation frequency) Range: 10000 Hz, cumulative number: 256), terminal hydroxyl group-derived peak a (7.06, 7.05 ppm), terminal bisphenol A phenyl hydrogen peak (6.67, 6.65 ppm) and c ( 4.87 ppm).
(B) Polyolefin resin containing epoxy group or glycidyl group and / or polyolefin elastomer B-1: ethylene-GMA copolymer [manufactured by Sumitomo Chemical Co., Ltd., Bond First E, GMA content 12 mass%]
B-2: Polypropylene-GMA graft copolymer [polypropylene, GMA and organic peroxide (manufactured by NOF Corporation, Perhexa 25B), blended and melt-kneaded by batch kneading, GMA content 9 mass %]
(C) Polyolefin resin C-1: Polypropylene block polymer [manufactured by Prime Polymer Co., Ltd., E-185G, MFR = 0.3 g / 10 min (230 ° C., load 21.18 N)]
C-2: High density polyethylene produced by Ziegler catalyst [Prime Polymer Co., Ltd., 640 UF, MFR = 0.21 g / 10 min (190 ° C., load 49 N)]
(D) Styrenic resin D-1: acrylonitrile-styrene copolymer (AS resin): [manufactured by UMG ABS Co., Ltd., S200N]
D-2: Acrylonitrile-butadiene-styrene copolymer (ABS resin) [manufactured by Nippon A & L Co., Ltd., Santac AT-05, MFR = 18 g / 10 min (220 ° C., 5 kg load)]
(E) Phosphorus flame retardant E-1: aromatic condensed phosphate ester flame retardant [manufactured by Daihachi Chemical Industry Co., Ltd., CR-741]
(F) Inorganic filler F-1: Talc [Fuji Talc Kogyo Co., Ltd., TPA-25]
(G) Activator (G1) Component G-1: Monooctyldiphenyl phosphite [manufactured by ADEKA, Adeka Stub C]
G-2: Distearyl pentaerythritol diphosphite [manufactured by ADEKA, PEP-8]
G-3: Tridecyl phosphite [manufactured by ADEKA Corporation, 3010]
(G2) Component G-4: Additives (antioxidants) other than butyl p-toluenesulfonate (G) component
g-1: Tris (2,4-di-t-butylphenyl) phosphite [BASF, Irgaphos 168]
g-2: 2,2′-methylenebis (4,6-dibutylphenyl) octyl phosphite [manufactured by ADEKA, HP-10]
(H) Ammonium hydroxides H-1: tetramethylammonium hydroxide [manufactured by Wako Pure Chemical Industries, Ltd., 3% aqueous solution]
(I) Fluorine-containing polymer I-1: Polytetrafluoroethylene [Asahi Glass Co., Ltd., PTFE CD076]

<Method for producing test piece for evaluation test>
As an extruder, a biaxial extruder with a vent having two supply ports [manufactured by Nippon Steel Works, TEX44] was used, the set temperature was 250 ° C., the screw rotation speed was 300 rpm, and the discharge rate was 100 kg / hour. The indicated components (A) to (I) and other components were melted and kneaded to obtain target pellets. After the obtained pellets were dried at 110 ° C. for 5 hours or longer, test pieces having a predetermined size in each evaluation were produced by injection molding at a molding temperature of 260 ° C. and a mold temperature of 60 ° C.

<Evaluation method>
(1) Fluidity (measurement of MVR)
Measurement was performed in accordance with ISO 1133 at a temperature of 280 ° C. and a load of 2.16 kg.

(2) Chemical resistance A test piece of 125 × 13 × 3.2 mm was prepared, and a chemical (Sumitomo 3M Limited) was applied with a strain amount of 1.3% using a three-point bending tester with a span distance of 80 mm. Manufactured, paste removing cleaner 30M, containing limonene). The sample was reciprocated 30 times and rubbed, and immediately covered with a plastic bag to prevent chemical volatilization, and the presence or absence of cracks after 168 hours at 23 ° C. was confirmed.

(3) Flame retardance Based on UL94, a 5V test was performed using a test piece having a thickness of 125 × 12.5 × 2 mm. In Table 1, those that passed the 5VB test were indicated as “◯”, and those that failed were indicated as “x”.

(4) Peeling resistance (peeling evaluation by bending test)
Using the pellets obtained as described above, a test piece 1B type in JIS K 7162 and having a thickness of 3.2 mm was molded.
The test piece was bent from the center until both ends were attached, and further bent in the opposite direction in the same manner, and the peelability was evaluated by the number of occurrences of wrinkles on the surface. In Table 1, when it was not peeled after bending 10 times or more, “10 <” was set.

[Examples 1-6, Comparative Examples 1-5]
The resin composition was blended at the blending ratio shown in Table 1 to produce pellets, and the test pieces were prepared and the physical properties were evaluated by the methods described above. The obtained results are shown in Table 1.

According to Table 1, the molded product obtained from the polycarbonate resin composition of the present invention can achieve high flame retardancy of 5 VB in the UL94 5V test, and the balance of fluidity, chemical resistance, and flame retardancy. It can be seen that even in the case of a thin molded product having a film gate, the layered peeling does not occur within 10 times of bending peeling.
On the other hand, since Comparative Examples 1 and 2 do not contain (F) inorganic filler, the flame retardancy is insufficient, and Comparative Examples 3 to 5 contain (F) inorganic filler and thus have high flame retardancy. However, chemical resistance and fluidity decreased.
Since Comparative Examples 2-5 did not contain a specific (G) component, the peel resistance was lowered. In Comparative Example 5, a phosphite compound in which one alkoxy group (octyloxy group) is bonded to a phosphorus atom, which is an antioxidant, is used instead of the component (G1). It has an aryloxy group bonded to a phosphorus atom, and since it has a substituent at the ortho position of the aryloxy group, it can be seen that sufficient peeling resistance cannot be obtained.

  The polycarbonate resin composition of the present invention has an excellent balance of fluidity, chemical resistance, and flame retardancy, and does not exhibit delamination even in the case of a thin molded product. It is useful for equipment housings.

Claims (10)

(A) Aromatic polycarbonate resin 60-95 mass%, (B) Polyolefin resin and / or polyolefin elastomer 2-10 mass% containing epoxy group or glycidyl group, (C) Polyolefin other than the component (B) (E) phosphorus flame retardant 5 to 20 parts by mass, (F) inorganic filler 3 with respect to 100 parts by mass of resin component consisting of 2 to 15% by mass of resin and (D) styrene resin 0 to 20% by mass A polycarbonate resin composition containing ˜20 parts by mass and (G) an activator, wherein the component (G) is the following (G1) and / or (G2).
(G1) At least one selected from the group consisting of a phosphite compound and a phosphate compound in which at least one alkoxy group is bonded to a phosphorus atom (provided that the compound has an aryloxy group bonded to a phosphorus atom; Compound in which all ortho positions of the aryloxy group are hydrogen atoms) 0.001 to 1 part by mass (G2) At least one selected from the group consisting of phosphoric acid, phosphorous acid, and organic sulfonic acid compounds. 000001-0.01 parts by mass   The polycarbonate resin composition according to claim 1, wherein the (A) aromatic polycarbonate resin contains a hydroxyl group as a molecular chain terminal group, and the content of the hydroxyl group with respect to all terminal groups is 20 to 80 mol%. object.   (A) The polycarbonate resin composition according to claim 1, wherein the aromatic polycarbonate resin includes a hydroxyl group as a molecular chain terminal group, and the content of the hydroxyl group with respect to all terminal groups is less than 20 mol%. .   0.0001 to 1 at least one selected from the group consisting of (H) aliphatic amine salt, aromatic amine salt, ammonium hydroxide, hydroxyammonium salt, and quaternary phosphonium salt with respect to 100 parts by mass of the resin component. The polycarbonate resin composition of Claim 3 formed by mix | blending a mass part.   The polycarbonate resin composition in any one of Claims 1-4 which contains 0.1-1 mass part of (I) fluorine-containing polymers with respect to 100 mass parts of said resin components.   (D) The group in which the styrene resin is composed of acrylonitrile-styrene copolymer (AS resin), acrylonitrile-butadiene-styrene copolymer (ABS resin), and methyl methacrylate-butadiene rubber-styrene copolymer (MBS resin). The polycarbonate resin composition in any one of Claims 1-5 which is at least 1 sort (s) chosen from.   The polycarbonate resin composition according to any one of claims 1 to 6, wherein the organic sulfonic acid compound as the component (G2) is an aryl sulfonic acid ester.   (F) The polycarbonate resin composition according to any one of claims 1 to 7, wherein the inorganic filler is talc and / or mica.   The polycarbonate resin composition according to any one of claims 1 to 8, wherein a melt volume flow rate (MVR) measured at a temperature of 280 ° C and a load of 2.16 kg is 2 to 30 ml / 10 minutes.   The molded object which consists of a polycarbonate resin composition in any one of Claims 1-9.