JP2012077265A - Polycarbonate resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polycarbonate resin composition capable of attaining compatibility between excellent shock resistance and excellent chemical resistance by covering a defect of an aromatic polycarbonate resin, not causing laminar peeling after molding even in the case of a thin molding, and having high fusion strength with an acrylic resin or a polycarbonate resin.SOLUTION: The polycarbonate resin composition contains: (A) a 50-98 mass% aromatic polycarbonate resin partially having hydroxy groups as molecular chain terminal groups, wherein the hydroxy group content in the whole terminal groups is 10-80 mol%, and having a viscosity average molecular weight of 11,000-30,000; (B) 1-30 mass% polyolefin resin and/or polyolefin elastomer containing an epoxy group or a glycidyl group; and (C) 1-40 mass% polyethylene resin whose melt index (MI) is <5 g/10 min.

Description

  The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition useful as a housing for automobile parts, electronic devices, information devices, and the like.

Polycarbonate (hereinafter sometimes abbreviated as “PC”) has the advantage of excellent mechanical properties such as impact strength, but has disadvantages such as poor fluidity and chemical resistance. For this reason, it has been difficult to simply replace filler-filled polypropylene, which is often used as, for example, automotive parts and has problems such as scratch-resistant whitening, texture transfer, and poor weld appearance, with polycarbonate.
PC / ABS (acrylonitrile butadiene styrene) alloy is used for improving the flow characteristics of PC, and PC / polyester (PBT: polybutylene terephthalate, PET: polyethylene terephthalate) alloy for chemical resistance. Has been proposed. However, PC / ABS alloy is inferior in chemical resistance and weather resistance, and gloss (gloss) is too high, so that it cannot be used as an interior material as it is, and requires painting, resulting in increased costs, and thus its use is restricted. Further, PC / polyester (PBT, PET) has a problem that the effect of improving the fluidity is small, the hydrolysis resistance is poor, the gloss is high, and it is difficult to reduce the gloss.

  Therefore, as a combination of materials that overcome these problems, an alloy of PC and polyolefin resin (PO), particularly an alloy of polypropylene (PP) or polyethylene (PE) and PC has been studied (for example, Patent Document 1). ~ 3). The polycarbonate resin compositions disclosed in Patent Documents 1 to 3 all have excellent impact resistance, bending strength, chemical resistance and fluidity.

JP 2009-275131 A JP 2009-298993 A JP 2010-024368 A

  However, the polycarbonate resin compositions (PC / PO alloys) disclosed in Patent Documents 1 to 3 have low fusion strength, and in particular, vibration fusion (vibration welding) that is most frequently used in general industrial products. In contrast, the fusion strength is insufficient. For this reason, for example, when trying to fuse a part made of PC / PO alloy and a part made of PC or polymethyl methacrylate (PMMA), the product is easily peeled off due to low fusion strength. However, it cannot be used as an industrial material for parts that require this.

  The object of the present invention is to make up for the shortcomings of the aromatic polycarbonate resin, achieve both excellent impact resistance and chemical resistance, and does not exhibit delamination even after being molded, and is an acrylic resin. Another object is to provide a polycarbonate resin composition having high fusion strength with the polycarbonate resin.

The reason why the PC / PO alloy disclosed in Patent Documents 1 to 3 has low vibration fusion strength and is easily peeled off even if it is fused with a part made of PC or PMMA is vibration friction on the fusion surface. This is probably because if the melted PO has too low viscosity, it will flow out and form a PO film.
As a result of intensive studies, the present inventors have (A) a specific aromatic polycarbonate resin containing a hydroxyl group as a molecular chain end group, (B) a specific polyolefin resin and / or a polyolefin elastomer, And (C) It discovered that the said subject could be solved by the polycarbonate resin composition which mix | blended the polyethylene-type resin which has predetermined | prescribed MI in a specific ratio. In addition, the inventors have (A ′) a specific aromatic polycarbonate resin, (B) a specific polyolefin resin and / or polyolefin elastomer, (C) a polyethylene resin having a predetermined MI, and (D) The above problem can also be solved by a polycarbonate resin composition in which at least one selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxide, hydroxylamine salts and quaternary phosphonium salts is blended in a specific ratio. I found it. The present invention has been completed based on such findings.
That is, the present invention provides the following polycarbonate resin composition and molded article.

[1] (A) An aromatic having a hydroxyl group as a molecular chain end group, the hydroxy group content with respect to all the end groups being 10 to 80 mol%, and the viscosity average molecular weight being 11000 to 30000 50 to 98% by weight of polycarbonate resin, (B) 1 to 30% by weight of polyolefin-based resin and / or polyolefin-based elastomer containing epoxy group or glycidyl group, and (C) Melt index (MI) of less than 5 g / 10 minutes A polycarbonate resin composition containing 1 to 40% by mass of a polyethylene resin.
[2] The polycarbonate according to [1], wherein the content of the epoxy group or glycidyl group in the polyolefin resin and / or polyolefin elastomer containing the epoxy group or glycidyl group is 1 to 15% by mass. Resin composition.
[3] The (A) aromatic polycarbonate resin is changed from (A ′) an aromatic polycarbonate resin having a terminal hydroxy group content of less than 10 mol% to (D) an aliphatic amine salt, an aromatic amine salt, an ammonium hydroxide. The polycarbonate resin composition according to the above [1] or [2], which is obtained by adding at least one selected from the group consisting of a hydroxylamine salt and a quaternary phosphonium salt, and melt-kneading.

[4] (A ′) The content of the terminal hydroxy group is less than 10 mol% and the viscosity average molecular weight is 16000 to 35000, 50 to 98 mass% of the aromatic polycarbonate resin, (B) contains an epoxy group or a glycidyl group 1 to 30% by mass of a polyolefin-based resin and / or polyolefin-based elastomer, and (C) 100 parts by mass of a resin component consisting of 1 to 40% by mass of a polyethylene-based resin having a melt index (MI) of less than 5 g / 10 min. (D) Polycarbonate resin obtained by melt-kneading at least one 0.001-1 part by mass selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxide, hydroxylamine salts and quaternary phosphonium salts Composition.
[5] The polycarbonate according to [4] above, wherein the content of the epoxy group or glycidyl group in the polyolefin resin and / or polyolefin elastomer containing the epoxy group or glycidyl group is 1 to 15% by mass. Resin composition.
[6] The polycarbonate resin composition according to any one of [1] to [5], wherein the MI of the resin composition is 1.0 to 20.0 g / 10 min.
[7] A molded article obtained by injection molding the polycarbonate resin composition according to any one of [1] to [6].

  The polycarbonate resin composition of the present invention has both excellent impact resistance and chemical resistance, does not exhibit delamination after molding, even if it is a thin molded product, and is fused with an acrylic resin or a polycarbonate resin. High strength.

The polycarbonate resin composition of the present invention comprises (A) a specific aromatic polycarbonate resin containing a hydroxyl group as a molecular chain terminal group, (B) a specific polyolefin resin and / or polyolefin elastomer, and (C ) Including a polyethylene resin having a predetermined MI (first invention).
The polycarbonate resin composition of the present invention includes (A ′) a specific aromatic polycarbonate resin, (B) a specific polyolefin resin and / or polyolefin elastomer, (C) a polyethylene resin having a predetermined MI, and (D) It contains at least one selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxide, hydroxylamine salts and quaternary phosphonium salts (second invention).

[(A) aromatic polycarbonate resin]
The (A) aromatic polycarbonate resin in the present invention includes those having a hydroxy group as a molecular chain end group, the content of the hydroxy group with respect to all the end groups is 10 to 80 mol%, and the viscosity average molecular weight is 11000. ~ 30,000.
Usually, as the component (A) in the present invention, various aromatic polycarbonate resins produced by a reaction between 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 -Bidoxyphenyl) -1,3,5-triisopropylbenzene, phloroglysin, trimellitic acid, and isatin bis (o-cresol).

  The molecular chain terminal group of the component (A) in the present invention includes those having a hydroxy group, and the content of the hydroxy group with respect to all terminal groups is 10 to 80 mol%, preferably 15 to 75 mol%, more Preferably it is 20-70 mol%. When the content is less than 10 mol%, the effect of improving compatibility is small, the tensile elongation rate and impact strength are low, and delamination tends to occur in the molded product. Moreover, when it exceeds 80 mol%, a problem may generate | occur | produce in a hydrolyzability and heat-resistant stability.

  In the component (A), adjustment of the content ratio of hydroxy groups with respect to all terminal groups is conventionally used as a terminal stopper when, for example, an aromatic polycarbonate resin is produced by reacting a dihydric phenol and a carbonate precursor. The monovalent phenols and the alcoholic hydroxy group-containing phenols are used, and the use ratio thereof and the use ratio relative to the divalent phenol can be controlled.

Examples of monohydric phenols conventionally used as a terminal terminator include phenol, p-cresol, p-tert-butylphenol, p-tert-octylphenol, p-cumylphenol, p-nonylphenol and p-tert-amyl. Phenol etc. are mentioned.
On the other hand, examples of the alcoholic hydroxy group-containing phenols include 2-hydroxybenzyl alcohol, 3-hydroxybenzyl alcohol, 4-hydroxybenzyl alcohol, 2- (4-hydroxyphenyl) ethyl alcohol, and 2,6-dihydroxy-4- Examples include methylphenol.

  The viscosity average molecular weight of the component (A) in the present invention is 11000 to 30000, preferably 12000 to 29000, from the viewpoint of achieving both excellent impact resistance and chemical resistance and preventing surface layer peeling of the molded product. More preferably, it is 13,000-28000.

The viscosity average molecular weight of the component (A) in the present invention is a specific viscosity (η _sp) measured using an Ubbelohde viscometer with a solution prepared by dissolving about 0.7 g of an aromatic polycarbonate resin in 100 cm ³ of methylene chloride at 20 ° C. ) Is inserted into the following equation.
(Η _sp ) / C = [η] + 0.45 × [η] ² C
[Η] = 1.23 × 10 ⁻⁵ M ^0.83
([Η] is the intrinsic viscosity, C is the polymer concentration, and M is the viscosity average molecular weight.)

  Moreover, (A) aromatic polycarbonate resin in this invention is mentioned later to aromatic polycarbonate resin whose (A ') terminal hydroxy group content is less than 10 mol%, and whose viscosity average molecular weight is 16000-35000 ( D) It can be obtained by adding at least one selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxide, hydroxylamine salts and quaternary phosphonium salts, and melt-kneading.

The viscosity average molecular weight of the component (A ′) is 16000 to 35000, preferably 17000 to 34000, so that the viscosity average molecular weight of the component (A) obtained after melt-kneading with the component (D) is in the above range. More preferably, it is 18000-33000.
The component (A ′) is the same as the aromatic polycarbonate resin of the component (A) except for the content of the terminal hydroxy group and the viscosity average molecular weight.

  Content of (A) component in this invention is 50-98 mass% in the total amount of (A)-(C) component, Preferably it is 55-94 mass%, More preferably, it is 60-90 mass%. is there. If the content is less than 50% by mass, the tensile strength and the elastic modulus are lowered, and if it exceeds 98% by mass, the effect of improving chemical resistance becomes insufficient.

[(B) polyolefin resin or polyolefin elastomer]
The (B) polyolefin resin and / or polyolefin elastomer in the present invention contains an epoxy group or a glycidyl group.

  The polyolefin resin in the component (B) is, 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, or an olefin polymer. May be copolymerized with an unsaturated monomer having an epoxy group or a glycidyl group, and such a copolymer may be a graft copolymer, a random copolymer, or a block copolymer. Good.

  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, and N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzyl] methacrylamide. These may be used alone or in combination of two or more.
In addition, these unsaturated monomers having an epoxy group or glycidyl group are used together with unsaturated monomers having no epoxy group or glycidyl group such as alkyl acrylate and alkyl methacrylate. It may be a polymer containing a group such as an acrylic ester or a methacrylic ester in addition to a glycidyl group.

  The content of the epoxy group or glycidyl group in the polyolefin resin and / or polyolefin elastomer as the component (B) in the present invention is preferably 1 to 15% by mass, more preferably 1.5 to 12% by mass, and still more preferably. Is 2.0-10 mass%. If the content is less than 1% by mass, the effect of improving the compatibility between the component (A) and the component (C) is not exhibited, the tensile elongation rate and the impact resistance are lowered, and delamination of the molded product occurs. Sometimes. On the other hand, if it exceeds 15% by mass, self-crosslinking may occur, the tensile elongation and impact resistance may be lowered, and delamination of the molded product may occur.

  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.
Among these, as the polyolefin resin, a polyethylene resin is preferable, and as the polyolefin elastomer, a polyethylene elastomer is preferable.

  Content of (B) component in this invention is 1-30 mass% in the total amount of (A)-(C) component, Preferably it is 2-25 mass%, More preferably, it is 3-20 mass%. is there. If it is less than 1% by mass, the compatibility between the component (A) and the component (C) cannot be improved sufficiently, the tensile elongation rate and impact resistance are lowered, and further, delamination of the molded product may occur. . If it exceeds 30% by mass, self-crosslinking tends to occur, the tensile strength and impact resistance are lowered, the elastic modulus is also lowered, and in some cases, delamination of the molded product may occur.

[(C) Polyethylene resin]
The (C) polyethylene resin in the present invention has a melt index (MI) of less than 5 g / 10 minutes. When MI is 5 g / 10 min or more, the vibration fusion (welding) property is lowered, and it is not possible to sufficiently fuse with different materials such as PC and PMMA, and the product is easily peeled off.
(C) MI of a component is measured by resin temperature 190 degreeC and load 21.18N based on ASTMD1238.
In the invention of the prior application (Japanese Patent Laid-Open No. 2010-024368), the fluidity is improved by setting the MI of the polyethylene resin to 5 g / 10 min or more. However, the invention of the prior application is insufficient in the fusion strength with the acrylic resin or the polycarbonate resin, and cannot be used for a part that requires fusion as a product. In contrast, in the present invention, the MI of the polyethylene resin is set to less than 5 g / 10 minutes, so that the fusion strength is improved while sacrificing the effect of improving the fluidity.
Further, the prior invention (JP 2009-275131 A) also describes an example in which the MI of the polypropylene resin is less than 5 g / 10 minutes. However, since polypropylene has a melting point higher than that of polyethylene, there is a problem that vibration fusion is poor when polypropylene is used. On the other hand, the present invention has a great advantage in that vibration fusion with PC or acrylic resin is improved by selecting a specific polyethylene having a lower melting point and higher molecular weight than polypropylene.

Component (C) may be a polymer obtained by polymerizing ethylene alone or may be a copolymer obtained by copolymerizing ethylene as a main component. For example, polyethylene resins such as high density polyethylene, medium density polyethylene, low density polyethylene, linear low density polyethylene, ethylene-α-olefin copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylate copolymer, etc. Is mentioned. In addition, examples of the ethylene-α-olefin copolymer include a copolymer of propylene and ethylene, and may be any of a graft copolymer, a random copolymer, and a block copolymer. Among these, high density polyethylene is particularly preferable.
In the present invention, as the component (C), one type of polyethylene resin may be used, or two or more types may be used in combination.

  Content of (C) component in this invention is 1-40 mass% in the total amount of (A)-(C) component, Preferably it is 5-35 mass%, More preferably, it is 7-30 mass%. is there. If the content is less than 1% by mass, the chemical resistance improving effect cannot be sufficiently exerted, and if it exceeds 40% by mass, the tensile elongation and elastic modulus are lowered, and in some cases, delamination of the molded product occurs.

[(D) Aliphatic amine salt, aromatic amine salt, ammonium hydroxide, hydroxylamine salt]
(D) component in this invention is at least 1 sort (s) chosen from the group which consists of an aliphatic amine salt, an aromatic amine salt, ammonium hydroxide, and a hydroxylamine salt. As described above, the component (D) is melt-kneaded with the aromatic polycarbonate resin (A ′) having a terminal hydroxy group content of less than 10 mol%, so that the aromatic polycarbonate resin of the component (A) in the present invention is used. Can be obtained.

(Aliphatic amine salts and aromatic amine salts)
The aliphatic amine salt and an aromatic amine salt is not particularly limited, may be used, for example the general formula ^{R 1 R 2 R 3 N ·} 1 / nA represented by ¹ compound. In the formula, R ^{1 to} R ³ each independently represent a hydrogen atom, an aliphatic group or an aromatic group (however, all of R ^{1 to} R ³ do not represent hydrogen atoms at the same time). Specifically, in the case of an aliphatic amine salt, R ^{1 to} R ³ each independently represent a hydrogen atom or an aliphatic group (however, all of R ^{1 to} R ³ do not represent a hydrogen atom at the same time). ). In the case of an aromatic amine salt, R ^{1 to} R ³ each independently represent a hydrogen atom, an aliphatic group or an aromatic group (provided that at least one of R ^{1 to} R ³ represents an aromatic group). . 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)
The ammonium hydroxide is not particularly limited, for example, the general formula ^{R 4 R 5 R 6 R 7} N + · OH - can be used represented by the compound. In the formula, R ^{4 to} R ⁷ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms (provided that all of R ^{4 to} R ⁷ simultaneously represent a hydrogen atom). Nothing.)
Specific examples of ammonium hydroxide include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetraisopropylammonium hydroxide, and the like.

(Hydroxylamine salt)
The hydroxylamine salt is not particularly limited, may be used, for example the formula ^{R 8 R 9 NOH · 1 /} mA represented by ² compound. In the formula, R ⁸ and R ⁹ each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms (provided that R ⁸ and R ⁹ simultaneously represent a hydrogen atom). No.) A ² represents an acid, and m is the valence of the anion of acid A ² .
Specific examples of the hydroxylamine salt include methylhydroxylamine hydrochloride, ethylhydroxylamine hydrochloride, n-propylhydroxylamine hydrochloride, isopropylhydroxylamine hydrochloride, dimethylhydroxylamine hydrochloride, diethylhydroxylamine hydrochloride and the like. Moreover, the hydroxylamine salt etc. which substituted the hydrochloric acid in these hydroxylamine salts with other acids, for example, a sulfuric acid, nitric acid, an acetic acid, a monoalkyl sulfuric acid, a sulfonic acid compound, etc. can be mentioned.

In the present invention, as the component (D), one type of the nitrogen-containing compound described above may be used, or two or more types may be used in combination.
The compounding amount of the component (D) in the present invention is 0.001 to 1 part by mass, preferably 0, per 100 parts by mass of the total amount of the component (A ′), the component (B) and the component (C). 0.002 to 0.8 parts by mass, and more preferably 0.003 to 0.5 parts by mass.
The If the blending amount is less than 0.001 part by mass, delamination of the molded product is likely to occur, and if it exceeds 1 part by mass, the tensile elongation and impact resistance may be reduced.

  In the polycarbonate resin composition of the present invention, various fillers, various flame retardants, and various additives can be blended within a range that does not impair the object of the present invention.

[Filler]
Examples of the filler that can be blended in the polycarbonate resin composition of the present invention include a spherical filler, a plate-like filler, and a fibrous filler.
Examples of the spherical filler include calcium carbonate, kaolin (aluminum silicate), silica, perlite, shirasu balloon, sericite, diatomaceous earth, calcium sulfite, calcined alumina, calcium silicate, crystalline zeolite, amorphous zeolite and the like. It is done.
Examples of the plate filler include talc, mica, and wollastonite.
Examples of the fibrous filler include needle-like materials such as glass fiber, carbon fiber, and wollastonite, fibrous materials such as magnesium oxysulfate, potassium titanate fiber, and fibrous calcium carbonate. .
As the glass fiber, any of materials containing alkali-containing glass, low alkali glass, non-alkali glass, or the like can be preferably used.
There is no restriction | limiting in particular in the form of these glass fibers, For example, the thing of any forms, such as roving, a milled fiber, and a chopped strand, can be used.
Examples of commercially available glass fibers include CSH-3PA (manufactured by Nitto Boseki Co., Ltd.), T511 (manufactured by Nippon Electric Glass Co., Ltd.), MA409C (manufactured by Asahi Fiber Glass Co., Ltd.), and the like.

[Flame retardants]
Examples of the flame retardant that can be blended in the polycarbonate resin composition of the present invention include halogen flame retardant, nitrogen flame retardant, metal hydroxide, phosphorus flame retardant, organic alkali metal salt, organic alkaline earth metal salt, Examples include silicone-based flame retardants, expansive graphite, phosphorus-based, metal salt-based, silicone-based and the like.

Examples of halogen flame retardants include tetrabromobisphenol A (TBA), halogenated polycarbonates and (co) polymers of halogenated polycarbonates, oligomers thereof (TBA carbonate oligomers), decabromodiphenyl ether, TBA epoxy oligomers, halogenated polystyrene, Examples thereof include halogenated polyolefins.
However, although the halogen flame retardant has a relatively good flame retardant efficiency, a flame retardant containing no halogen is preferable from the viewpoint of environmental pollution and safety.

Examples of the nitrogen-based flame retardant include melamine, an alkyl group, or an aromatic group-substituted melamine.
Examples of the metal hydroxide include magnesium hydroxide and aluminum hydroxide.

Examples of the phosphorus-based flame retardant include halogen-free organic phosphorus-based flame retardants.
As the halogen-free machine phosphorus-based flame retardant, any organic compound having a phosphorus atom and not containing a halogen can be used without particular limitation.
Among these, phosphate ester compounds having one or more ester oxygen atoms directly bonded to the phosphorus atom are preferably used.
The phosphate ester compound may be a monomer, dimer, oligomer, polymer, or a mixture thereof.
Specifically, trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, octyl diphenyl phosphate, tri (2-ethylhexyl) phosphate, diisopropyl Phenyl phosphate, trixylenyl phosphate, tris (isopropylphenyl) phosphate, trinaphthyl phosphate, bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, resorcinol-diphenyl phosphate, trioxybenzene triphosphate, or a substitution product thereof, condensation Such as things.
Examples of halogen-free phosphorus-based flame retardants other than organic phosphorus-based flame retardants include red phosphorus.

Examples of the organic alkali metal salt and the organic alkaline earth metal salt include various types, and an alkali metal salt or alkaline earth metal salt of an organic acid or organic acid ester having at least one carbon atom is preferably used. .
Here, organic sulfonic acid, organic carboxylic acid, etc. are mentioned as organic acid or organic acid ester.
Examples of the alkali metal salt include salts such as sodium, potassium, lithium and cesium, and examples of the alkaline earth metal salt include salts such as magnesium, calcium, strontium and barium. Of these, sodium, potassium and cesium salts are preferred.
The salt of the organic acid may be substituted with a halogen such as fluorine, chlorine or bromine. Examples thereof include perfluoromethanesulfonic acid, perfluoroethanesulfonic acid, and potassium salt of perfluorobutanesulfonic acid. Etc.

Examples of the silicone flame retardant include silicone oil and silicone resin.
Examples of the silicone flame retardant include (poly) organosiloxanes having a functional group.
Examples of the functional group include an alkoxy group, aryloxy, polyoxyalkylene group, hydrogen group, hydroxyl group, carboxyl group, cyano group, amino group, mercapto group, and epoxy group.
Said flame retardant may be used individually by 1 type, and may be used in combination of 2 or more type.

[Additive]
Other additives that can be blended in the polycarbonate resin composition of the present invention include antioxidants, ultraviolet absorbers, light stabilizers, flame retardant aids, colorants, antistatic agents, antiblocking agents, mold release agents. Agents and lubricants.

<Polycarbonate resin composition and molded article>
The polycarbonate resin composition of the present invention is the above component (A), component (B) and component (C), or component (A ′), component (B), component (C) and component (D), It can be obtained by blending various fillers, flame retardants and additives as necessary, and melt-kneading.
Examples of the melt kneader 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 suitably 220 to 300 ° C.

The MI of the polycarbonate resin composition of the present invention is preferably 1.0 to 20.0 g / 10 min from the viewpoint of achieving both excellent impact resistance and chemical resistance and preventing the surface layer from peeling off the molded product. Preferably it is 1.5-18.0 g / 10min, More preferably, it is 2.0-15.0 g / 10min.
The MI of the resin composition is measured at a resin temperature of 280 ° C. and a load of 21.18 N in accordance with ASTM D 1238.

The fusion (welding) strength of the polycarbonate resin composition of the present invention to the acrylic resin or polycarbonate resin is preferably 300 N / cm ² or more, more preferably 500 N / cm ² or more. When the fusion strength is less than 300 N / cm ² , when the product is used for a long period of time, it may be peeled off at the fusion part and may be broken.

  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. It can be a body. In particular, a molding method by injection molding is preferable.

The polycarbonate resin composition of the present invention has both excellent impact resistance and chemical resistance, and even if it is a thin-walled molded product, it does not exhibit delamination after molding, so these characteristics are required by injection molding. It can be suitably used as a housing for automobile parts, electronic equipment and information equipment.
Moreover, since the polycarbonate resin composition of the present invention has high fusion strength with an acrylic resin or polycarbonate resin, it can be used as an industrial material for parts that require fusion as a product.

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to these examples.
In the following, GMA represents glycidyl methacrylate. MI represents a melt index (230 ° C., 21.18 N).

Components (A) to (D) used in Examples and Comparative Examples are shown below.
(A) Aromatic polycarbonate resin a-1: viscosity average molecular weight (Mv) 18000, terminal hydroxyl group 25 mol%
a-2: Viscosity average molecular weight (Mv) 14000, terminal hydroxyl group 45 mol%
a-3: Viscosity average molecular weight (Mv) 10,000, terminal hydroxyl group 13 mol%
a-4: Viscosity average molecular weight (Mv) 30000, terminal hydroxyl group 5 mol% or less; Taflon FN-3000 [trade name, manufactured by Idemitsu Kosan Co., Ltd.]
a-5: Viscosity average molecular weight (Mv) 22000, terminal hydroxyl group 5 mol% or less; Taflon FN-2200 [trade name, manufactured by Idemitsu Kosan Co., Ltd.]
a-6: Viscosity average molecular weight (Mv) 15000, terminal hydroxyl group 5 mol% or less; Taflon FN-1500 [trade name, manufactured by Idemitsu Kosan Co., Ltd.]

(B) polyolefin resin or polyolefin elastomer b-1: ethylene-GMA copolymer [GMA content: 12% by mass (5.46% by mass as glycidyl group)]; Bond First BF-E [trade name, Sumitomo Chemical Co., Ltd.)
b-2: Polyethylene-GMA graft copolymer [GMA content: 6.4% by mass (2.91% by mass as glycidyl group)]
b-3: Polyethylene-GMA graft copolymer [GMA content: 1.8% by mass (0.82% by mass as glycidyl group)]
The above b-2 and b-3 are high-density polyethylene [MI: 12 g / 10 min; manufactured by Prime Polymer Co., Ltd., trade name: Hi-Zex 1300J], GMA and organic peroxide, blended and then biaxially extruded. It was manufactured by melt-kneading at 200 ° C. using a machine.

(C) Polyethylene resin c-1: high density polyethylene, MI: 0.2 g / 10 min; Hi-Zex 640UF [trade name, manufactured by Prime Polymer Co., Ltd.]
c-2: linear low density polyethylene, MI: 2 g / 10 min; Moatech 0248Z [trade name, manufactured by Prime Polymer Co., Ltd.]
c-3: High density polyethylene, MI: 40 g / 10 min; Suntech J300 [trade name, manufactured by Asahi Kasei Chemicals Corporation]
c-4: Low-density polyethylene, MI: 15 g / 10 min; Ultzex 15150L [trade name, manufactured by Prime Polymer Co., Ltd.]

(D) At least one selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxide, and hydroxylamine salts d-1: ammonium hydroxide; tetramethylammonium hydroxide [manufactured by Wako Pure Chemical Industries, Ltd.]
d-2: aliphatic amine salt; cation BB [trade name, manufactured by NOF Corporation]

Examples 1-6 and Comparative Examples 1-6
After the components are dry blended according to the blending ratios shown in Tables 1 and 2, kneading is performed using a twin-screw kneader (TEX44, trade name, manufactured by Nippon Steel) to increase the residence time at a set temperature of 250 ° C. A large number of blocks were set, and melt kneading was performed while suppressing the discharge amount to obtain pellets.
After the obtained pellets were dried at 120 ° C. for 6 hours or longer, test pieces were prepared by injection molding (injection molding temperature 280 ° C., mold temperature 80 ° C.), and physical properties were evaluated by the following methods.
The obtained results are shown in Tables 1 and 2.

<Evaluation method>
(1) Melt index (MI)
Conforms to ASTM D 1238 (2) Tensile strength / tensile elongation (test piece thickness: 3.0 mm)
Conforms to JIS K 7162 (3) Izod impact strength (notched) (test piece thickness: 3.0 mm)
Conforms to JIS K 7110

(4) Chemical resistance A test piece of 125 × 12.5 × 3 mm is used, and Magiclin [Bath Magiclin (trade name, manufactured by Kao Corporation, 9% fatty acid amidopropyl betaine)] and ethanol are used as the immersion liquid. used.
Chemical resistance-1 was determined by visually observing the situation after 168 hours while maintaining the amount of strain at 1% in a three-point bending test with a span distance of 80 mm using magic phosphorus. The case where a crack was not recognized was evaluated as ◯, and the case where a crack was generated was evaluated as ×.
Chemical resistance-2 was evaluated in the same manner as chemical resistance-1 using ethanol.

(5) Surface peeling A 150 × 150 × 1.5 mm thin plate was produced by injection molding, and the surface peeling state in the vicinity of the gate was visually observed. The case where peeling was not observed was evaluated as ◯, and the case where peeling was observed even a little was evaluated as x.

(6) Vibration fusion strength Using a 100 × 10 × 3 mm polycarbonate resin composition test piece and a polymethyl methacrylate test piece, the test pieces were vibration welded to each other at an area of 10 × 10 mm, and then tensioned. A test was conducted and the strength required for peeling (vibration fusion strength) was measured. As the welding conditions, pressure bonding was performed at a frequency of 230 Hz, an amplitude width of 1.8 mm, and a load of 1 kN for 5 seconds.

  As is clear from Tables 1 and 2, the polycarbonate resin composition of the present invention has excellent tensile strength, elongation, impact resistance, and chemical resistance, and exhibits delamination after molding even for thin molded products. And has high fusion strength with acrylic resin or polycarbonate resin.

The polycarbonate resin composition of the present invention has both excellent impact resistance and chemical resistance, and even if it is a thin-walled molded product, it does not exhibit delamination after molding, so these characteristics are required by injection molding. It can be suitably used as a housing for automobile parts, electronic equipment and information equipment.
Moreover, since the polycarbonate resin composition of the present invention has high fusion strength with an acrylic resin or polycarbonate resin, it can be used as an industrial material for parts that require fusion as a product.

Claims (7)

  (A) Aromatic polycarbonate resin 50 having a hydroxyl group as a molecular chain terminal group, the hydroxy group content with respect to all terminal groups being 10 to 80 mol%, and the viscosity average molecular weight being 11000 to 30000 -98% by mass, (B) a polyolefin-based resin containing an epoxy group or a glycidyl group and / or 1-30% by mass of a polyolefin-based elastomer, and (C) a polyethylene-based resin having a melt index (MI) of less than 5 g / 10 min. A polycarbonate resin composition containing 1 to 40% by mass.   The polycarbonate resin composition according to claim 1, wherein the content of the epoxy group or glycidyl group in the polyolefin resin and / or polyolefin elastomer containing the epoxy group or glycidyl group is 1 to 15% by mass.   The (A) aromatic polycarbonate resin is converted into (A ′) an aromatic polycarbonate resin having a terminal hydroxy group content of less than 10 mol%, and (D) an aliphatic amine salt, aromatic amine salt, ammonium hydroxide, hydroxylamine. The polycarbonate resin composition according to claim 1 or 2, which is obtained by adding at least one selected from the group consisting of a salt and a quaternary phosphonium salt, and melt-kneading.   (A ′) A content of the terminal hydroxy group is less than 10 mol%, and an aromatic polycarbonate resin having a viscosity average molecular weight of 16000 to 35000 is 50 to 98% by mass, (B) a polyolefin system containing an epoxy group or a glycidyl group. With respect to 100 parts by mass of a resin component consisting of 1 to 30% by mass of a resin and / or polyolefin elastomer and (C) 1 to 40% by mass of a polyethylene resin having a melt index (MI) of less than 5 g / 10 minutes, (D ) A polycarbonate resin composition obtained by melt-kneading at least one 0.001-1 part by mass selected from the group consisting of aliphatic amine salts, aromatic amine salts, ammonium hydroxides, hydroxylamine salts and quaternary phosphonium salts.   The polycarbonate resin composition according to claim 4, wherein the content of the epoxy group or glycidyl group in the (B) polyolefin resin and / or polyolefin elastomer containing an epoxy group or glycidyl group is 1 to 15% by mass.   The polycarbonate resin composition according to any one of claims 1 to 5, wherein the MI of the resin composition is 1.0 to 20.0 g / 10 min.   The molded object formed by injection-molding the polycarbonate resin composition in any one of Claims 1-6.