WO2017169912A1 - Composition de résine thermoplastique de renfort et son article moulé - Google Patents

Composition de résine thermoplastique de renfort et son article moulé Download PDF

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WO2017169912A1
WO2017169912A1 PCT/JP2017/010958 JP2017010958W WO2017169912A1 WO 2017169912 A1 WO2017169912 A1 WO 2017169912A1 JP 2017010958 W JP2017010958 W JP 2017010958W WO 2017169912 A1 WO2017169912 A1 WO 2017169912A1
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Prior art keywords
mass
parts
reinforced thermoplastic
resin composition
thermoplastic resin
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PCT/JP2017/010958
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English (en)
Japanese (ja)
Inventor
正仁 中本
川口　英一郎
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ユーエムジー・エービーエス株式会社
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Priority claimed from JP2016067942A external-priority patent/JP6145532B1/ja
Priority claimed from JP2016067941A external-priority patent/JP2017179105A/ja
Application filed by ユーエムジー・エービーエス株式会社 filed Critical ユーエムジー・エービーエス株式会社
Publication of WO2017169912A1 publication Critical patent/WO2017169912A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/14—Glass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates

Definitions

  • the present invention relates to a reinforced thermoplastic resin composition and a molded article using the same.
  • This application claims priority based on Japanese Patent Application No. 2016-067941 filed in Japan on March 30, 2016 and Japanese Patent Application No. 2016-067942 filed on March 30, 2016 in Japan. The contents are incorporated herein.
  • Thermoplastic resin composition (ABS resin, polycarbonate resin / ABS resin, polyamide resin) as a housing material for mobile devices (notebook and tablet personal computers, mobile phones including smart phones, digital cameras, digital video cameras, etc.) , Polycarbonate resin / polyester resin, etc.) or those obtained by reinforcing the thermoplastic resin composition with an inorganic filler are widely used.
  • a method for producing the casing a method is generally employed in which the thermoplastic resin composition is molded by injection molding that can be molded to some extent freely.
  • thermoplastic resin composition used for the casing has high rigidity, impact resistance, mechanical strength, flame resistance, and good moldability at the time of molding.
  • excellent adhesive strength with a windshield adhesive is required.
  • thermoplastic resin composition such as ABS resin, polycarbonate resin / ABS resin, polyamide resin, polycarbonate resin / polyester resin and the like not reinforced by the inorganic filler has low rigidity when formed into a molded product, It cannot respond to the demand for thinning.
  • polyamide resin since the polyamide resin has high hygroscopicity, after molding, the molded product is likely to warp, change in dimensions, and deteriorate in appearance over time.
  • a reinforced thermoplastic resin composition obtained by adding an inorganic filler such as glass fiber or carbon fiber to the above-described thermoplastic resin composition has improved rigidity when formed into a molded product.
  • a reinforced thermoplastic resin composition mainly composed of ABS resin, polycarbonate resin / ABS resin, or polycarbonate resin / polyester resin has high rigidity when formed into a molded product, and can reduce the thickness of the casing, but it can be used as a molded product. The impact resistance is insufficient.
  • a reinforced thermoplastic resin composition mainly composed of a polycarbonate resin / polyester resin has poor thermal stability.
  • a reinforced thermoplastic resin composition containing a polyamide resin as a main component is excellent in mechanical strength when formed into a molded product, but cannot solve the above-described problems of warpage, dimensional change, and appearance deterioration. This is a problem caused by moisture absorption of the molded product after molding, and is not a problem that can be solved even if the molding material is dried before molding. Furthermore, the adhesive strength with the windshield adhesive is low.
  • the following are proposed as the reinforced thermoplastic resin composition capable of obtaining a molded article excellent in impact resistance.
  • Reinforced thermoplastic resin composition containing specific amounts of polycarbonate resin, graft copolymer, glass fiber surface-treated with water-soluble polyurethane, glycidyl ether unit-containing polymer, and phosphate ester flame retardant (Patent Document 1).
  • Reinforced thermoplastic resin composition comprising a specific amount
  • the following are proposed as the reinforced thermoplastic resin composition capable of obtaining a molded article having excellent mechanical strength and molding stability.
  • a reinforced thermoplastic resin composition comprising a specific amount of polycarbonate resin, a rubber-containing polymer, and carbon fibers converged with a nylon sizing agent (Patent Document 3).
  • a reinforced thermoplastic resin composition comprising a specific amount of a polycarbonate resin, a polyethylene terephthalate resin subjected to a deactivation treatment of a polycondensation catalyst, and carbon black (Patent Document 4).
  • the reinforced thermoplastic resin composition (1) has insufficient impact resistance when formed into a molded product.
  • the reinforced thermoplastic resin composition of (2) has a problem that mechanical strength (such as bending strength) when formed into a molded product is lowered.
  • the reinforced thermoplastic resin composition (3) had insufficient impact resistance when formed into a molded product.
  • the reinforced thermoplastic resin composition (4) has low rigidity when formed into a molded product.
  • reinforced thermoplastic resin compositions (1) to (4) In addition to the reinforced thermoplastic resin compositions (1) to (4), many reinforced thermoplastic resin compositions to which an epoxy compound is added have been proposed for the purpose of improving the mechanical strength of molded articles. However, a reinforced thermoplastic resin composition having an excellent balance of moldability and the rigidity, impact resistance, mechanical strength, heat resistance, flame resistance, and adhesive strength of windshield adhesives is still available. Not proposed.
  • the present invention is a reinforced thermoplastic resin composition that has good moldability and can increase the rigidity, impact resistance, mechanical strength, heat resistance, flame retardancy, and adhesive strength with an adhesive for a windshield of the obtained molded product. Products, and molded articles thereof.
  • a monomer mixture (Am1) containing an aromatic alkenyl compound and a vinyl cyanide compound is polymerized in the presence of 80 to 100% by mass of the polycarbonate resin (AA) and the rubbery polymer (AG1).
  • Resin main component comprising 0 to 20% by mass of the obtained graft copolymer (AG) (however, the total of the polycarbonate resin (AA) and the graft copolymer (AG) is 100% by mass).
  • thermoplastic resin containing component AC
  • polyethylene terephthalate resin AB
  • inorganic filler D
  • glycidyl ether unit-containing polymer E
  • phosphate ester flame retardant AF
  • a composition comprising: The polyethylene terephthalate resin (AB) is recycled and / or re-pelletized, and the content of the polyethylene terephthalate resin (AB) is 5 to 30 parts by mass with respect to 100 parts by mass of the resin main component (AC).
  • the content of the inorganic filler (D) is 20 to 55% by mass in 100% by mass of the reinforced thermoplastic resin composition
  • the mass average molecular weight of the glycidyl ether unit-containing polymer (E) is 3,800 to 60,000, and the content of the glycidyl ether unit-containing polymer (E) is 100 parts by mass of the resin main component (AC).
  • the phosphate ester flame retardant (AF) has a mass average molecular weight exceeding 326, and the content of the phosphate ester flame retardant (AF) is 3 to 25 mass with respect to 100 mass parts of the resin main component (AC).
  • a reinforced thermoplastic resin composition which is a part.
  • the resin main component (AC) is composed of 80 to 95% by mass of the polycarbonate resin (AA) and 5 to 20% by mass of the graft copolymer (AG). Reinforced thermoplastic resin composition.
  • a monomer mixture (Bm1) containing an aromatic alkenyl compound and a vinyl cyanide compound is polymerized in the presence of 80 to 95% by mass of the polycarbonate resin (BA) and the rubbery polymer (BB1). Resin main component comprising 5 to 20% by mass of the obtained graft copolymer (BB) (however, the total of the polycarbonate resin (BA) and the graft copolymer (BB) is 100% by mass).
  • thermoplastic resin containing component (BC), inorganic filler (D), glycidyl ether unit-containing polymer (E), polyethylene terephthalate resin (BF), and phosphate ester flame retardant (BG) A composition comprising: The rubbery polymer (BB1) is a silicone-acrylic composite rubber, The content of the inorganic filler (D) is 20 to 55% by mass in 100% by mass of the reinforced thermoplastic resin composition B, The mass average molecular weight of the glycidyl ether unit-containing polymer (E) is 3,800 to 60,000, and the content of the glycidyl ether unit-containing polymer (E) is 100 parts by mass of the resin main component (BC).
  • the rubbery polymer (BB1) is a silicone-acrylic composite rubber
  • the content of the inorganic filler (D) is 20 to 55% by mass in 100% by mass of the reinforced thermoplastic resin composition B
  • the polyethylene terephthalate resin (BF) is recycled and / or re-pelletized, and the content of the polyethylene terephthalate resin (BF) is 5 to 30 masses with respect to 100 mass parts of the resin main component (BC).
  • the phosphate ester flame retardant (BG) has a mass average molecular weight exceeding 326, and the content of the phosphate ester flame retardant (BG) is 3 to 25 mass with respect to 100 mass parts of the resin main component (BC).
  • Part of a reinforced thermoplastic resin composition [4] The reinforced thermoplastic resin composition according to any one of [1] to [3], wherein the inorganic filler (D) is carbon fiber.
  • the reinforced thermoplastic resin composition of the present invention has good moldability, and the resulting molded article has the rigidity, impact resistance, mechanical strength, heat resistance, flame resistance, and adhesive strength with an adhesive for windshield. Can be high.
  • the molded article of the present invention has high rigidity, impact resistance, mechanical strength, heat resistance, flame retardancy, and adhesive strength with an adhesive for windshield.
  • (meth) acrylate is a general term for acrylate and methacrylate.
  • the “molded product” is formed by molding the reinforced thermoplastic resin composition of the present invention.
  • the reinforced thermoplastic resin composition of this invention shows "the reinforced thermoplastic resin composition A” and / or “the reinforced thermoplastic resin composition B” demonstrated below, it is limited to these. It is not a thing.
  • the reinforced thermoplastic resin composition A is a superordinate concept of the reinforced thermoplastic resin composition B.
  • the reinforced thermoplastic resin composition A of the present invention comprises a resin main component (AC), a polyethylene terephthalate resin (AB), an inorganic filler (D), a glycidyl ether unit-containing polymer (E), and a phosphate ester type. Flame retardant (AF).
  • the resin main component (AC) is composed of 80 to 100% by mass of the polycarbonate resin (AA) and 0 to 20% by mass of the graft copolymer (AG) (provided that the polycarbonate resin (AA) and the graft copolymer are combined). The total amount with the polymer (AG) is 100% by mass).
  • the graft copolymer (AG) is obtained by polymerizing the monomer mixture (Am1) in the presence of the rubbery polymer (AG1).
  • the reinforced thermoplastic resin composition B of the present invention comprises a resin main component (BC), an inorganic filler (D), a glycidyl ether unit-containing polymer (E), a polyethylene terephthalate resin (BF), and a phosphate ester type. Flame retardant (BG).
  • BC resin main component
  • D inorganic filler
  • E glycidyl ether unit-containing polymer
  • BF polyethylene terephthalate resin
  • BG Flame retardant
  • the resin main component (BC) comprises 80 to 95% by mass of the polycarbonate resin (BA) and 5 to 20% by mass of the graft copolymer (BB) (provided that the polycarbonate resin (BA) and the graft copolymer The total with the polymer (BB) is 100% by mass.)
  • the graft copolymer (BB) is obtained by polymerizing the monomer mixture (Bm1) in the presence of the rubbery polymer (BB1).
  • the reinforced thermoplastic resin composition A of the present invention preferably further contains a flame retardant aid (H).
  • the reinforced thermoplastic resin composition A of the present invention may contain a flame retardant (I) other than the phosphate ester-based flame retardant (AF), as necessary, within a range not impairing the effects of the present invention. Good.
  • the reinforced thermoplastic resin composition A according to the present invention is a resin main component (AC), polyethylene terephthalate resin (AB), inorganic filler (D), glycidyl as long as the effects of the present invention are not impaired.
  • Other components other than the ether unit-containing polymer (E), the phosphate ester flame retardant (AF), the flame retardant aid (H), and the other flame retardant (I) may be contained.
  • each component ((AA) to (I), (AG1), (Am1), etc.) will be described.
  • the reinforced thermoplastic resin composition B of the present invention further contains a flame retardant aid (H).
  • the reinforced thermoplastic resin composition B of the present invention may contain a flame retardant (I) other than the phosphoric ester-based flame retardant (BG) as necessary, as long as the effects of the present invention are not impaired. Good.
  • the reinforced thermoplastic resin composition B of the present invention is, as necessary, a resin main component (BC), an inorganic filler (D), a glycidyl ether unit-containing polymer (E) as long as the effects of the present invention are not impaired. ), Polyethylene terephthalate resin (BF), phosphate ester flame retardant (BG), flame retardant aid (H), and other flame retardant (I) may be included.
  • each component ((BA) to (I), (BB1), (Bm1), etc.) will be described.
  • the polycarbonate resin (AA) and the polycarbonate resin (BA) may be unbranched or branched.
  • Polycarbonate resin (AA) and polycarbonate resin (BA) may be used individually by 1 type, and may use 2 or more types together.
  • commercially available products may be used, or those produced by a known production method may be used.
  • Examples of the method for producing the polycarbonate resin (AA) and the polycarbonate resin (BA) include a method of reacting a dihydroxy compound such as dihydroxydiarylalkane or a polyhydroxy compound with phosgene or a diester of carbonic acid, and a melt polymerization method.
  • Examples of the dihydroxydiarylalkane include those having an alkyl group at the ortho position relative to the hydroxy group.
  • Specific examples of preferred dihydroxydiarylalkanes include 4,4-dihydroxy2,2-diphenylpropane (ie, bisphenol A), tetramethylbisphenol A, bis- (4-hydroxyphenyl) -p-diisopropylbenzene, and the like. .
  • the branched polycarbonate resin (AA) and the polycarbonate resin (BA) are produced, for example, by substituting a part (for example, 0.2 to 2 mol%) of a dihydroxy compound with a polyhydroxy compound.
  • a part for example, 0.2 to 2 mol%) of a dihydroxy compound
  • the polyhydroxy compound include phloroglicinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzene and the like.
  • a polycarbonate resin (AA) or a polycarbonate resin (BA) recycled from a compact disk or the like may be used.
  • the viscosity average molecular weight (Mv) of the polycarbonate resin (AA) or the polycarbonate resin (BA) is preferably 15,000 to 35,000. If the viscosity average molecular weight of the polycarbonate resin (AA) or the polycarbonate resin (BA) is 15,000 or more, the impact resistance of the molded product is further increased. If the viscosity average molecular weight of polycarbonate resin (AA) or polycarbonate resin (BA) is 35,000 or less, the moldability of a reinforced thermoplastic resin composition will become still higher. The viscosity average molecular weight of the polycarbonate resin (AA) and the polycarbonate resin (BA) is 17,000 because the balance of mechanical strength, impact resistance, and fluidity of the reinforced thermoplastic resin composition is particularly excellent.
  • the viscosity average molecular weight of the polycarbonate resin (AA) or the polycarbonate resin (BA) can be determined by, for example, a solution viscosity method. When using a commercially available polycarbonate resin (AA) or polycarbonate resin (BA), catalog values may be used.
  • examples of the rubbery polymer (AG1) include butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, isoprene rubber, chloroprene rubber, butyl rubber, ethylene-propylene rubber, acrylic rubber, ethylene-propylene-nonconjugated diene rubber, epichlorohydrin.
  • examples thereof include rubber, diene-acrylic composite rubber, and silicone-acrylic composite rubber.
  • the diene rubber component of the diene-acrylic composite rubber contains 50% by mass or more of butadiene units.
  • examples of the diene rubber component include butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, and the like.
  • the acrylic rubber component of the diene-acrylic composite rubber is obtained by polymerizing an alkyl (meth) acrylate (f) and a polyfunctional monomer (g).
  • the rubber polymer (BB1) is a silicone-acrylic composite rubber. Since the rubber polymer (BB1) is a silicone-acrylic composite rubber, the flame retardancy and high temperature of the molded product obtained from the reinforced thermoplastic resin composition B are higher than when other rubber polymers are used. Increased durability under humidity.
  • the silicone rubber component of the silicone-acrylic composite rubber is mainly composed of polyorganosiloxane, and among them, polyorganosiloxane containing a vinyl polymerizable functional group is preferable.
  • the acrylic rubber component in the silicone-acrylic composite rubber is obtained by polymerizing an alkyl (meth) acrylate (f) and a polyfunctional monomer (g).
  • alkyl (meth) acrylate (f) examples include alkyl acrylate (methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, etc.), alkyl methacrylate (hexyl methacrylate, 2-ethylhexyl methacrylate, n-lauryl methacrylate, etc.).
  • Alkyl (meth) acrylate (f) may be used individually by 1 type, and may use 2 or more types together.
  • polyfunctional monomer (g) examples include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, And triallyl isocyanurate.
  • a polyfunctional monomer (g) may be used individually by 1 type, and may use 2 or more types together.
  • the diene-acrylic composite rubber composite structure includes a core-shell structure in which the periphery of the diene component is covered with an acrylic rubber component; a core-shell structure in which the periphery of the acrylic rubber component is covered with a diene component; a diene component and an acrylic rubber component Examples of structures that are entangled with each other; a copolymer structure in which diene monomer units and alkyl (meth) acrylate monomer units are randomly arranged.
  • a core-shell structure in which the periphery of the core layer of the silicone rubber component is covered with an acrylic rubber component; a core-shell structure in which the periphery of the core layer of the acrylic rubber component is covered with a silicone rubber component; A structure in which the silicone rubber component and the acrylic rubber component are intertwined with each other; a polyorganosiloxane segment and a polyalkyl (meth) acrylate segment are linearly and sterically bonded to each other to form a network rubber structure And the like.
  • the rubber polymer (AG1) is prepared, for example, by emulsion polymerization of a monomer that forms the rubber polymer (AG1) in the presence of a radical polymerization initiator. According to the preparation method by the emulsion polymerization method, the particle diameter of the rubber-like polymer (AG1) can be easily controlled.
  • the average particle diameter of the rubber polymer (AG1) is preferably 0.1 to 0.6 ⁇ m from the viewpoint that the impact resistance of the molded product can be further increased.
  • the rubber polymer (BB1) is prepared, for example, by emulsion polymerization of a monomer that forms the rubber polymer (BB1) in the presence of a radical polymerization initiator. According to the preparation method by the emulsion polymerization method, it is easy to control the particle diameter of the rubber-like polymer (BB1).
  • the average particle size of the silicone-acrylic composite rubbery polymer (BB1) is preferably 0.1 to 0.6 ⁇ m because the impact resistance of the reinforced thermoplastic resin composition B can be further increased.
  • the monomer mixture (Am1) contains an aromatic alkenyl compound (hereinafter also referred to as monomer (a)) and a vinyl cyanide compound (hereinafter also referred to as monomer (b)). As needed, you may further contain the other monomer (henceforth the monomer (c)) copolymerizable with the monomer (a) and the monomer (b).
  • the monomer mixture (Bm1) contains an aromatic alkenyl compound (hereinafter also referred to as monomer (a)) and a vinyl cyanide compound (hereinafter also referred to as monomer (b)). As needed, you may further contain the other monomer (henceforth the monomer (c)) copolymerizable with the monomer (a) and the monomer (b).
  • Examples of the monomer (a) include styrene, ⁇ -methylstyrene, vinyltoluene and the like, and styrene is preferable.
  • Examples of the monomer (b) include acrylonitrile and methacrylonitrile, and acrylonitrile is preferable.
  • the proportion of the monomer (a) is 50 to 90% by mass
  • the proportion of the monomer (b) is 10 to 50% by mass
  • the proportion of the other monomer (c) is 0 to 40% by mass. (However, the total of the monomers (a) to (c) is 100% by mass).
  • the graft copolymer (AG) is obtained by polymerizing the monomer mixture (Am1) in the presence of the rubbery polymer (AG1). That is, the graft copolymer (AG) is obtained by grafting the molecular chain (AG2) formed from the monomer mixture (Am1) to the rubbery polymer (AG1).
  • a graft copolymer (AG) may be used individually by 1 type, and may use 2 or more types together.
  • the graft copolymer (BB) is obtained by polymerizing the monomer mixture (Bm1) in the presence of the rubbery polymer (BB1). That is, the graft copolymer (BB) is obtained by grafting the polymer (BB2) formed from the monomer mixture (Bm1) to the rubbery polymer (BB1).
  • a graft copolymer (BB) may be used individually by 1 type, and may use 2 or more types together.
  • the content of the rubber polymer (AG1) is preferably 0.5 to 3.5% by mass in the resin main component (AC) (100% by mass).
  • the content of the rubbery polymer (AG1) is 0.5% by mass or more, the impact resistance of the molded product can be further increased.
  • the content of the rubbery polymer (AG1) is 3.5% by mass or less, the moldability of the reinforced thermoplastic resin composition A is further improved, and the appearance of the molded product is improved.
  • the content of the rubber polymer (BB1) is preferably 5 to 25% by mass in the resin main component (BC) (100% by mass).
  • the content of the rubbery polymer (BB1) is 5% by mass or more, the impact resistance of the molded product can be further increased.
  • content of rubber-like polymer (BB1) is 25 mass% or less, the moldability of the reinforced thermoplastic resin composition B will become higher, and the external appearance of a molded article will become favorable.
  • the molecular chain (AG2) has a monomer (a) unit and a monomer (b) unit as essential components, and another monomer (c) unit copolymerizable therewith as an optional component.
  • the preferred range of the proportion (mass%) of each monomer unit in the molecular chain (AG2) is the same as the preferred range of the proportion of each monomer in the monomer mixture (Am1).
  • the polymer (BB2) has a monomer (a) unit and a monomer (b) unit as essential components, and another monomer (c) unit copolymerizable therewith as an optional component.
  • the preferred range of the proportion (mass%) of each monomer unit in the polymer (BB2) is the same as the preferred range of the proportion of each monomer in the monomer mixture (Bm1).
  • the graft copolymer (AG) and the graft copolymer (BB) contain 1 to 30% by mass of an acetone-soluble component, and a 0.2 g / dl N, N-dimethylformamide solution containing an acetone-soluble component.
  • the reduced viscosity measured at 25 ° C. is preferably 0.3 to 0.7 dl / g. If the acetone-soluble content is 30% by mass or less (acetone-insoluble content is 70% by mass or more), the surface appearance of the molded product is improved, and the moldability of the reinforced thermoplastic resin composition is further improved.
  • the tear strength of the molded product is improved.
  • the reduced viscosity of the acetone-soluble component is 0.3 dl / g or more
  • the tear strength of the molded product is improved.
  • the reduced viscosity of the acetone-soluble component is 0.7 dl / g or less
  • the moldability of the reinforced thermoplastic resin composition is further improved, and the surface appearance of the obtained molded product is improved.
  • the method for measuring acetone-soluble matter is as follows. 2.5 g of the graft copolymer is immersed in 90 ml of acetone, heated at 65 ° C. for 3 hours, and then centrifuged at 1500 rpm for 30 minutes using a centrifuge. Thereafter, the supernatant is removed, and the residue is dried in a vacuum dryer at 65 ° C. for 12 hours, and the dried sample is precisely weighed. From the mass difference ([2.5 g of graft copolymer] ⁇ [mass of sample after drying]), the proportion (%) of acetone-soluble matter in the graft copolymer can be determined. The reduced viscosity of the acetone-soluble matter is measured at 25 ° C. using a 0.2 g / dl N, N-dimethylformamide solution.
  • the acetone-soluble component is a polymer similar to the molecular chain (AG2), and is a polymer that is not grafted to the rubbery polymer (AG1). Acetone-soluble components are often generated simultaneously when the molecular chain (AG2) is grafted to the rubbery polymer (AG1). Therefore, the graft copolymer (AG) contains an acetone-soluble component and an acetone-insoluble component.
  • AG it is difficult to specify how the rubber polymer (AG1) and the monomer mixture (Am1) are polymerized. That is, there are circumstances (impossible / impractical circumstances) where the graft copolymer (AG) cannot be directly identified by its structure or properties, or is almost impractical.
  • the acetone-soluble component is a polymer similar to the polymer (BB2), and is a polymer that is not grafted to the rubbery polymer (BB1). Acetone-soluble components are often generated simultaneously with the grafting of the polymer (BB2) to the rubbery polymer (BB1). Therefore, the graft copolymer (BB) includes an acetone-soluble component and an acetone-insoluble component.
  • the rubbery polymer (BG1) and the monomer mixture (Bm1) are polymerized. That is, there are circumstances (impossible / impractical circumstances) that the graft copolymer (BB) cannot be directly specified by its structure or characteristics, or is almost impractical.
  • the graft copolymer (AG) can be obtained by graft polymerization of the monomer mixture (Am1) in the presence of the rubbery polymer (AG1).
  • As the graft polymerization method an emulsion polymerization method is preferred.
  • various chain transfer agents may be added in order to adjust the molecular weight of the graft copolymer (AG), the graft ratio, and the reduced viscosity of the acetone-soluble component.
  • the graft copolymer (BB) is obtained by graft polymerization of the monomer mixture (Bm1) in the presence of the rubbery polymer (BB1).
  • the graft polymerization method is not particularly limited, but an emulsion polymerization method is preferable.
  • various chain transfer agents may be added in order to adjust the molecular weight of the graft copolymer (BB), the graft ratio, and the reduced viscosity of the acetone-soluble component.
  • the resin main component (AC) is composed of 80 to 100% by mass of the polycarbonate resin (AA) and 0 to 20% by mass of the graft copolymer (AG) (provided that the polycarbonate resin (AA) and the graft copolymer are combined).
  • the total amount with respect to the polymer (AG) is 100% by mass), 80 to 95% by mass of the polycarbonate resin (AA), and 5 to 20% by mass of the graft copolymer (AG). More preferably, it is 90 to 95% by mass of the polycarbonate resin (AA) and 5 to 10% by mass of the graft copolymer (AG).
  • the ratio of the polycarbonate resin (AA) is within the above range, the impact resistance of the reinforced thermoplastic resin composition A is good.
  • the ratio of the polycarbonate resin (AA) is equal to or higher than the lower limit value of the above range, the flame retardancy, mechanical strength, and rigidity of the molded product increase, and if the ratio is equal to or lower than the upper limit value, the reinforced thermoplastic resin composition A The moldability is further improved.
  • the ratio of the graft copolymer (AG) is within the above range, the moldability of the reinforced thermoplastic resin composition A is good.
  • the proportion of the graft copolymer (AG) is not more than the upper limit of the above range, the flame retardancy, mechanical strength and rigidity of the molded product will be high, and if it is not less than the lower limit, the reinforced thermoplastic resin composition The formability of A is further improved.
  • the resin main component (BC) is composed of 80 to 95% by mass of the polycarbonate resin (BA) and 5 to 20% by mass of the graft copolymer (BB) (provided that the polycarbonate resin (BA) and the graft copolymer)
  • the total amount of the polymer (BB) is 100% by mass), 90 to 95% by mass of the polycarbonate resin (BA), and 5 to 10% by mass of the graft copolymer (BB). If the proportion of the polycarbonate resin (BA) is 80% by mass or more, the impact resistance, flame retardancy, mechanical strength, and rigidity of the molded product are increased. If the proportion is 95% by mass or less, the reinforced thermoplastic resin composition The moldability of B is good.
  • the proportion of the graft copolymer (BB) is 5% by mass or more, the moldability of the reinforced thermoplastic resin composition B is good, and if it is 20% by mass or less, the impact resistance and flame retardancy of the molded product. Property, mechanical strength and rigidity are good.
  • PET resin (AB) and BF are recycled and / or re-pelletized. Specific examples include recycled PET resin, re-pelleted PET resin, recycled and re-pelleted PET resin, and the like.
  • the recycled PET resin is obtained by collecting and recycling a PET resin product obtained through the molding process of the PET resin.
  • Typical PET resin products include used PET bottles, food trays, etc., but are not limited to them, and also covers off-grade PET resin products and waste materials generated in the molding process. be able to. Therefore, resources can be effectively utilized by using recycled and / or re-pelleted polyethylene terephthalate resin (AB) or polyethylene terephthalate resin (BF).
  • AB polyethylene terephthalate resin
  • BF polyethylene terephthalate resin
  • the shape of the recycled PET resin is generally flaky, and the average particle size is preferably 2 to 5 mm. Moreover, you may use what was once pelletized (repellet) for the foreign material removal. Examples of the re-pelleted PET resin include those obtained by pelletizing the recycled PET resin and those obtained by pelletizing a commercially available pellet-shaped product (virgin material). Pelletization can be performed using an extruder or the like. PET resin (AB) and polyethylene terephthalate resin (BF) may be used individually by 1 type, and may use 2 or more types together.
  • Inorganic fillers (D) include glass fibers, carbon fibers and other inorganic fibers, inorganic fibers coated with metal, wollastonite, talc, mica, glass flakes, glass beads, potassium titanate, calcium carbonate, magnesium carbonate, carbon Examples thereof include inorganic substances such as black and ketjen black, metals and alloys such as iron, copper, zinc and aluminum, and fibers and powders of oxides thereof. Of these, glass fibers and carbon fibers are preferably used because high rigidity can be obtained with a small amount of blending.
  • inorganic fibers, inorganic fibers coated with metal, inorganic materials, metals and alloys, and oxide fibers, powders, and the like have their surfaces coated with known coupling agents (eg, silane coupling agents, titanates). System coupling agents and the like) and other surface treatment agents.
  • the glass fiber and the carbon fiber may be coated or bundled with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or polyamide, or a thermosetting resin such as a polyurethane resin or an epoxy resin.
  • the ratio of the major axis to the minor axis (major axis / minor axis) in the fiber cross section of glass fiber and carbon fiber is preferably 2 to 6, and more preferably 2 to 4. If the major axis / minor axis is 2 or more, good impact properties and strength can be obtained. If the major axis / minor axis is 6 or less, good formability (extrusion workability) can be obtained.
  • the major axis / minor axis in the fiber cross section is obtained, for example, by observing the fiber cross section at eight locations using an electron microscope and averaging the major axis / minor axis at eight locations. When using a commercial product, a catalog value may be used.
  • the glass fiber or carbon fiber may be either a long fiber or a short fiber.
  • As glass fiber or carbon fiber short fiber with little anisotropy is preferable, and chopped fiber is more preferable.
  • An inorganic filler (D) may be used individually by 1 type, and may use 2 or more types together.
  • the glycidyl ether unit-containing polymer (E) is a polymer having a glycidyl ether unit in the molecule.
  • the glycidyl ether unit-containing polymer (E) preferably does not have a halogen atom (bromine or the like).
  • the glycidyl ether unit-containing polymer (E) is preferably not a block type polymer.
  • the glycidyl ether type epoxy resin obtained by reaction of the compound which has a hydroxyl group, and epichlorohydrin is mentioned, for example.
  • the glycidyl ether type epoxy resin include bisphenol type epoxy resins; novolac type epoxy resins; polyglycidyl ethers of aliphatic polyhydric alcohols; biphenyl type epoxy resins and the like, which are represented by the following formula (1). And the like (for example, epoxy group-containing phenoxy resin) having a molecular chain having such a unit in the molecule.
  • n is an integer of 1 or more.
  • Examples of the bisphenol type epoxy resin include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, an epoxy resin having a structure of bisphenol A and bisphenol F, and the like.
  • Examples of novolac type epoxy resins include phenol novolac type epoxy resins and cresol novolac type epoxy resins.
  • polyglycidyl ethers of aliphatic polyhydric alcohols include alkylene glycol diglycidyl ether (for example, ethylene glycol diglycidyl ether), polyoxyalkylene glycol diglycidyl ether (for example, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether). , Dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc.) and glycerin triglycidyl ether.
  • alkylene glycol diglycidyl ether for example, ethylene glycol diglycidyl ether
  • polyoxyalkylene glycol diglycidyl ether for example, diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether.
  • bisphenol A type epoxy resin bisphenol F type epoxy resin, epoxy resin having a structure of bisphenol A and bisphenol F, and phenol are used because the mechanical strength of the molded product is further increased.
  • the glycidyl ether unit-containing polymer (E) may be liquid at normal temperature (20 ° C.), may be semi-solid, or may be solid. In consideration of workability during mixing and kneading, a solid material is preferable.
  • a glycidyl ether unit containing polymer (E) may be used individually by 1 type, and may use 2 or more types together.
  • the mass average molecular weight of the glycidyl ether unit-containing polymer (E) is 3,800 to 60,000, preferably 5,500 to 50,000.
  • the mass average molecular weight of the glycidyl ether unit-containing polymer (E) is 3,800 or more, the impact resistance of the molded article is increased.
  • the mass average molecular weight of the glycidyl ether unit-containing polymer (E) is 60,000 or less, the moldability of the reinforced thermoplastic resin composition and the flame retardancy of the molded product are improved.
  • the mass average molecular weight of the glycidyl ether unit-containing polymer (E) can be determined by mass spectrometry. When using a commercially available glycidyl ether unit-containing polymer (E), catalog values may be used.
  • glycidyl ether unit-containing polymer (E) a commercially available product may be used, or a polymer produced by a known production method may be used.
  • examples of commercially available glycidyl ether unit-containing polymers (E) include, for example, jER (registered trademark) series manufactured by Mitsubishi Chemical Corporation, Epototo (registered trademark) series, phenototo (registered trademark) series manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.
  • Examples include AER (registered trademark) series manufactured by Asahi Kasei E-Materials, and Epicron (registered trademark) series manufactured by DIC.
  • AF phosphoric acid ester system flame retardant
  • BG phosphate ester flame retardant
  • R 1 , R 2 , R 3 and R 4 are each independently a hydrogen atom or a monovalent organic group, and all of R 1 , R 2 , R 3 and R 4 are simultaneously hydrogen atoms.
  • A is a (q + 1) -valent organic group, p is 0 or 1, q is an integer of 1 or more, and r is an integer of 0 or more.
  • Examples of the monovalent organic group include an optionally substituted alkyl group (for example, a methyl group, an ethyl group, a butyl group, and an octyl group), a cycloalkyl group (for example, a cyclohexyl group), and an aryl group (for example, , Phenyl group, alkyl group-substituted phenyl group, etc.).
  • Examples of the substituent include an alkoxy group, an alkylthio group, an aryloxy group, and an arylthio group.
  • the substituted organic group is a group in which two or more of these substituents are combined (for example, an arylalkoxyalkyl group), or a combination of these substituents bonded by an oxygen atom, a nitrogen atom, a sulfur atom, or the like It may be a group (for example, an arylsulfonylaryl group).
  • Examples of the (q + 1) -valent organic group include a functional group having a structure in which q hydrogen atoms bonded to carbon atoms are removed from the monovalent organic group. The position of the carbon atom from which the hydrogen atom is removed is arbitrary.
  • Specific examples of the (q + 1) -valent organic group include an alkylene group and a (substituted) phenylene group.
  • phosphate ester flame retardants include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate.
  • Trixyl phosphate cresyl diphenyl phosphate, xyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl-2-ethyl cresyl phosphate, tris (isopropylphenyl) phosphate, resorcinyl diphenyl phosphate, polyphosphate and the like.
  • Polyphosphates include bisphenol A bisphosphate, hydroquinone bisphosphate, resorcin bisphosphate, trioxybenzene triphosphate, bisphenol A bis (dicresyl phosphate), bisphenol A bis (diphenyl phosphate), phenylene bis (diphenyl phosphate), phenylene bis (Ditolyl phosphate), phenylenebis (dixyl phosphate), and the like.
  • Polyphosphate is obtained, for example, by dehydration condensation of various diols such as polynuclear phenols (for example, bisphenol A) and orthophosphoric acid.
  • diol examples include hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxybiphenyl, p, p′-dihydroxydiphenylsulfone, dihydroxynaphthalene and the like.
  • phosphoric acid ester flame retardants AF
  • BG phosphoric acid ester flame retardants
  • triphenyl phosphate bisphenol A bis (diphenyl phosphate), phenylene bis (diphenyl phosphate), phenylene bis (dixyl phosphate)
  • AF phosphoric acid ester flame retardants
  • BG phosphoric acid ester flame retardants
  • triphenyl phosphate bisphenol A bis (diphenyl phosphate), phenylene bis (diphenyl phosphate), phenylene bis (dixyl phosphate)
  • the mass average molecular weight of the phosphate ester flame retardant (AF) or the phosphate ester flame retardant (BG) is preferably more than 326, more preferably 550 or more. If a phosphoric ester-based flame retardant (AF) or a phosphoric ester-based flame retardant (BG) having a mass average molecular weight of 326 or more, particularly exceeding 326, is used, the moldability of the reinforced thermoplastic resin composition becomes better and the appearance is improved. An excellent molded product can be obtained.
  • the mass average molecular weight of the phosphate ester flame retardant (AF) or the phosphate ester flame retardant (BG) is preferably 692 or less, more preferably 690 or less, and particularly preferably 686 or less, from the viewpoint of flame retardancy of the molded product. .
  • the mass average molecular weight of the phosphate ester flame retardant (AF) and the phosphate ester flame retardant (BG) can be determined by mass spectrometry. When using commercially available phosphate ester flame retardant (AF) or phosphate ester flame retardant (BG), catalog values may be used.
  • phosphate ester flame retardant (AF) and the phosphate ester flame retardant (BG) commercially available products may be used, or those produced by a known production method may be used.
  • Commercially available products of phosphate ester flame retardant (AF) and phosphate ester flame retardant (BG) include, for example, FP series manufactured by ADEKA, Clontex (registered trademark) series manufactured by Ajinomoto Fine Techno Co., Chemtura Japan The Reofos (registered trademark) series manufactured by the company, the CR series manufactured by Daihachi Chemical Co., Ltd., the PX series, and the like.
  • the flame retardant aid (H) is a component that prevents drip during combustion of the reinforced thermoplastic resin composition.
  • Examples of the flame retardant aid (H) include polytetrafluoroethylene, a copolymer having a tetrafluoroethylene unit, and a silicone-based polymer.
  • the phosphate ester flame retardant (AF) Non-halogen flame retardants other than phosphate ester flame retardants (BG) are preferred.
  • the non-halogen flame retardant include phosphazene compounds, phosphorus-containing polyesters, inorganic flame retardants (red phosphorus, aluminum hydroxide, etc.) and the like.
  • red phosphorus flame retardant those stabilized by being coated with a thermosetting resin or those stabilized by being coated with a thermosetting resin and a metal hydroxide are used. Since red phosphorus flame retardants are ignitable by themselves, they are mixed in advance with resin main component (AC), at least part of resin main component (BC), polycarbonate resin (AA), or polycarbonate resin (BA). May be converted into a master batch.
  • ⁇ Other ingredients examples include other modifiers, mold release agents, stabilizers against light or heat, antistatic agents, dyes, and pigments.
  • the content of the PET resin (AB) is preferably 5 to 30 parts by mass and more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the resin main component (AC).
  • the impact resistance is excellent.
  • the content of the PET resin (BF) is preferably 5 to 30 parts by mass and more preferably 10 to 20 parts by mass with respect to 100 parts by mass of the resin main component (BC). If the content of the PET resin (BF) is 5 parts by mass or more and 30 parts by mass or less, the impact resistance is excellent.
  • the content of the inorganic filler (D) is preferably 20 to 55% by mass and more preferably 30 to 50% by mass in 100% by mass of the reinforced thermoplastic resin composition. If content of an inorganic filler (D) is 20 mass% or more, the rigidity etc. of a molded article will become high. If content of an inorganic filler (D) is 55 mass% or less, the moldability of a reinforced thermoplastic resin composition will become favorable.
  • the content of the glycidyl ether unit-containing polymer (E) is preferably 3 to 10 parts by mass and more preferably 6 to 8 parts by mass with respect to 100 parts by mass of the resin main component (AC). If content of a glycidyl ether unit containing polymer (E) is 3 mass parts or more, the impact resistance of a molded article will become high. If content of a glycidyl ether unit containing polymer (E) is 10 mass parts or less, the moldability of the reinforced thermoplastic resin composition A and the flame retardance of a molded article will become favorable.
  • the content of the glycidyl ether unit-containing polymer (E) is preferably 3 to 10 parts by mass and more preferably 6 to 8 parts by mass with respect to 100 parts by mass of the resin main component (BC). If content of a glycidyl ether unit containing polymer (E) is 3 mass parts or more, the impact resistance of a molded article will become high. If content of a glycidyl ether unit containing polymer (E) is 10 mass parts or less, the moldability of the reinforced thermoplastic resin composition B and the flame retardance of a molded article will become favorable.
  • the content of the phosphate ester flame retardant (AF) is preferably 3 to 25 parts by mass, and more preferably 5 to 23 parts by mass with respect to 100 parts by mass of the resin main component (AC).
  • the content of the phosphate ester flame retardant (AF) is 25 parts by mass or less, the impact resistance and heat resistance of the molded article are increased. If the content of the phosphate ester flame retardant (AF) is 3 parts by mass or more, the flame retardancy and moldability of the molded product are further improved.
  • the content of the phosphate ester flame retardant (BG) is preferably 3 to 25 parts by mass, more preferably 5 to 23 parts by mass with respect to 100 parts by mass of the resin main component (BC).
  • the content of the phosphoric ester-based flame retardant (BG) is 25 parts by mass or less, the impact resistance and heat resistance of the molded product are increased.
  • the content of the phosphate ester flame retardant (BG) is 3 parts by mass or more, the flame retardancy and moldability of the molded product are further improved.
  • the content of the flame retardant aid (H) is determined by molding.
  • the amount is preferably 1 part by mass or less with respect to 100 parts by mass of the resin main component (AC).
  • a minimum is not specifically limited, 0.1 mass part or more is preferable with respect to 100 mass parts of resin main components (AC) at the point by which the effect by a flame-retardant adjuvant (H) is easy to be acquired.
  • the reinforced thermoplastic resin composition B contains a polytetrafluoroethylene or a copolymer having a tetrafluoroethylene unit as the flame retardant aid (H), the content of the flame retardant aid (H) is molded.
  • 1 part by mass or less is preferable with respect to 100 parts by mass of the resin main component (BC).
  • a minimum is not specifically limited, 0.1 mass part or more is preferable with respect to 100 mass parts of resin main components (BC) at the point by which the effect by a flame-retardant adjuvant (H) is easy to be acquired.
  • the reinforced thermoplastic resin composition A of the present invention comprises a resin main component (AC) (a polycarbonate resin (AA) and, if necessary, a graft polymer (AG)), and a recycled and / or repelleted PET resin (AB).
  • each component can be obtained by mixing using a mixing device (for example, a Henschel mixer, a tumbler mixer, a nauter mixer, etc.).
  • kneading may be performed using a kneading apparatus (for example, a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or the like).
  • the reinforced thermoplastic resin composition B of the present invention comprises a polycarbonate resin (BA), a graft polymer (BB), an inorganic filler (D), a glycidyl ether unit-containing polymer (E), and a PET resin (BF). ), A phosphate ester flame retardant (BG), and, if necessary, a flame retardant aid (H), another flame retardant (I), and other components.
  • each component can be obtained by mixing using a mixing device (for example, a Henschel mixer, a tumbler mixer, a nauter mixer, etc.).
  • kneading may be performed using a kneading apparatus (for example, a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or the like).
  • the polymer containing the glycidyl ether unit having a mass average molecular weight (E) and the phosphate ester flame retardant (AF) are contained in a specific ratio, the moldability is good, and the rigidity of the obtained molded product is Impact resistance, mechanical strength, heat resistance, flame resistance, and adhesive strength with windshield adhesive can be increased.
  • the moldability is good, appearance defects such as silver streaks are unlikely to occur in the obtained molded product.
  • a resin main component (BC) comprising a specific amount of a polycarbonate resin (BA) and a graft copolymer (BB), an inorganic filler (D),
  • BC resin main component
  • BA polycarbonate resin
  • BB graft copolymer
  • D inorganic filler
  • E glycidyl ether unit-containing polymer
  • BF recycled and / or repelleted PET resin
  • BG phosphate ester flame retardant
  • the molded article of the present invention is obtained by molding the reinforced thermoplastic resin composition of the present invention.
  • the molding process of the reinforced thermoplastic resin composition include, for example, an injection molding method (including insert molding of films, glass plates, etc.), an injection compression molding method, an extrusion method, a blow molding method, a vacuum molding method, and a pneumatic molding method. Method, calender molding method, inflation molding method and the like.
  • the injection molding method and the injection compression molding method are preferable because they are excellent in mass productivity and can obtain a molded product with high dimensional accuracy.
  • the reinforced thermoplastic resin composition of the present invention since the reinforced thermoplastic resin composition of the present invention is used, rigidity, impact resistance, mechanical strength, heat resistance, flame retardancy, adhesion with an adhesive for windshield High strength. Also, the appearance is good.
  • the molded article of the present invention includes, for example, a personal computer (including notebook type and tablet type), a projector (including a liquid crystal projector), a television, a printer, a facsimile, a copying machine, an audio device, a game machine, a camera (video). Cameras, digital cameras, etc.), video equipment (videos, etc.), musical instruments, mobile devices (electronic notebooks, personal digital assistants (PDAs), etc.), lighting equipment, communication equipment (phones (including mobile phones, smartphones)) Etc.), fishing gear, playground equipment (pachinko items, etc.), vehicle products, furniture products, sanitary products, building material products, etc.
  • the present invention is particularly suitable for housings of mobile devices (notebook and tablet personal computers, portable devices including smartphones, etc.) because they are particularly effective.
  • Parts and % described below mean “parts by mass” and “% by mass”, respectively, unless otherwise specified.
  • the methods used for various measurements and evaluations and the components used are as follows.
  • Charpy impact strength was measured in accordance with ISO 179-1: 2013 edition.
  • Formability A liquid crystal display cover (thickness 1 mm) of an A4 size notebook personal computer was molded. Formability was evaluated by the presence or absence of short shots (unfilled portions) during molding and the presence or absence of sink marks, silver streaks, or gas burns. A: There was no unfilling, sink, or gas burn. B: Sink was seen in part. C: Gas filling or silver streak was observed.
  • a reinforced thermoplastic resin composition A is molded by an injection molding method to produce a test piece (width 12.7 mm, length 127 mm, thickness 1.8 mm), which complies with UL94 and is flame retardant as follows. Evaluated. A burner flame was applied to the lower end of the vertically supported test piece for 10 seconds, and then the burner flame was separated from the test piece. After the flame disappeared, the burner flame was applied again and the same operation was performed. Is it equivalent to V94 in UL94 depending on the flammable combustion duration after the end of the first flame contact, the sum of the second flammable combustion duration and the flameless combustion duration, and the presence or absence of combustion fallen objects? The flame retardance was evaluated based on the following evaluation criteria.
  • V-1 the standard of V-1 is “the first flammable combustion duration is over 10 seconds within 30 seconds, and the total of the second flammable combustion duration and flameless combustion duration is over 30 seconds and within 60 seconds. There is no burning fallen object. " A: It had flame retardancy of V-1 level. B: V-1 level flame retardancy was not exhibited.
  • a reinforced thermoplastic resin composition B is molded by an injection molding method to produce a test piece (width 12.7 mm, length 127 mm, thickness 1.6 mm), which complies with UL94 and is flame retardant as follows. Evaluated. A burner flame was applied to the lower end of the vertically supported test piece for 10 seconds, and then the burner flame was separated from the test piece. After the flame disappeared, the burner flame was applied again and the same operation was performed. Is it equivalent to V94 in UL94 depending on the flammable combustion duration after the end of the first flame contact, the sum of the second flammable combustion duration and the flameless combustion duration, and the presence or absence of combustion fallen objects? The flame retardance was evaluated based on the following evaluation criteria.
  • V-1 the standard of V-1 is “the first flammable combustion duration is over 10 seconds within 30 seconds, and the total of the second flammable combustion duration and flameless combustion duration is over 30 seconds and within 60 seconds. There is no burning fallen object. " A: It had flame retardancy of V-1 level. B: V-1 level flame retardancy was not exhibited.
  • a reinforced thermoplastic resin composition is molded by an injection molding method to produce a test piece (width 12.7 mm, length 127 mm, thickness 2.0 mm), and an adhesive with an adhesion area of 169 mm 2 (length 13 mm ⁇ width 13 mm). And the adhesive strength with the adhesive was evaluated by the maximum point test force (N) when pulled at a distance of 178 mm and a speed of 5 mm / min.
  • N maximum point test force
  • the obtained enlarged butadiene rubber polymer (AG1-1) latex was charged into a reactor, 100 parts distilled water, 4 parts wood rosin emulsifier, demole N (manufactured by Kao Corporation, naphthalenesulfonic acid formalin condensate) 0.4 Part, 0.04 part of sodium hydroxide and 0.7 part of dextrose.
  • the mixture was heated with stirring, and at an internal temperature of 60 ° C., 0.1 part of ferrous sulfate, 0.4 part of sodium pyrophosphate and 0.06 part of sodium dithionite were added, and then a mixture containing the following components: Was continuously added dropwise over 90 minutes, and then cooled for 1 hour to obtain a graft copolymer (AG-1) latex. 30 parts acrylonitrile. 70 parts of styrene. Cumene hydroperoxide 0.4 parts. 1 part tert-dodecyl mercaptan.
  • the graft copolymer (AG-1) latex was coagulated with dilute sulfuric acid, washed, filtered and dried to obtain a dry powder of the graft copolymer (AG-1).
  • the acetone soluble content of the graft copolymer (AG-1) was 27%.
  • the reduced viscosity of the acetone soluble component was 0.3 dl / g.
  • the polymerization rate was 99%.
  • a graft copolymer (AG-3) using a polybutadiene / polybutylacrylate composite rubber as a rubbery polymer (AG1-3) was obtained by the following method.
  • a copolymer latex having an average particle size of 0.10 ⁇ m consisting of 82% n-butyl acrylate units and 18% methacrylic acid units on a polybutadiene latex (solid content 20 parts) having a solid content concentration of 35% and an average particle size of 0.08 ⁇ m. 0.4 parts as solids) was added with stirring. Stirring was continued for 30 minutes to obtain an enlarged diene rubber latex having an average particle size of 0.36 ⁇ m.
  • the graft copolymer (AG-3) latex was put into a coagulation tank charged with a 0.5% aqueous solution of sulfuric acid (90 ° C.) in an amount three times that of the total latex with stirring, and coagulated. After all the latex was added, the temperature in the coagulation tank was raised to 93 ° C. and left as it was for 5 minutes. After cooling, the solution was removed by a centrifuge, washed, and dried to obtain a dry powder of the graft copolymer (AG-3). The acetone soluble content of the graft copolymer (AG-3) was 20%. Moreover, the reduced viscosity of the acetone soluble part was 0.7 dl / g.
  • PET resin (AB) As recycled PET resin (AB-1), PET-NPR manufactured by Yamaichi Co., Ltd. was used. As the re-pelleted PET resin (AB-2), GM502S manufactured by Mitsubishi Chemical Corporation was re-pelleted at 260 ° C. with a twin screw extruder. GM502S manufactured by Mitsubishi Chemical Corporation was used as a PET resin (AB-3) that was neither recycled nor repellet.
  • the obtained enlarged butadiene rubber polymer (BB1-1) latex was charged into a reactor, 100 parts distilled water, 4 parts wood rosin emulsifier, demole N (manufactured by Kao Corporation, naphthalenesulfonic acid formalin condensate) 0.4 Part, 0.04 part of sodium hydroxide and 0.7 part of dextrose.
  • a mixture containing the following components was heated with stirring, and at an internal temperature of 60 ° C., 0.1 part of ferrous sulfate, 0.4 part of sodium pyrophosphate and 0.06 part of sodium dithionite were added, and then a mixture containing the following components: Was continuously added dropwise over 90 minutes, and then cooled by holding for 1 hour to obtain a graft copolymer (BB-1) latex. 30 parts acrylonitrile. 70 parts of styrene. Cumene hydroperoxide 0.4 parts. 1 part tert-dodecyl mercaptan.
  • the graft copolymer (BB-1) latex was coagulated with dilute sulfuric acid, washed, filtered and dried to obtain a dry powder of the graft copolymer (BB-1).
  • the acetone soluble content of the graft copolymer (BB-1) was 27%.
  • the reduced viscosity of the acetone soluble component was 0.3 dl / g.
  • BG1-2 rubber polymer latex by a metering pump. After all the monomer mixture was added, the temperature in the reactor was raised to 80 ° C., and stirring was continued for 30 minutes to obtain a graft copolymer (BG-2) latex.
  • the polymerization rate was 99%.
  • Graft copolymer (BB-2) latex is charged with stirring into a coagulation tank charged with 0.15% aqueous solution (90 ° C) of aluminum chloride (AlCl 3 ⁇ 6H 2 O) 3 times the total latex. And solidified. After all the latex was added, the temperature in the coagulation tank was raised to 93 ° C. and left as it was for 5 minutes. After cooling, the solution was removed by a centrifuge, washed, and dried to obtain a dry powder of the graft copolymer (BB-2). The acetone-soluble content of the graft copolymer (BB-2) was 21%. Moreover, the reduced viscosity of the acetone-soluble component was 0.70 dl / g.
  • a graft copolymer (BB-3) in which a composite rubber of polybutadiene / polybutylacrylate was used as a rubbery polymer (BB1-3) was obtained by the following method.
  • a copolymer latex having an average particle size of 0.10 ⁇ m consisting of 82% n-butyl acrylate units and 18% methacrylic acid units on a polybutadiene latex (solid content 20 parts) having a solid content concentration of 35% and an average particle size of 0.08 ⁇ m. 0.4 parts as solids) was added with stirring. Stirring was continued for 30 minutes to obtain an enlarged diene rubber latex having an average particle size of 0.36 ⁇ m.
  • a solution prepared by dissolving 0.0002 part of ferrous sulfate, 0.0006 part of ethylenediaminetetraacetic acid disodium salt and 0.25 part of Rongalite in 10 parts of ion exchange water was added to the reactor and reacted.
  • the internal temperature at the end of the reaction was 75 ° C. Further, the temperature was raised to 80 ° C., and the reaction was continued for 1 hour to obtain a rubbery polymer (BB1-3) latex comprising a composite rubber of an enlarged diene rubber and a polybutyl acrylate rubber.
  • the polymerization rate was 98.8%.
  • the graft copolymer (BB-3) latex was poured into a coagulation tank charged with a 0.5% aqueous solution of sulfuric acid (90 ° C.) in an amount three times that of the total latex with stirring to coagulate. After all the latex was added, the temperature in the coagulation tank was raised to 93 ° C. and left as it was for 5 minutes. After cooling, the solution was removed by a centrifuge, washed and dried to obtain a dry powder of the graft copolymer (BB-3). The acetone soluble content of the graft copolymer (BB-3) was 20%. Moreover, the reduced viscosity of the acetone soluble part was 0.7 dl / g.
  • a graft copolymer (BB-4) using a composite rubber of polysiloxane rubber and polybutyl acrylate rubber as a rubbery polymer was obtained by the following method. 96 parts of octamethyltetracyclosiloxane, 2 parts of ⁇ -methacryloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane mixture.
  • aqueous solution was heated to 85 ° C.
  • the premixed organosiloxane latex was added dropwise over 4 hours, and the temperature was maintained for 1 hour after the completion of the addition and cooled.
  • the reaction solution was allowed to stand at room temperature for 48 hours and then neutralized with an aqueous sodium hydroxide solution to obtain a polyorganosiloxane latex (BL-1).
  • a part of the polyorganosiloxane latex (BL-1) was dried at 170 ° C. for 30 minutes and the solid content concentration was determined to be 17.3%.
  • a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene, and 0.1 part of tertiary butyl hydroperoxide was added dropwise over about 40 minutes for polymerization. After the completion of dropping, the mixture was held for 1 hour and then cooled to obtain a graft copolymer (BB-4) latex in which an acrylonitrile-styrene copolymer was grafted to the composite rubber (BB1-4).
  • 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred.
  • PET resin (BF) As recycled PET resin (BF-1), Yamaichi's PET-NPR was used. As the re-pelleted PET resin (BF-2), GM502S manufactured by Mitsubishi Chemical Corporation was re-pelleted at 260 ° C. with a twin screw extruder. GM502S manufactured by Mitsubishi Chemical Corporation was used as a PET resin (BF-3) that was neither recycled nor repelletized.
  • Inorganic filler (D) Carbon fiber chopped fiber (manufactured by Mitsubishi Rayon Co., Ltd., TR06U, surface treatment agent: polyurethane) was used as the inorganic filler (D-1). As the inorganic filler (D-2), glass fiber chopped fiber (manufactured by Nitto Boseki Co., Ltd., CSG 3PA-820, surface treatment agent: polyurethane, ratio of major axis / minor axis: 4) was used.
  • inorganic filler (D-3) glass fiber chopped fiber (manufactured by Nitto Boseki Co., Ltd., CSH 3PA-870, surface treatment agent: polyurethane, ratio of major axis / minor axis: 2) was used.
  • inorganic filler (D-4) a glass fiber chopped fiber (manufactured by Nitto Boseki Co., Ltd., CSH 3PA-850, surface treatment agent: epoxy resin, major axis / minor axis ratio: 2) was used.
  • glass fiber chopped fiber manufactured by Nitto Boseki Co., Ltd., CS3PE-455, surface treatment agent: polyurethane, major axis / minor axis ratio: 1) was used.
  • Glycidyl ether unit-containing polymer (E) As the glycidyl ether unit-containing polymer (E-1), an epoxy group-containing phenoxy resin (manufactured by Mitsubishi Chemical Corporation, jER4250, mass average molecular weight: 60,000) was used. As the glycidyl ether unit-containing polymer (E-2), an epoxy group-containing phenoxy resin (manufactured by Mitsubishi Chemical Corporation, jER1256, mass average molecular weight: 50,000) was used. As the glycidyl ether unit-containing polymer (E-3), a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER1010, mass average molecular weight: 5,500) was used.
  • glycidyl ether unit-containing polymer (E-4) a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER1009, mass average molecular weight: 3,800) was used.
  • glycidyl ether unit-containing polymer (E-5) a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER1004, mass average molecular weight: 1,650) was used.
  • the glycidyl ether unit-containing polymer (E-6) was produced by the following method. In a 500 ml separable flask equipped with a stirrer, thermometer, nitrogen inlet and condenser, 82.42 parts of bisphenol A type epoxy resin (epoxy equivalent: 467 g / eq), bisphenol A type liquid epoxy resin (epoxy equivalent) : 210 g / eq, hydrolyzable chlorine: 1.79%) 6.3 parts, bisphenol A 13.95 parts, p-cumylphenol 19.6 parts, polyester resin (manufactured by Iupika Japan, GV-335, acid value) : 30 KOHmg / g) 7.5 parts and 30 parts of xylene were charged and heated to raise the temperature in a nitrogen atmosphere.
  • bisphenol A type epoxy resin epoxy equivalent: 467 g / eq
  • bisphenol A type liquid epoxy resin epoxy equivalent
  • hydrolyzable chlorine 1.79%) 6.3 parts
  • phosphate ester flame retardant (AF) Bisphenol A bis (diphenyl phosphate) (manufactured by Ajinomoto Fine Techno Co., BAPP, mass average molecular weight: 692, catalog value) was used as the phosphate ester flame retardant (AF-1).
  • phenylene bis (dixylyl phosphate) manufactured by Daihachi Chemical Co., Ltd., PX-200, mass average molecular weight: 686, catalog value
  • phosphate ester flame retardant phenylene bis (diphenyl phosphate) (manufactured by Daihachi Chemical Co., Ltd., CR-733S, mass average molecular weight: 574, catalog value) was used.
  • Triphenyl phosphate manufactured by Daihachi Chemical Co., TPP, mass average molecular weight: 326, catalog value was used as the phosphate ester flame retardant (AF-4).
  • BG phosphate ester flame retardant
  • BAPP phosphate ester flame retardant
  • BG-2 phenylene bis (dixylyl phosphate) (manufactured by Daihachi Chemical Co., Ltd., PX-200, mass average molecular weight: 686, catalog value) was used.
  • phosphate ester flame retardant phenylene bis (diphenyl phosphate) (manufactured by Daihachi Chemical Co., Ltd., CR-733S, mass average molecular weight: 574, catalog value) was used.
  • phosphate ester flame retardant BG-4
  • triphenyl phosphate manufactured by Daihachi Chemical Co., TPP, mass average molecular weight: 326, catalog value
  • Examples A1 to A26, Comparative Examples A1 to A12> The components described above were blended as shown in Tables 1 to 3 and kneaded using a twin screw extruder to obtain pellets of reinforced thermoplastic resin composition A. The obtained pellets were dried at 100 ° C. for 3 hours, and the moldability was evaluated by injection molding. Further, the Charpy impact strength, bending strength, flexural modulus, heat resistance, flame retardancy, and adhesive strength of the obtained molded product were measured. The evaluation results are shown in Tables 1 to 3.
  • Examples B1 to B22 and Comparative Examples B1 to B12 The components described above were blended as shown in Tables 4 to 6 and kneaded using a twin screw extruder to obtain pellets of reinforced thermoplastic resin composition B. The obtained pellets were dried at 100 ° C. for 3 hours, and the moldability was evaluated by injection molding. Moreover, the Charpy impact strength, bending strength, bending elastic modulus, heat resistance, and flame retardance of the obtained molded product were measured. The evaluation results are shown in Tables 4-6.
  • the amounts of the inorganic filler (D), glycidyl ether unit-containing polymer (E), phosphate ester flame retardant (AF), and flame retardant aid (H) in Tables 1 to 3 are the resin main component (AC) 100. This is the amount (parts) relative to the part. Further, “the ratio of (D)” is the ratio (%) of the inorganic filler (D) in 100% of the reinforced thermoplastic resin composition A.
  • the amounts of the inorganic filler (D), the glycidyl ether unit-containing polymer (E), the phosphate ester flame retardant (BF), and the flame retardant aid (H) in Tables 4 to 6 are the resin main component (BC) 100. This is the amount (parts) relative to the part. Further, “the ratio of (D)” is the ratio (%) of the inorganic filler (D) in 100% of the reinforced thermoplastic resin composition B.
  • the reinforced thermoplastic resin composition obtained in each example was excellent in moldability. Moreover, from the reinforced thermoplastic resin composition obtained in each Example, a molded article excellent in impact resistance, rigidity, mechanical strength, heat resistance, flame retardancy, and adhesive strength was obtained.
  • Comparative Examples A1 to A12 are inferior in any of the items of moldability of the reinforced thermoplastic resin composition A, impact resistance, rigidity, mechanical strength, heat resistance, flame resistance, and adhesive strength of the molded product. It was a thing. Specifically, in the case of Comparative Example A1 in which the proportion of the polycarbonate resin (AA) is small and the proportion of the graft copolymer (AG) is large, the molded product is inferior in heat resistance, flame retardancy, rigidity, and mechanical strength. It was. In the case of Comparative Example A2 having a large proportion of the inorganic filler (D), the moldability and the flame retardancy of the molded product were inferior.
  • the content of the glycidyl ether unit-containing polymer (E) is 12 parts with respect to 100 parts of the resin main component (AC), and the mass average molecular weight of the glycidyl ether unit-containing polymer (E) is 70,200.
  • the moldability and the flame retardancy of the molded product were inferior.
  • the heat resistance of the molded product was inferior.
  • Comparative Example A7 where the mass average molecular weight of the glycidyl ether unit-containing polymer (E) was 1,650, the molded article was inferior in impact resistance.
  • Comparative Example A8 in which the content of the glycidyl ether unit-containing polymer (E) was 12 parts with respect to 100 parts of the resin main component (AC), the flame retardancy of the molded product was inferior.
  • Comparative Examples B1 to B12 are inferior in any of the items of moldability of the reinforced thermoplastic resin composition B, impact resistance, rigidity, mechanical strength, heat resistance and flame resistance of the molded product. It was. Specifically, in the case of Comparative Example B1 in which the proportion of the polycarbonate resin (BA) is small and the proportion of the graft copolymer (BB) is large, the molded product is inferior in heat resistance, flame retardancy, rigidity, and mechanical strength. It was. In the case of Comparative Example B2 having a large proportion of the inorganic filler (D), the moldability and the flame retardancy of the molded product were inferior.
  • Comparative Example B5 In the case of Comparative Example B5 in which the mass average molecular weight of the glycidyl ether unit-containing polymer (E) is 70,200 and the content is 12 parts with respect to 100 parts of the resin main component (BC), the moldability and the molded product It was inferior in flame retardancy. In the case of Comparative Example B6 in which the content of the phosphate ester flame retardant (BG) was 30 parts with respect to 100 parts of the resin main component (BC), the heat resistance of the molded product was inferior. In the case of Comparative Example B7 in which the mass average molecular weight of the glycidyl ether unit-containing polymer (E) was 1,650, the molded article was inferior in impact resistance.
  • BG phosphate ester flame retardant
  • Example A12 and Comparative Example A3 the reinforced thermoplastic resin composition A of the present invention was formed into a molded product rather than the reinforced thermoplastic resin composition not containing the glycidyl ether unit-containing polymer (E). It can be seen that it has excellent impact resistance.
  • the reinforced thermoplastic resin composition A of the present invention is molded more than the reinforced thermoplastic resin composition containing the PET resin (AB) which is not recycled or repellet. It can be seen that the material has excellent impact resistance when formed into a molded product.
  • the reinforced thermoplastic resin composition B of the present invention is more resistant to molding when formed into a molded product than the reinforced thermoplastic resin composition not containing the glycidyl ether unit-containing polymer. It can be seen that the impact is excellent. From a comparison between Example B9 and Comparative Example B4, the reinforced thermoplastic resin composition B of the present invention is more moldable and molded than a reinforced thermoplastic resin composition containing a PET resin that is neither recycled nor repellet. It can be seen that it is excellent in impact resistance.
  • the reinforced thermoplastic resin composition of the present invention is more flame retardant when formed into a molded article than a reinforced thermoplastic resin composition containing a graft copolymer using a rubbery polymer other than a silicone-acrylic composite rubber. It turns out that it is excellent in.
  • the reinforced thermoplastic resin composition of the present invention is particularly useful as a housing material for mobile devices (notebook and tablet personal computers, mobile phones including smartphones, digital cameras, digital video cameras, and the like).

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention décrit : une composition de résine thermoplastique renforcée qui présente une aptitude favorable au moulage et qui est capable d'accroître dans un article moulé obtenu à partir de ce dernier, la rigidité, la résistance aux chocs, la résistance mécanique, la résistance à la chaleur, l'ignifugation, et la force d'adhésion avec des adhésifs de vitre de façade ; et un article moulé présentant une rigidité, une résistance aux chocs, une résistance mécanique, une résistance à la chaleur, une ignifugation, et une force adhésive élevées avec des adhésifs de vitre de façade. La composition de résine thermoplastique renforcée contient, sous un certain rapport : un constituant principal de résine (AC) comprenant de 80 à 100 % en masse d'une résine de polycarbonate (AA) et de 0 à 20 % en masse d'un copolymère greffé spécifique (AG) ; une résine de poly(téréphtalate d'éthylène) recyclée et/ou refondue (AB) ; une charge inorganique (D) ; un polymère contenant un motif éther de glycidyle (E) présentant un poids moléculaire moyen en masse de 3 800 à 60 000 ; et un agent ignifuge à base d'ester phosphate (AF) ayant un poids moléculaire moyen en masse supérieur à 326.
PCT/JP2017/010958 2016-03-30 2017-03-17 Composition de résine thermoplastique de renfort et son article moulé WO2017169912A1 (fr)

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CN110423451A (zh) * 2019-08-14 2019-11-08 上海华合复合材料有限公司 一种基于酯交换控制的高耐候、高环保性的阻燃聚碳酸酯合金材料及其制备方法

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CN110423451A (zh) * 2019-08-14 2019-11-08 上海华合复合材料有限公司 一种基于酯交换控制的高耐候、高环保性的阻燃聚碳酸酯合金材料及其制备方法

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