JP6145532B1 - Reinforced thermoplastic resin composition and molded article thereof - Google Patents

Abstract

The present invention relates to a reinforced thermoplastic resin composition having good moldability and capable of enhancing the rigidity, impact resistance, mechanical strength, heat resistance, and flame retardancy of the obtained molded product, and rigidity, impact resistance, mechanical properties. To provide a molded product having high strength, heat resistance, flame retardancy, and high adhesive strength with an adhesive for windshield. A monomer mixture containing an aromatic alkenyl compound and a vinyl cyanide compound in the presence of 80 to 95% by mass of a polycarbonate resin (A) and a rubbery polymer (B1) which is a silicone-acrylic composite rubber. m1) a graft copolymer (B) obtained by polymerizing 5-20% by mass of a resin main component (C); an inorganic filler (D); and a mass average molecular weight of 3,800-60, A glycidyl ether unit-containing polymer (E) of 000; a recycled and / or re-pelleted polyethylene terephthalate resin (F); and a phosphate ester flame retardant (G) having a mass average molecular weight of more than 326 A reinforced thermoplastic resin composition. [Selection figure] None

Description

  The present invention relates to a reinforced thermoplastic resin composition and a molded article using the same.

  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. As 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.

  In recent years, with the aim of further reducing the thickness of mobile device casings, being able to withstand shocks and loads when placed in bags, etc., and preventing the windshield from being removed when the product is dropped. There is a demand for non-coating. In order to satisfy these requirements, the thermoplastic resin composition used for the casing has high rigidity, impact resistance, mechanical strength, flame resistance, and good moldability at the time of molding. In addition, excellent adhesive strength with a windshield adhesive is required.

  However, since the 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. Moreover, 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.
However, 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.
In particular, a reinforced thermoplastic resin composition mainly composed of a polycarbonate resin / polyester resin has poor thermal stability. Further, when the molding process is held at a high temperature in the cylinder, a decomposition gas is generated due to a transesterification reaction between the polycarbonate resin and the polyester resin, and the appearance of the molded product called foam or silver streak tends to be poor. In addition, due to a decrease in the molecular weight of the polycarbonate resin, the original impact resistance and heat resistance of the polycarbonate resin may be impaired. Furthermore, there is a problem that the viscosity of the polycarbonate resin changes due to retention at a high temperature, the molding stability at the time of injection molding is impaired, and short shots and burrs of the obtained molded product are generated.
On the other hand, 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.
(1) 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).
(2) an aromatic polycarbonate resin, a fibrous filler surface-treated with polyamide, and a lubricant having at least one functional group selected from a carboxyl group, a carboxylic anhydride group, an epoxy group, and an oxazoline group Reinforced thermoplastic resin composition comprising a specific amount (Patent Document 2).

The following are proposed as the reinforced thermoplastic resin composition capable of obtaining a molded article having excellent mechanical strength and molding stability.
(3) 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).
(4) 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).

JP 2013-14747 A JP 2001-240738 A JP 60-88062 A JP 2012-77242 A

However, 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.

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 the molded article.
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 that has good moldability and can increase the rigidity, impact resistance, mechanical strength, heat resistance, flame retardancy, and excellent adhesive strength with an adhesive for windshields of the resulting molded product. A resin composition and a molded product thereof are provided.

The present invention includes the following aspects.
[1] A monomer mixture (m1) 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 (A) and the rubbery polymer (B1). The resin main component comprising 5 to 20% by mass of the obtained graft copolymer (B) (however, the total of the polycarbonate resin (A) and the graft copolymer (B) is 100% by mass). Reinforced thermoplastic resin containing component (C), inorganic filler (D), glycidyl ether unit-containing polymer (E), polyethylene terephthalate resin (F), and phosphate ester flame retardant (G) A composition comprising:
The rubbery polymer (B1) is a silicone-acrylic composite rubber,
Content of the said inorganic filler (D) is 20-55 mass% in 100 mass% of the said 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 (C). 3 to 10 parts by mass with respect to
The polyethylene terephthalate resin (F) is recycled and / or re-pelletized, and the content of the polyethylene terephthalate resin (F) is 5 to 30 masses with respect to 100 mass parts of the resin main component (C). Department,
The phosphoric ester-based flame retardant (G) has a mass average molecular weight exceeding 326, and the content of the phosphoric ester-based flame retardant (G) is 3 to 25 mass with respect to 100 parts by mass of the resin main component (C). Part of a reinforced thermoplastic resin composition.
[2] The reinforced thermoplastic resin composition according to [1], wherein the inorganic filler (D) is carbon fiber.
[3] The reinforced thermoplastic resin composition according to [1], wherein the inorganic filler (D) is glass fiber.
[4] A molded article obtained by molding the reinforced thermoplastic resin composition according to any one of [1] to [3].

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.

Hereinafter, the present invention will be described in detail.
In the following description, “(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.

"Reinforced thermoplastic resin composition"
The reinforced thermoplastic resin composition of the present invention comprises a resin main component (C), an inorganic filler (D), a glycidyl ether unit-containing polymer (E), a polyethylene terephthalate resin (F), and a phosphate ester-based difficulty. And a flame retardant (G).
The resin main component (C) comprises 80 to 95% by mass of the polycarbonate resin (A) and 5 to 20% by mass of the graft copolymer (B) (however, the polycarbonate resin (A) and the graft copolymer The total with the polymer (B) is 100% by mass).
The graft copolymer (B) is obtained by polymerizing the monomer mixture (m1) in the presence of the rubbery polymer (B1).

The reinforced thermoplastic resin composition of the present invention preferably further contains a flame retardant aid (H).
The reinforced thermoplastic resin composition of the present invention may contain a flame retardant (I) other than the phosphoric ester-based flame retardant (G), as necessary, within a range not impairing the effects of the present invention. .
The reinforced thermoplastic resin composition of the present invention is a resin main component (C), an inorganic filler (D), a glycidyl ether unit-containing polymer (E) as long as it does not impair the effects of the present invention. , Polyethylene terephthalate resin (F), phosphate ester flame retardant (G), flame retardant aid (H) and other components other than flame retardant (I) may be included.
Hereinafter, each component ((A) to (I), (B1), (m1), etc.) will be described.

<Polycarbonate resin (A)>
The polycarbonate resin (A) is a resin obtained from dihydroxydiarylalkane. The polycarbonate resin (A) may be unbranched or branched. A polycarbonate resin (A) may be used individually by 1 type, and may use 2 or more types together.
As the polycarbonate resin (A), a commercially available product may be used, or a product produced by a known production method may be used.

Examples of the method for producing the polycarbonate resin (A) include a method in which a dihydroxy compound such as dihydroxydiarylalkane or a polyhydroxy compound is reacted 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. Preferable specific examples of the dihydroxydiarylalkane include 4,4-dihydroxy2,2-diphenylpropane (that is, bisphenol A), tetramethylbisphenol A, bis- (4-hydroxyphenyl) -p-diisopropylbenzene, and the like. .
The branched polycarbonate resin (A) is produced, for example, by substituting a part (for example, 0.2 to 2 mol%) of a dihydroxy compound with a polyhydroxy compound. Specific examples of the polyhydroxy compound include phloroglucinol, 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.
As the polycarbonate resin (A), one recycled from a compact disk or the like may be used.

The viscosity average molecular weight (Mv) of the polycarbonate resin (A) is preferably 15,000 to 35,000. When the viscosity average molecular weight of the polycarbonate resin (A) is 15,000 or more, the impact resistance of the molded product is further increased. If the viscosity average molecular weight of polycarbonate resin (A) 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 (A) is more preferably 17,000 to 25,000 in view of particularly excellent balance between the mechanical strength of the molded article, the impact resistance, and the fluidity of the reinforced thermoplastic resin composition. .
The viscosity average molecular weight of the polycarbonate resin (A) can be determined, for example, by a solution viscosity method. When using a commercially available polycarbonate resin (A), a catalog value may be used.

<Rubber polymer (B1)>
The rubber polymer (B1) is a silicone-acrylic composite rubber. Since the rubber polymer (B1) is a silicone-acrylic composite rubber, the flame retardancy and high temperature and high humidity of the molded product obtained from the reinforced thermoplastic resin composition are compared with the case where other rubber polymers are used. Increased durability under.
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).

  Examples of the alkyl (meth) acrylate (f) include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; hexyl methacrylate, 2-ethylhexyl methacrylate, and n-lauryl methacrylate. And alkyl methacrylates such as These may be used individually by 1 type and may be used in combination of 2 or more type.

  Examples of the polyfunctional monomer (g) include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol dimethacrylate, triallyl cyanurate, And triallyl isocyanurate. These may be used individually by 1 type and may be used in combination of 2 or more type.

  The composite structure of the silicone-acrylic composite rubber includes 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 (B1) is prepared, for example, by emulsion polymerization of a monomer that forms the rubber polymer (B1) 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 (B1).
The average particle size of the silicone-acrylic composite rubbery polymer (B1) is preferably 0.1 to 0.6 μm because the impact resistance of the reinforced thermoplastic resin composition can be further increased.

<Monomer mixture (m1)>
The monomer mixture (m1) 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, α-methylstyrene, vinyltoluene, and the like, and styrene is preferable.
Examples of the monomer (b) include acrylonitrile and methacrylonitrile, and acrylonitrile is preferable.
As the monomer (c), for example, alkyl methacrylate (methyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, etc.), alkyl acrylate (methyl acrylate, ethyl acrylate, butyl acrylate, etc.), maleimide compound (N-phenylmaleimide, etc.) Etc.

  The proportion of each monomer in the monomer mixture (m1) is such that the proportion of the monomer (a) is excellent in the balance between the impact resistance of the molded product and the moldability of the reinforced thermoplastic resin composition. It is preferable that the proportion of the monomer (b) is 50 to 90% by mass, the proportion of the other monomer (c) is 0 to 40% by mass (however, the monomer (The sum of (a) to (c) is 100% by mass.)

<Graft copolymer (B)>
The graft copolymer (B) is obtained by polymerizing the monomer mixture (m1) in the presence of the rubbery polymer (B1). That is, the graft copolymer (B) is obtained by grafting the polymer (B2) formed from the monomer mixture (m1) to the rubbery polymer (B1). A graft copolymer (B) may be used individually by 1 type, and may use 2 or more types together.

  The content of the rubber polymer (B1) is preferably 5 to 25% by mass in the resin main component (C) (100% by mass). When the content of the rubber polymer (B1) is 5% by mass or more, the impact resistance of the molded product can be further increased. If content of a rubber-like polymer (B1) is 25 mass% or less, the moldability of a reinforced thermoplastic resin composition will become higher, and the external appearance of a molded article will become favorable.

  A polymer (B2) has a monomer (a) unit and a monomer (b) unit as an essential component, and has another monomer (c) unit copolymerizable with these as an arbitrary component. The preferred range of the proportion (mass%) of each monomer unit in the polymer (B2) is the same as the preferred range of the proportion of each monomer in the monomer mixture (m1).

The graft copolymer (B) contains 1 to 30% by mass of an acetone-soluble component and has a reduced viscosity measured at 25 ° C. as a 0.2 g / dl N, N-dimethylformamide solution of the acetone-soluble component. It is preferable that it is 0.3-0.7 dl / g.
If the acetone soluble content is 30% by mass or less (the acetone insoluble content is 70% by mass or more), the moldability of the reinforced thermoplastic resin composition and the surface appearance of the molded product are improved. When the acetone-soluble content is 1% by mass or more (acetone-insoluble content is 99% by mass or less), the tear strength of the molded product is improved.
If the reduced viscosity of the acetone-soluble component is 0.3 dl / g or more, the tear strength of the molded product is improved, and if it is 0.7 dl / g or less, the moldability of the reinforced thermoplastic resin composition and the molded product are improved. The surface appearance of 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 ([graft copolymer 2.5 g] − [mass of sample after drying]), the content ratio (%) of the acetone-soluble component relative to the graft copolymer can be determined.
The reduced viscosity of the acetone-soluble component is measured at 25 ° C. using a 0.2 g / dl N, N-dimethylformamide solution.
Here, the acetone-soluble component is a polymer similar to the polymer (B2), and is a polymer not grafted to the rubbery polymer (B1). Acetone-soluble components are often generated simultaneously with the grafting of the polymer (B2) to the rubbery polymer (B1). Therefore, the graft copolymer (B) contains an acetone-soluble component and an acetone-insoluble component.
In the graft copolymer (B), it is difficult to specify how the rubber polymer (G1) and the monomer mixture (m1) are polymerized. That is, there is a situation (impossible / unpractical situation) that the graft copolymer (B) cannot be directly specified by its structure or characteristics, or is almost impractical.

(Method for producing graft copolymer (B))
The graft copolymer (B) is obtained by graft polymerization of the monomer mixture (m1) in the presence of the rubbery polymer (B1).
The graft polymerization method is not particularly limited, but an emulsion polymerization method is preferable. Moreover, at the time of graft polymerization, various chain transfer agents may be added in order to adjust the molecular weight of the graft copolymer (B), the graft ratio, and the reduced viscosity of the acetone-soluble component.

<Resin main component (C)>
The resin main component (C) is composed of 80 to 95% by mass of the polycarbonate resin (A) and 5 to 20% by mass of the graft copolymer (B) (however, the polycarbonate resin (A) and the graft copolymer) The total with the polymer (B) is 100% by mass.), Preferably 90 to 95% by mass of the polycarbonate resin (A) and 5 to 10% by mass of the graft copolymer (B).
If the proportion of the polycarbonate resin (A) 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. Good moldability.
If the proportion of the graft copolymer (B) is 5% by mass or more, the moldability of the reinforced thermoplastic resin composition is good, and if it is 20% by mass or less, the impact resistance and flame retardancy of the molded product. Good mechanical strength and rigidity.

<Inorganic filler (D)>
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.

The above-mentioned 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.
Further, 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 the 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 the 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.

<Glycidyl ether unit-containing polymer (E)>
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.

As a glycidyl ether unit containing polymer (E), the glycidyl ether type epoxy resin obtained by reaction of the compound which has a hydroxyl group, and epichlorohydrin is mentioned, for example.
Examples of 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.

  However, m is an integer greater than or equal to 1.

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.

  Examples of 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.

  As the glycidyl ether unit-containing polymer (E), 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. A novolak type epoxy resin, a cresol novolak type epoxy resin, and an epoxy group-containing phenoxy resin are preferable.

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. When 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. When 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.

As the 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.

<Polyethylene terephthalate resin (F)>
The polyethylene terephthalate (hereinafter also referred to as PET) resin (F) is 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 the recycled and / or re-pelleted polyethylene terephthalate resin (F).
Regarding recycled materials obtained by collecting used PET bottles, food trays, etc., it is necessary to avoid mixing of different materials and metals by sorting. Moreover, when it wash | cleans with alkaline water etc., after performing sufficient water washing, a drying process is required so that the alkali component which accelerates | stimulates hydrolysis of PET resin may not remain.
The shape of the recycled PET resin is generally flaky, and the average particle diameter 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 (F) may be used individually by 1 type, and may use 2 or more types together.

<Phosphate ester flame retardant (G)>
A well-known thing can be used as a phosphate ester type flame retardant (G), for example, the compound represented by following formula (2) is mentioned.

However, 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.). There is no limitation on the number of substituents when substituted. 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 the like), 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.

  Specific examples of the phosphate ester flame retardant (G) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixyl phosphate, cresyl diphenyl phosphate, Examples include xyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl-2-ethylcresyl phosphate, tris (isopropylphenyl) phosphate, resorcinyl diphenyl phosphate, and polyphosphate.

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. Examples of the diol include hydroquinone, resorcinol, diphenylolmethane, diphenyloldimethylmethane, dihydroxybiphenyl, p, p′-dihydroxydiphenylsulfone, dihydroxynaphthalene and the like.

  Among the above, as the phosphoric ester-based flame retardant (G), triphenyl phosphate, bisphenol A bis (diphenyl phosphate), phenylene bis (diphenyl phosphate), and phenylene bis (dixyl phosphate) are preferable.

The mass average molecular weight of the phosphate ester flame retardant (G) is preferably more than 326, and more preferably 550 or more. If the phosphate ester flame retardant (G) 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 a molded product having an excellent appearance can be obtained.
The mass average molecular weight of the phosphate ester flame retardant (G) 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 (G) can be determined by mass spectrometry. When using a commercially available phosphate ester flame retardant (G), a catalog value may be used.

As the phosphate ester flame retardant (G), a commercially available product may be used, or a product produced by a known production method may be used.
Examples of commercially available phosphoric ester-based flame retardants (G) include: FP series manufactured by ADEKA, Clontex (registered trademark) series manufactured by Ajinomoto Fine Techno Co., Leophos (registered trademark) series manufactured by Chemtura Japan, Examples include CR series and PX series manufactured by Daihachi Chemical.

<Flame Retardant (H)>
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.

<Other flame retardants (I)>
As the flame retardant (I) other than the phosphate ester flame retardant (G), various known flame retardants can be used, and non-halogen flame retardants other than the phosphate ester flame retardant (G) are preferable. Examples of the non-halogen flame retardant include phosphazene compounds, phosphorus-containing polyesters, inorganic flame retardants (red phosphorus, aluminum hydroxide, etc.) and the like.
As the 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 the red phosphorus flame retardant alone is ignitable, it may be mixed in advance with at least a part of the resin main component (C) or the polycarbonate resin (A) to form a master batch.

<Other ingredients>
Examples of other components include other modifiers, mold release agents, stabilizers against light or heat, antistatic agents, dyes, and pigments.

<Content of each component>
In the reinforced thermoplastic resin composition, 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.

  3-10 mass parts is preferable with respect to 100 mass parts of resin main components (C), and, as for content of a glycidyl ether unit containing polymer (E), 6-8 mass parts is more preferable. 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 a reinforced thermoplastic resin composition and the flame retardance of a molded article will become favorable.

  5-30 mass parts is preferable with respect to 100 mass parts of resin main components (C), and, as for content of PET resin (F), 10-20 mass parts is more preferable. If content of PET resin (F) is 5 to 30 mass parts, it is excellent in impact resistance.

  3-25 mass parts is preferable with respect to 100 mass parts of resin main components (C), and, as for content of a phosphate ester type flame retardant (G), 5-23 mass parts is more preferable. When the content of the phosphate ester flame retardant (G) is 25 parts by mass or less, the impact resistance and heat resistance of the molded article are increased. When the content of the phosphoric ester-based flame retardant (G) is 3 parts by mass or more, the flame retardancy and moldability of the molded product are further improved.

  When the reinforced thermoplastic resin composition contains a copolymer having polytetrafluoroethylene or a tetrafluoroethylene unit as the flame retardant aid (H), the content of the flame retardant aid (H) is a molded product. From the viewpoint of the surface appearance, 1 part by mass or less is preferable with respect to 100 parts by mass of the resin main component (C). Although a minimum is not specifically limited, 0.1 mass part or more is preferable with respect to 100 mass parts of resin main components (C) at the point by which the effect by a flame-retardant adjuvant (H) is easy to be acquired.

<Method for producing reinforced thermoplastic resin composition>
The reinforced thermoplastic resin composition of the present invention comprises a polycarbonate resin (A), a graft polymer (B), an inorganic filler (D), a glycidyl ether unit-containing polymer (E), and a PET resin (F). And a phosphate ester flame retardant (G) and, if necessary, a flame retardant aid (H), another flame retardant (I), and other components. Specifically, each component can be obtained by mixing using a mixing device (for example, a Henschel mixer, a tumbler mixer, a nauter mixer, etc.). Furthermore, 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).

<Effect>
In the reinforced thermoplastic resin composition of the present invention described above, the resin main component (C) comprising a specific amount of the polycarbonate resin (A) and the graft copolymer (B), and the inorganic filler (D) And a glycidyl ether unit-containing polymer (E) having a specific mass average molecular weight, a recycled and / or re-pelleted PET resin (F), and a phosphate ester flame retardant (G) in a specific ratio Therefore, the moldability is good and the rigidity, impact resistance, mechanical strength, heat resistance, and flame retardance of the molded product obtained can be increased.
Moreover, since the moldability is good, appearance defects such as silver streaks are unlikely to occur in the obtained molded product.

"Molding"
The molded article of the present invention is obtained by molding the reinforced thermoplastic resin composition of the present invention.
Examples of 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. Among these, 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.

  In the molded article of the present invention, since the reinforced thermoplastic resin composition of the present invention is used, rigidity, impact resistance, mechanical strength, heat resistance, and flame retardancy are high. 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. Among these applications, 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.

Hereinafter, an example is shown concretely. However, the present invention is not limited to these examples.
“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.

<Measurement method, evaluation method>
[Acetone solubles]
2.5 g of the graft copolymer was 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 was removed, and the residue was dried at 65 ° C. for 12 hours in a vacuum dryer, and the dried sample was precisely weighed. From the mass difference (2.5 g-mass of sample after drying (g)), the proportion (%) of acetone-soluble matter in the graft copolymer was determined. The reduced viscosity of the acetone-soluble component was measured at 25 ° C. using a 0.2 g / dl N, N-dimethylformamide solution.

[Charpy impact strength]
The Charpy impact strength was measured according to ISO 179-1: 2013 edition.

[Bending strength and flexural modulus]
In accordance with ISO 178: 2013 version, bending strength and bending elastic modulus were measured. The bending strength is an index of mechanical strength of the molded product, and the flexural modulus is an index of rigidity of the molded product.

[Heat-resistant]
In accordance with ISO 75-2: 2013 edition, the deflection temperature was measured by the 1.80 MPa load flatwise method.

[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.
(Double-circle): There was no unfilling, sink, and gas burning.
○: Some sink marks were observed.
X: Unfilled or gas burned or silver streak was observed.

[Flame retardance]
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 1.6 mm), which is flame retardant according to UL94 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. And whether it is equivalent to V-1 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. In addition, the standard of V-1 is “the first flammable combustion duration is within 10 seconds within 30 seconds, and the total of the second flammable combustion duration and the flameless combustion duration is within 30 seconds and within 60 seconds. There is no burning fallen object. "
○: V-1 level flame retardancy was exhibited.
X: V-1 level flame retardancy was not exhibited.
[Adhesive strength]
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. As the adhesive, urethane adhesive “Pandeau 156A” manufactured by Three Bond Co., Ltd. was used.

<Each component>
[Polycarbonate resin (A)]
As the polycarbonate resin (A-1), Novalex 7021PJ (viscosity average molecular weight: 18,800) manufactured by Mitsubishi Engineering Plastics was used.

[Production of Graft Copolymer (B-1)]
Copolymer latex having an average particle size of 0.08 μm consisting of 85% n-butyl acrylate units and 15% methacrylic acid units in a polybutadiene latex (solid content: 100 parts) having a solid content concentration of 35% and an average particle size of 0.08 μm. (2 parts as solids) was added with stirring. Stirring was continued for 30 minutes to obtain an enlarged butadiene rubber polymer (B1-1) latex having an average particle size of 0.28 μm.
The obtained enlarged butadiene rubber polymer (B1-1) latex was charged into a reactor, and 100 parts of distilled water, 4 parts of a 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 by holding for 1 hour to obtain a graft copolymer (B-1) latex.
30 parts acrylonitrile.
70 parts of styrene.
Cumene hydroperoxide 0.4 parts.
1 part tert-dodecyl mercaptan.

The graft copolymer (B-1) latex was coagulated with dilute sulfuric acid, then washed, filtered and dried to obtain a dry powder of the graft copolymer (B-1).
The acetone soluble part of the graft copolymer (B-1) was 27%. Moreover, the reduced viscosity of the acetone soluble component was 0.3 dl / g.

[Production of Graft Copolymer (B-2)]
Raw materials were charged into the reactor at the following ratio and polymerized with stirring at 50 ° C. for 4 hours under nitrogen substitution to obtain a rubbery polymer (B1-2) latex.
98 parts of n-butyl acrylate.
1 part of 1,3-butylene glycol dimethacrylate.
1 part of allyl methacrylate.
2.0 parts of sodium dioctyl sulfosuccinate.
300 parts deionized water.
0.3 parts of potassium persulfate.
Disodium phosphate 12-hydrate 0.5 parts.
Sodium hydrogen phosphate 12 hydrate 0.3 parts.

The resulting rubbery polymer (B1-2) latex (100 parts as a solid content) was charged into another reactor, diluted with 280 parts of ion-exchanged water, and heated to 70 ° C.
Separately, 0.7 parts of benzoyl peroxide was dissolved in 100 parts of a monomer mixture composed of acrylonitrile / styrene = 29/71 (mass ratio), and after nitrogen substitution, the monomer mixture was 30 parts / hour. Was added to the reactor containing the rubber polymer (G1-2) latex by a metering pump. After all of 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 (G-2) latex. The polymerization rate was 99%.

The graft copolymer (B-2) latex is added to a coagulation tank charged with 0.15% aqueous solution (90 ° C.) of aluminum chloride (AlCl ₃ .6H ₂ O) three times as much as the total latex while stirring. 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 then dried to obtain a dry powder of the graft copolymer (B-2).
The acetone soluble content of the graft copolymer (B-2) was 21%. Moreover, the reduced viscosity of the acetone-soluble component was 0.70 dl / g.

[Production of Graft Copolymer (B-3)]
A graft copolymer (B-3) using a polybutadiene / polybutylacrylate composite rubber as a rubbery polymer (B1-3) was obtained by the following method.
Copolymer latex having an average particle size of 0.10 μm consisting of 82% n-butyl acrylate units and 18% methacrylic acid units on a polybutadiene latex having a solid content concentration of 35% and an average particle size of 0.08 μm (20 parts as the solid content) 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 μm.

Charge the resulting enlarged diene rubber latex (20 parts as a solid content) to a reactor, add 1 part of disproportionated potassium rosin acid, 150 parts of ion-exchanged water, and a monomer mixture having the following composition, and replace with nitrogen. The temperature was raised to 50 ° C. (internal temperature).
80 parts of n-butyl acrylate.
Allyl methacrylate 0.32 parts.
0.16 parts of ethylene glycol dimethacrylate.

  Furthermore, 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. Furthermore, the temperature was raised to 80 ° C., and the reaction was continued for 1 hour to obtain a rubbery polymer (B1-3) latex composed of a composite rubber of an enlarged diene rubber and a polybutyl acrylate rubber. The polymerization rate was 98.8%.

Rubber polymer (B1-3) latex (50 parts as a solid content) was charged into a reactor, diluted with 140 parts of ion-exchanged water, and heated to 70 ° C.
Separately from this, 0.35 part of benzoyl peroxide was dissolved in 50 parts of a monomer mixture composed of acrylonitrile / styrene = 29/71 (mass ratio) and purged with nitrogen. The monomer mixture was added at a rate of 15 parts / hour to the reactor containing the rubber polymer (B1-3) latex by a metering pump. After all of 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 (B-3) latex. The polymerization rate was 99%.

The graft copolymer (B-3) latex was put into a coagulation tank charged with a 0.5% aqueous solution of sulfuric acid (90 ° C.) three times as much as the total latex to be 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 (B-3).
The acetone soluble part of the graft copolymer (B-3) was 20%. Moreover, the reduced viscosity of the acetone soluble part was 0.7 dl / g.

[Production of Graft Copolymer (B-4)]
A graft copolymer (B-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 γ-methacryloxypropyldimethoxymethylsilane and 2 parts of ethyl orthosilicate were mixed to obtain 100 parts of a siloxane mixture. To this was added 300 parts of distilled water in which 0.67 parts of sodium dodecylbenzenesulfonate was dissolved, and the mixture was stirred at 10000 rpm for 2 minutes with a homomixer, and then passed once through the homogenizer at a pressure of 30 MPa. A siloxane latex was obtained.
In addition, 2 parts of dodecylbenzenesulfonic acid and 98 parts of distilled water were injected into a reactor equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirrer to prepare a 2% aqueous solution of dodecylbenzenesulfonic acid. . While this 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 (L-1). A part of the polyorganosiloxane latex (L-1) was dried at 170 ° C. for 30 minutes to obtain a solid content concentration of 17.3%.

Next, 119.5 parts of polyorganosiloxane latex (L-1) and 0.8 part of sodium polyoxyethylene alkylphenyl ether sulfate were placed in a reactor equipped with a reagent injection container, a condenser, a jacket heater and a stirrer. Charge, 203 parts of distilled water was added and mixed. Thereafter, a mixture consisting of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1,3-butylene glycol dimethacrylate and 0.13 part of tertiary butyl hydroperoxide was added. The atmosphere was purged with nitrogen by passing a nitrogen stream through the reactor, and the temperature was raised to 60 ° C. An aqueous solution in which 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.24 part of Rongalite are dissolved in 10 parts of distilled water when the temperature inside the reactor reaches 60 ° C. Was added to initiate radical polymerization. The liquid temperature rose to 78 ° C. by polymerization of the acrylate component. This state was maintained for 1 hour to complete the polymerization of the acrylate component to obtain a composite rubber (B1-4) latex of polyorganosiloxane and polybutyl acrylate rubber.
After the liquid temperature inside the reactor dropped to 60 ° C., an aqueous solution in which 0.4 part of Rongalite was dissolved in 10 parts of distilled water was added. Subsequently, 11.1 parts of acrylonitrile, 33.2 parts of styrene, and 0.2 part of tertiary butyl hydroperoxide were dropped and polymerized over about 1 hour. After holding for 1 hour after the completion of dropping, an aqueous solution in which 0.0002 parts of ferrous sulfate, 0.0006 parts of ethylenediaminetetraacetic acid disodium salt and 0.25 parts of Rongalite were dissolved in 10 parts of distilled water was added. Next, 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 (B-4) latex in which an acrylonitrile-styrene copolymer was grafted to the composite rubber (B1-4).
Next, 150 parts of an aqueous solution in which calcium acetate was dissolved at a rate of 5% was heated to 60 ° C. and stirred. In the calcium acetate aqueous solution, 100 parts of the graft copolymer (B-4) latex was gradually dropped and solidified. The obtained solidified product was separated, washed, and dried to obtain a dry powder of the graft copolymer (B-4).
The acetone soluble part of the graft copolymer (B-4) was 26%. Further, the reduced viscosity of the acetone-soluble component was 0.60 dl / g.

[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.
As the 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.
As the inorganic filler (D-4), glass fiber chopped fiber (manufactured by Nitto Boseki Co., Ltd., CSH 3PA-850, surface treatment agent: epoxy resin, ratio of major axis / minor axis: 2) was used.
As the inorganic filler (D-5), glass fiber chopped fiber (manufactured by Nitto Boseki Co., Ltd., CS3PE-455, surface treatment agent: polyurethane, ratio of major axis / minor axis: 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.
As the 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.
As the 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. When the internal temperature of the reaction system reached 80 ° C., 0.18 part of 5% aqueous lithium chloride solution was added, and the temperature was further raised. When the internal temperature of the reaction system reached 130 ° C., the pressure inside the reaction system was reduced, and xylene and water were extracted out of the system. The reaction was carried out while maintaining the reaction temperature at 160 ° C., and after 1 hour, nitrogen was introduced into the reaction system to return the internal pressure of the reaction system to normal pressure. When 7 hours have passed since the reaction temperature reached 160 ° C., 20.25 parts of a high molecular weight bisphenol A type epoxy resin (epoxy equivalent: 2700 g / eq) was added and stirred for 1 hour, and then a polyester resin (Nippon Iupika) (Manufactured, GV-730, acid value: 3 KOH mg / g) 100 parts were added and reacted at 180 ° C. for 10 hours to obtain a high molecular weight epoxy resin. In order to use the obtained high molecular weight epoxy resin for molecular weight measurement by GPC, 0.1 g of a sample was dissolved in 10 ml of tetrahydrofuran, and about 0.05 g was insoluble. After filtration with 5C filter paper, the filtrate was subjected to molecular weight measurement by GPC. As a result, the mass average molecular weight was 70,200.

[PET resin (F)]
As recycled PET resin (F-1), Yamaichi Co., Ltd. PET-NPR was used.
As the re-pelleted PET resin (F-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 (F-3) that was neither recycled nor repelletized.

[Phosphate ester flame retardant (G)]
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 (G-1).
As the phosphate ester flame retardant (G-2), phenylene bis (dixylyl phosphate) (manufactured by Daihachi Chemical Co., Ltd., PX-200, mass average molecular weight: 686, catalog value) was used.
As the phosphate ester flame retardant (G-3), 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 (G-4).

[Flame Retardant (H)]
Polytetrafluoroethylene (PTFE) was used as the flame retardant aid (H-1).

<Examples 1 to 22 and Comparative Examples 1 to 15>
Each component mentioned above was mix | blended as shown in Tables 1-3, and it knead | mixed using the twin-screw extruder, and obtained the pellet of the reinforced thermoplastic resin composition. 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 1-3.

  The amounts of the inorganic filler (D), glycidyl ether unit-containing polymer (E), phosphate ester flame retardant (F), and flame retardant aid (H) in Tables 1 to 3 are the resin main component (C) 100. This is the amount (parts) relative to the part. The “ratio of (D)” is the ratio (%) of the inorganic filler (D) in 100% of the reinforced thermoplastic resin composition.

  As shown in Tables 1 to 3, 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, and flame retardancy was obtained.

On the other hand, in the case of Comparative Examples 1-15, it was inferior in any item of the moldability of a reinforced thermoplastic resin composition, the impact resistance of a molded article, rigidity, mechanical strength, heat resistance, and a flame retardance. .
Specifically, in the case of Comparative Example 1 in which the proportion of the polycarbonate resin (A) is small and the proportion of the graft copolymer (B) is large, the molded product is inferior in heat resistance, flame retardancy, rigidity, and mechanical strength. It was.
In the case of Comparative Example 2 in which the ratio of the inorganic filler (D) was large, the moldability and the flame retardancy of the molded product were inferior.
In the case of Comparative Example 5 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 (C), the moldability and the molded product It was inferior in flame retardancy.
In the case of Comparative Example 6 in which the content of the phosphate ester flame retardant (G) was 30 parts with respect to 100 parts of the resin main component (C), the heat resistance of the molded product was inferior.
In the case of Comparative Example 7 where the mass average molecular weight of the glycidyl ether unit-containing polymer (E) was 1,650, the impact resistance of the molded product was inferior.
In the case of Comparative Examples 8 to 10 in which the rubbery polymer forming the graft copolymer (B) is a rubbery polymer other than the silicone-acrylic composite rubber, the flame retardancy of the molded product was inferior.
In the case of Comparative Example 11 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 (C), the flame retardancy of the molded product was inferior.

Further, from the comparison between Example 12 and Comparative Example 3, the reinforced thermoplastic resin composition of the present invention is more resistant to impact when formed into a molded product than the reinforced thermoplastic resin composition not containing the glycidyl ether unit-containing polymer. It turns out that it is excellent in property.
From a comparison between Example 12 and Comparative Example 4, the reinforced thermoplastic resin composition of the present invention was made more moldable and molded than a reinforced thermoplastic resin composition containing a PET resin that was not recycled or re-pelletized. It can be seen that it has excellent impact resistance.
From the comparison between Example 12 and Comparative Examples 8 to 10, the reinforced thermoplastic resin composition of the present invention is 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 flame retardance at the time of making a molded article rather than a thing.

  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).

Claims (4)

Obtained by polymerizing a monomer mixture (m1) containing an aromatic alkenyl compound and a vinyl cyanide compound in the presence of 80 to 95% by mass of the polycarbonate resin (A) and the rubbery polymer (B1). Resin main component (C) comprising 5 to 20% by mass of the graft copolymer (B) (however, the total of the polycarbonate resin (A) and the graft copolymer (B) is 100% by mass). ), An inorganic filler (D), a glycidyl ether unit-containing polymer (E), a polyethylene terephthalate resin (F), and a phosphate ester flame retardant (G). There,
The rubbery polymer (B1) is a silicone-acrylic composite rubber,
Content of the said inorganic filler (D) is 20-55 mass% in 100 mass% of the said 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 (C). 3 to 10 parts by mass with respect to
The polyethylene terephthalate resin (F) is recycled and / or re-pelletized, and the content of the polyethylene terephthalate resin (F) is 5 to 30 masses with respect to 100 mass parts of the resin main component (C). Department,
The phosphoric ester-based flame retardant (G) has a mass average molecular weight exceeding 326, and the content of the phosphoric ester-based flame retardant (G) is 3 to 25 mass with respect to 100 parts by mass of the resin main component (C). Part of a reinforced thermoplastic resin composition.   The reinforced thermoplastic resin composition according to claim 1, wherein the inorganic filler (D) is carbon fiber.   The reinforced thermoplastic resin composition according to claim 1, wherein the inorganic filler (D) is a glass fiber.   A molded article obtained by molding the reinforced thermoplastic resin composition according to any one of claims 1 to 3.