JP2011231283A - Reinforced thermoplastic resin composition and molded product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a reinforced thermoplastic resin composition excellent in flame retardancy and durability under high temperature and high humidity.SOLUTION: The reinforced thermoplastic resin composition comprises 50-90 mass% polycarbonate resin (A) and 10-50 mass% graft copolymer (B) [wherein the sum total of the components (A) and (B) is 100 mass%], in addition, 0.1-50 pts.mass inorganic filler (D) and 0.1-40 pts.mass specific phosphate ester-based flame retardant (E) based on 100 pts.mass sum total of the polycarbonate resin (A) and the graft copolymer (B). In the graft copolymer (B), a graft polymer (B2) comprising an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide compound monomer (b) unit is graft polymerized in the presence of the rubbery polymer (B1) of a silicone-acrylic composite rubber.

Description

  The present invention relates to a reinforced thermoplastic resin composition and a molded product used as a resin material for an electronic device casing such as a notebook personal computer, a mobile phone, a camera, and a liquid crystal projector.

  As a resin material for casings of electronic devices such as notebook personal computers, mobile phones, cameras, and liquid crystal projectors, a thermoplastic resin composition such as ABS resin or polycarbonate resin / ABS resin, or the thermoplastic resin composition is used as an inorganic filler. Reinforced thermoplastic resin compositions reinforced with are widely used. In general, as a method for manufacturing a casing, an injection molding method is employed in which the resin composition can be molded into an arbitrary shape to some extent.

In recent years, electronic devices are required to be further reduced in weight, thickness, and durability. However, among conventional resin materials for electronic equipment casings, ABS resin and polycarbonate resin / ABS resin that are not reinforced with inorganic fillers have low rigidity and can meet the demands for thinner electronic equipment casings. There wasn't.
A resin composition reinforced with glass fiber may be used as a resin material for an electronic device casing, but the balance between rigidity and mass is insufficient, and it is difficult to reduce the weight when the rigidity is increased. .

  In addition, the resin material for an electronic device casing may be required to have flame retardancy. As a flame retardant for imparting flame retardancy, in recent years, phosphorus-based flame retardants having a low environmental load are frequently used from the viewpoint of environmental considerations. Known phosphorous flame retardants include resorcinol derivatives and phosphate ester flame retardants of bisphenol A derivatives. However, the combination of the phosphoric ester-based flame retardant and the ABS resin has low heat resistance and impact resistance and is not necessarily suitable for a thin electronic device casing material. On the other hand, the combination of the above phosphoric ester flame retardant and polycarbonate resin / ABS resin significantly reduces physical properties in environmentally accelerated tests (for example, tests under high temperature and high humidity environments) assuming reduced heat resistance and long-term use. It sometimes occurred. Since the higher the quality of the casing, the better. Therefore, it is preferable that the deterioration of physical properties in the environmental promotion test is suppressed as much as possible.

Patent Document 1 proposes a resin composition that includes a polycarbonate resin, an ABS resin, an AS resin, a phosphate ester flame retardant, and a fluorinated polyolefin, and is excellent in flame retardancy, impact resistance, and moldability. Yes.
Patent Document 1 describes that the graft polymer is desirably a butadiene polymer containing a butadiene group. However, these graft polymers do not provide sufficient flame retardancy, and in addition, in the environmental acceleration test. The physical properties were also greatly reduced. Furthermore, in Patent Document 1, a phosphoric ester-based flame retardant of a diphenyl derivative is used in order to suppress a decrease in heat resistance, but durability has not been improved.

Japanese Patent No. 4257688

  An object of the present invention is to provide a reinforced thermoplastic resin composition excellent in flame retardancy and durability under high temperature and high humidity. It is another object of the present invention to provide a molded article excellent in flame retardancy and durability under high temperature and high humidity.

The present invention includes the following aspects.
[1] Polycarbonate resin (A) 50 to 90% by mass and graft copolymer (B) 10 to 50% by mass (provided that the total of component (A) and component (B) is 100% by mass). And 0.1 to 50 parts by mass of inorganic filler (D) and phosphoric acid represented by the following formula (I) with respect to a total of 100 parts by mass of polycarbonate resin (A) and graft copolymer (B) 0.1 to 40 parts by mass of an ester-based flame retardant (E), and the graft copolymer (B) is an aromatic alkenyl compound in the presence of a rubbery polymer (B1) of a silicone-acrylic composite rubber. A reinforced thermoplastic resin composition, wherein the graft polymer (B2) having a monomer (a) unit and a vinyl cyanide compound monomer (b) unit is graft-polymerized.
(Wherein R ¹ and R ² each independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 5)

[2] The reinforced thermoplastic resin composition according to [1], comprising a polymer (F) having a glycidyl ether unit.
[3] The reinforced thermoplastic resin composition according to [1] or [2], wherein the inorganic filler (D) is carbon fiber.
[4] A molded product obtained by molding the reinforced thermoplastic resin composition according to any one of [1] to [3].

The reinforced thermoplastic resin composition and molded article of the present invention are excellent in flame retardancy and durability under high temperature and high humidity.
The molded product of the present invention is excellent in flame retardancy and durability under high temperature and high humidity.

"Reinforced thermoplastic resin composition"
The reinforced thermoplastic resin composition of the present invention comprises a polycarbonate resin (A), a graft copolymer (B), an inorganic filler (D), and a phosphate ester flame retardant represented by the above formula (I) ( E) as an essential component.

<Polycarbonate resin (A)>
The polycarbonate resin (A) is a resin obtained from dihydroxydiarylalkane, and may be arbitrarily branched.
The polycarbonate resin (A) is produced by a known method. For example, it is produced by a method of reacting a dihydroxy or polyhydroxy compound with phosgene or a diester of carbonic acid or a melt polymerization method. In addition, recycled ones from compact discs can be used.
As the dihydroxydiarylalkane, for example, one having an alkyl group at the ortho position relative to the hydroxy group is used. Preferable specific examples of the dihydroxydiarylalkane include 4,4-dihydroxy2,2-diphenylpropane (that is, bisphenol A), tetramethylbisphenol A and bis- (4-hydroxyphenyl) -p-diisopropylbenzene. .

A branched polycarbonate is produced, for example, by substituting a part of a dihydroxy compound, for example, 0.2 to 2 mol% with polyhydroxy. 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.
Polycarbonate resin (A) may be used individually by 1 type, and may mix and use 2 or more types.

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 reinforced thermoplastic resin composition becomes higher, and when it is 35,000 or less, the moldability of the reinforced thermoplastic resin composition. Becomes higher.
The viscosity average molecular weight (Mv) of the polycarbonate resin (A) is more preferably 17,000 to 25,000 because the balance between mechanical strength, surface impact strength by a falling ball test, and fluidity is particularly excellent. .

[Content of Polycarbonate Resin (A)]
The content of the polycarbonate resin (A) is the total amount of the component (A) and the component (B) (hereinafter, the component composed of the component (A) and the component (B) is referred to as “resin main component (C)”). When it is 100% by mass, it is 50 to 90% by mass, and preferably 80 to 90% by mass. When the content of the polycarbonate resin (A) is less than 50% by mass, the impact resistance of the reinforced thermoplastic resin composition is lowered, and when it exceeds 90% by mass, the moldability of the reinforced thermoplastic resin composition is lowered. .

<Graft copolymer (B)>
The graft copolymer (B) contains an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide compound monomer (b) unit in the presence of a rubber-like polymer (B1) of a silicone-acrylic composite rubber. The graft polymer (B2) possessed is graft polymerized.
When the rubber polymer is a silicone-acrylic composite rubber polymer, flame retardancy and durability under high temperature and high humidity are improved.

[Rubber polymer (B1)]
The silicone 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).
Here, 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, n -Alkyl methacrylates such as lauryl methacrylate. 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 polyorganosiloxane rubber is covered with an alkyl (meth) acrylate rubber, and the periphery of the core layer of the alkyl (meth) acrylate rubber is poly Core-shell structure covered with organosiloxane rubber, structure where polyorganosiloxane rubber and alkyl (meth) acrylate rubber are entangled with each other, segment of polyorganosiloxane and segment of polyalkyl (meth) acrylate are linear and three-dimensional For example, a structure having a net-like rubber structure bonded to each other can be used.

The silicone-acrylic composite rubbery polymer (B1) is prepared, for example, by subjecting a monomer forming the silicone-acrylic composite rubbery polymer (B1) to emulsion polymerization by acting a radical polymerization initiator. . According to the preparation method by the emulsion polymerization method, it is easy to control the particle diameter of the silicone-acrylic composite rubber 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.

  The content of the silicone-acrylic composite rubber polymer (B1) is preferably 5 to 25% by mass when the resin main component (C) is 100% by mass. If the content of the silicone-acrylic composite rubber polymer (B1) is 5% by mass or more, the impact resistance of the reinforced thermoplastic resin composition can be further increased, and if it is 25% by mass or less, the moldability is more improved. It becomes higher and the appearance of the molded product becomes better.

[Graft polymer (B2)]
The graft polymer (B2) has an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide compound monomer (b) unit as essential components, and a monomer (c ) Unit as an optional component. These composition ratios are not particularly limited, but preferably 50 to 90% by mass of the aromatic alkenyl compound monomer (a) unit and the vinyl cyanide compound unit because of excellent balance between impact resistance and moldability. The monomer (b) unit is 10 to 50% by mass and the monomer (c) unit is 0 to 40% by mass (provided that the total of (a), (b) and (c) is 100% by mass). .
Examples of the aromatic alkenyl compound monomer (a) include styrene, α-methylstyrene, vinyltoluene, and the like, and preferably styrene.
Examples of the vinyl cyanide compound monomer (b) include acrylonitrile and methacrylonitrile, with acrylonitrile being preferred.
Monomers (c) copolymerizable with these include methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and 2-ethylhexyl methacrylate, acrylic acid esters such as methyl acrylate, ethyl acrylate and butyl acrylate, N-phenylmaleimide and the like. And maleimide compounds.
A graft copolymer (B) may be used individually by 1 type, and may use 2 or more types together.

[Acetone insoluble and acetone soluble in graft copolymer (B)]
The graft copolymer (B) has a reduced viscosity measured at 25 ° C. as a 0.2 g / dl N, N-dimethylformamide solution containing 70 to 99% by mass of an insoluble content in an acetone solvent and having an acetone soluble content of 0.2 g / dl. Is preferably 0.3 to 0.7 dl / g. If the insoluble content in the acetone solvent is 70% by mass or more, the molding appearance and moldability of the reinforced thermoplastic resin composition are further improved. On the other hand, if it is 99% by mass or less, the tear strength of the reinforced thermoplastic resin composition. Will improve.
Further, if the reduced viscosity of acetone-soluble component is 0.3 dl / g or more, the tear strength of the reinforced thermoplastic resin composition is improved, and if it is 0.7 dl / g or less, the reinforced thermoplastic resin composition. The molding appearance and moldability of the are further improved.

In addition, the measuring method of an acetone soluble part 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 is measured at 25 ° C. using a 0.2 g / dl N, N-dimethylformamide solution.
Here, the soluble part with respect to an acetone solvent is a polymer similar to the graft polymer (B2), and is a polymer not grafted to the rubbery polymer (B1). The soluble component in the acetone solvent is often generated at the same time when the graft polymer (B2) is graft polymerized with the rubbery polymer (B1).

[Production method of graft copolymer (B)]
In the presence of the rubbery polymer (B1), the graft copolymer (B) is an aromatic alkenyl compound monomer (a), a vinyl cyanide compound monomer (b), and if necessary, It can be obtained by graft polymerization with another monomer (c).
Although there is no restriction | limiting in the polymerization method of a graft copolymer (B), 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 and graft ratio of the graft copolymer (B).

[Content of Graft Copolymer (B)]
The content of the graft copolymer (B) in the resin main component (C) is 10 to 50% by mass, preferably 10 to 20% by mass (provided that the components (A) and (B) Is 100% by mass.). When the content of the graft copolymer (B) in the resin main component (C) is less than 10% by mass, the moldability of the reinforced thermoplastic resin composition is not sufficient, and when it exceeds 50% by mass, The flame retardancy of the reinforced thermoplastic resin composition is reduced.

<Inorganic filler (D)>
Examples of the inorganic filler (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, Examples thereof include inorganic substances such as magnesium carbonate, carbon black and ketjen black, metals and alloys such as iron, copper, zinc and aluminum, and fibers and powders of oxides thereof. A preferable form of the untreated inorganic filler includes fibrous ones, and among these, carbon fibers that can obtain high rigidity with less blending are preferable. An inorganic filler (D) may be used individually by 1 type, and may use 2 or more types together.

The inorganic filler (D) can also be used by treating the surface with a surface treatment agent such as a coupling agent (for example, a silane coupling agent or a titanate coupling agent).
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 a thermosetting resin such as a polyurethane resin or an epoxy resin.

  Content of an inorganic filler (D) is 0.1-50 mass parts with respect to 100 mass parts of resin main components (C), Preferably it is 5-30 mass parts. If the content of the inorganic filler (D) is less than 0.1 parts by mass, the rigidity and the like of the reinforced thermoplastic resin composition cannot be sufficiently improved, and if it exceeds 50 parts by mass, the reinforced thermoplastic resin The moldability of the composition decreases.

<Phosphate ester flame retardant (E)>
The phosphate ester flame retardant is a compound represented by the above formula (I), and both R ¹ and R ² may be a hydrogen atom, both may be a methyl group, A hydrogen atom and the other may be a methyl group.

  Content of a phosphate ester type flame retardant (E) is 0.1-40 mass parts with respect to 100 mass parts of resin main components (C), and it is preferable that it is 15-25 mass parts. If the content of the phosphate ester flame retardant (E) is less than 0.1 parts by mass, flame retardancy cannot be obtained, and even if it exceeds 40 parts by mass, the flame retardancy may be reduced. Heat resistance tends to decrease.

<Other flame retardants>
The reinforced thermoplastic resin composition of the present invention may contain a known non-halogen flame retardant in addition to the phosphate ester flame retardant (E), and may be used in combination with the phosphate ester flame retardant (E). Absent. Examples of non-halogen flame retardants include inorganic flame retardants such as red phosphorus and aluminum hydroxide.
As the red phosphorus flame retardant, a thermosetting resin or a material that is stabilized by being coated with a thermosetting resin and a metal hydroxide is 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.

<Flame retardant aid>
The reinforced thermoplastic resin composition of the present invention may contain a flame retardant aid (G) for preventing drip during combustion. Examples of the flame retardant aid include polytetrafluoroethylene, a compound containing tetrafluoroethylene, and a silicone polymer.
When blending polytetrafluoroethylene or a compound containing tetrafluoroethylene as the flame retardant aid (G), the blending amount is 0 with respect to 100 parts by mass of the resin main component (C) in terms of surface appearance. It is preferably 5 parts by mass or less.

<Glycidyl ether unit-containing polymer (F)>
The reinforced thermoplastic resin composition of the present invention may contain a glycidyl ether unit-containing polymer (F). As a glycidyl ether unit containing polymer (F), 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 high molecular weight substances such as bisphenol type epoxy resin, novolac type epoxy resin, polyglycidyl ether of aliphatic polyhydric alcohol, and biphenyl type epoxy resin, which are represented by the following formula (II). And those having a polymer having such a repeating unit (for example, an epoxy group-containing phenoxy resin).

（ｍは１以上の整数を表す。）

(M represents an integer of 1 or more.)

Furthermore, 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 (eg, ethylene glycol diglycidyl ether), polyoxyalkylene glycol diglycidyl ether (eg, 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.
These glycidyl ether type epoxy resins may be used alone or in combination of two or more.

  Preferred glycidyl ether unit-containing polymer (F) is bisphenol A type epoxy resin, bisphenol F type epoxy resin, epoxy resin having a structure of bisphenol A and bisphenol F, phenol novolac type epoxy resin, cresol novolac type epoxy resin, epoxy group Containing phenoxy resin. If these preferable polymers are used, the durability under high temperature and high humidity is further improved.

  As the glycidyl ether unit-containing polymer (F), a liquid, semi-solid, and solid polymer can be used at room temperature (20 ° C.). However, when considering the workability at the time of extrusion, it is solid. Those are preferred.

  The glycidyl ether unit-containing polymer (F) is, for example, “jER” series manufactured by Japan Epoxy Resin Co., Ltd., “Epototo” series manufactured by Tohto Kasei Co., Ltd., “Phenototo” series, “AER” manufactured by Asahi Kasei Chemicals Corporation. ”Series,“ Epicron ”series manufactured by Dainippon Ink and Chemicals, Inc. are commercially available.

  The content of the glycidyl ether unit-containing polymer (F) in the reinforced thermoplastic resin composition is preferably 1 to 12 parts by mass, and 3 to 9 parts by mass with respect to 100 parts by mass of the resin main component (C). More preferably. If the content of the glycidyl ether unit-containing polymer (F) is 1 part by mass or more, the durability of the molded product obtained from the reinforced thermoplastic resin composition under high temperature and high humidity can be sufficiently improved, If it is 12 mass parts or less, the moldability of a reinforced thermoplastic resin composition is securable. In addition, if the content of the glycidyl ether unit-containing polymer (F) is within the above range, durability under high temperature and high humidity due to a synergistic effect with the phosphate ester flame retardant (E) represented by the formula (I) Can be higher.

<Other ingredients>
The reinforced thermoplastic resin composition of the present invention may contain other modifiers, mold release agents, stabilizers against light or heat, antistatic agents, dyes, pigments and the like, if necessary.

<Manufacturing method>
The reinforced thermoplastic resin composition of the present invention includes a polycarbonate resin (A), a graft copolymer (B), an inorganic filler (D), a phosphate ester flame retardant (E), and others as required. Are mixed using a mixing apparatus (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>
As described above, the reinforced thermoplastic resin composition of the present invention containing the polycarbonate resin (A), the graft copolymer (B), the inorganic filler (D), and the phosphate ester flame retardant (E) is difficult. Excellent flammability and durability under high temperature and high humidity.

"Molding"
The molded article of the present invention is obtained by molding the above reinforced thermoplastic resin composition.
Examples of the molding method of the reinforced thermoplastic resin composition include an injection molding method, an injection compression molding method, an extrusion method, a blow molding method, a vacuum molding method, a pressure molding method, a calendar molding method, and an inflation molding method. . 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.

  The molded article of the present invention includes, for example, a personal computer (including a notebook 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 camera, digital camera, etc.) ), Video equipment such as video, musical instruments, mobile equipment (electronic notebook, personal digital assistant (PDA), etc.), lighting equipment, communication equipment such as telephone (including mobile phone), fishing gear, pachinko goods It can be applied to play equipment such as vehicles, products for vehicles, products for furniture, sanitary products, products for building materials. Among these uses, the effects of the present invention are particularly exerted, so that it is suitable for a casing of an electronic component such as a notebook personal computer, a portable device, or a camera.

  Hereinafter, an example is shown concretely. The present invention is not limited to these examples. Further, “part” and “%” described below mean “part by mass” and “% by mass”, respectively.

In the following examples, the following components were used.
[Polycarbonate resin (A)]
As the polycarbonate resin (A), “Novalex 7021PJ” manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used.

[Production of Graft Copolymer (B-1)]
A graft copolymer (B-1) using a polysiloxane rubber / polybutyl acrylate composite rubber as a rubber 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, and a composite rubber latex of polyorganosiloxane and butyl acrylate rubber was obtained.
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 latex obtained by grafting acrylonitrile-styrene copolymer to a composite rubber composed of polyorganosiloxane and butyl acrylate rubber.
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. 100 parts of the latex of the graft copolymer was gradually dropped into the calcium acetate aqueous solution to be coagulated. The obtained solidified product was separated, washed, and dried to obtain a dry powder of the graft copolymer (B-1).
The acetone soluble part of this graft copolymer (B-1) was 26%. Moreover, the reduced viscosity of the acetone-soluble component was 0.60 dl / g.

[Production of Graft Copolymer (B-2)]
Copolymer having an average particle size of 0.08 μm consisting of 85% n-butyl acrylate units and 15% methacrylic acid units in 100 parts (as solid content) of polybutadiene latex having a solid content concentration of 35% and an average particle size of 0.08 μm. 2 parts of latex (as solids) was added with stirring. Next, stirring was continued for 30 minutes to obtain an enlarged butadiene rubber polymer latex having an average particle size of 0.28 μm.
The obtained enlarged butadiene rubber polymer latex was charged into a reactor, and further 100 parts of distilled water, 4 parts of a wood rosin emulsifier, and Demol N (trade name, manufactured by Kao Corporation, naphthalenesulfonic acid formalin condensate) 4 parts, 0.04 part of sodium hydroxide and 0.7 part of dextrose were added. Next, the temperature was raised with stirring, and at the time when the internal temperature was 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 the following components were added. The containing mixture was dripped continuously over 90 minutes and then held for 1 hour to cool.
Acrylonitrile 30 parts Styrene 70 parts Cumene hydroperoxide 0.4 parts tert-dodecyl mercaptan 1 part The graft copolymer latex thus obtained is coagulated with dilute sulfuric acid, washed, filtered and dried to obtain a graft copolymer. A dry powder of (B-2) was obtained.
The acetone soluble part of this graft copolymer (B-2) was 27%. Moreover, the reduced viscosity of the acetone-soluble component was 0.3 dl / g.

In addition, the measuring method of acetone soluble part is as follows.
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 of graft copolymer) − [mass of sample after drying]), the content ratio (%) of acetone-soluble content relative to the graft copolymer was determined.
The reduced viscosity was measured at 25 ° C. using a 0.2 g / dl N, N-dimethylformamide solution.

[Production of Graft Copolymer (B-3)]
The raw materials were charged into the reactor in the following proportions and polymerized while stirring at 50 ° C. for 4 hours under nitrogen substitution to obtain rubber latex.
n-butyl acrylate 98 parts 1,3-butylene glycol dimethacrylate 1 part allyl methacrylate 1 part sodium dioctyl sulfosuccinate 2.0 parts deionized water 300 parts potassium persulfate 0.3 parts disodium phosphate 12-hydrate 0.5 Part Sodium hydrogen phosphate 12-hydrate 0.3 part 100 parts of the rubber latex obtained (in terms of solid content) was charged into another reactor, diluted with 280 parts of ion-exchanged water, and heated to 70 ° C. Warm up.
Separately, 0.7 part of benzoyl peroxide is dissolved in 100 parts of a monomer mixture composed of acrylonitrile / styrene = 29/71 (mass ratio), and after nitrogen substitution, 30 parts of the monomer mixture is added. It was added by a metering pump to the reactor containing the above rubber latex at a rate of / hour. After all the monomers were added, the temperature in the reactor was raised to 80 ° C., and stirring was continued for 30 minutes to obtain a graft copolymer latex. The polymerization rate was 99%.
The above graft copolymer latex, the coagulation bath charged with 3 volumes of aluminum chloride of the total latex _{(AlCl 3 .6H 2 O) 0.15} % aqueous solution (90 ° C.), was charged with stirring, solidified I let you. 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 and washed with a centrifuge, and then dried to obtain a dry powder of the graft copolymer (B-3).
The acetone soluble part of this graft copolymer (B-3) was 21%. Moreover, the reduced viscosity of the acetone-soluble component was 0.70 dl / g.

[Production of Graft Copolymer (B-4)]
A graft copolymer (B-4) using a polybutadiene / polybutyl acrylate composite rubber as a rubbery polymer was obtained by the following method.
Copolymer latex having an average particle size of 0.10 μm consisting of 82% of n-butyl acrylate units and 18% of methacrylic acid units in 20 parts of polybutadiene latex having a solid content concentration of 35% and an average particle size of 0.08 μm (as solid content). 0.4 parts (as solids) were added with stirring. Next, stirring was continued for 30 minutes to obtain an enlarged diene rubber latex having an average particle size of 0.36 μm.
Charge 20 parts (in terms of solid content) of the resulting enlarged diene rubber latex into 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). Further, a solution in which 0.0002 part of ferrous sulfate, 0.0006 part of ethylenediaminetetraacetic acid disodium salt and 0.25 part of Rongalite was added to 10 parts of ion exchange water was added to the reactor and reacted. .
n-Butyl acrylate 80 parts Allyl methacrylate 0.32 parts Ethylene glycol dimethacrylate 0.16 parts Although the internal temperature at the end of the reaction was 75 ° C., the temperature was further raised to 80 ° C. and the reaction was continued for 1 hour to enlarge. A composite rubber of a modified diene rubber and a polybutyl acrylate rubber was obtained. The polymerization rate was 98.8%.
Next, 50 parts (in terms of solid content) of a composite rubber latex of enlarged diene rubber and polybutyl acrylate rubber was charged into the reactor, diluted by adding 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 latex by a metering pump. After all the monomers were added, the temperature in the reactor was raised to 80 ° C., and stirring was continued for 30 minutes to obtain a graft copolymer latex. The polymerization rate was 99%.
The graft copolymer 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 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 this, the solution was removed and washed with a centrifuge, and then dried to obtain a dry powder of the graft copolymer (B-4).
The acetone soluble part of this graft copolymer (B-4) was 20%. Moreover, the reduced viscosity of the acetone-soluble component was 0.7 dl / g.

[Inorganic filler (D)]
As the inorganic filler (D), carbon fiber, “HTA-C6-U” manufactured by Toho Tenax Co., Ltd. was used.

[Phosphate ester flame retardant (E) and flame retardant aid (G)]
As the phosphate ester flame retardant (E-1), “FP-800” (biphenyl derivative, solid at room temperature) manufactured by ADEKA Corporation was used.
As the phosphate ester flame retardant (E-2), “PX-200” (resorcinol derivative, solid at room temperature) manufactured by Daihachi Chemical Co., Ltd. was used.
As the phosphate ester flame retardant (E-3), “CR-741” (bisphenol A derivative, liquid at room temperature) manufactured by Daihachi Chemical Co., Ltd. was used.
Polytetrafluoroethylene (PTFE) was used as the flame retardant aid (G).

[Other ingredients]
About the following Example 2 and Comparative Examples 2 and 4, Japan Epoxy Resin Co., Ltd. "1256" was mix | blended as a glycidyl ether unit containing polymer (F).

  Each component mentioned above was mix | blended as shown in Table 1, and the reinforced thermoplastic resin composition was obtained. The tensile strength and flame retardancy before and after the high temperature and high humidity treatment of the obtained reinforced thermoplastic resin composition were evaluated by the following methods. The evaluation results are shown in Table 1.

[Tensile strength retention after high temperature and high humidity treatment]
The test piece was allowed to stand for 800 hours in a high-temperature and high-humidity atmosphere at a temperature of 80 ° C. and a relative humidity of 95%. Measured according to The retention rate was calculated as follows.
Retention rate (%) = (Tensile strength after high-temperature and high-humidity treatment × 100) / Tensile strength before high-temperature and high-humidity treatment

[Flame retardance]
A test piece (width 12.7 mm, length 127 mm, thickness 1.0 mm) was produced by injection molding the reinforced thermoplastic resin composition, and the following vertical combustion test based on UL94 was performed.

-Vertical combustion test The burner flame was applied to the lower end of the said test piece supported perpendicularly, and it kept for 10 seconds, and the burner flame was separated from the test piece after that. After the flame disappeared, the burner flame was applied again and the same operation was performed. The determination was made based on the flaming combustion duration after the completion of the first flame contact, the sum of the second flaming combustion duration and the flameless combustion duration, and the presence or absence of combustion fallen objects. The standards for each grade in UL94 are as follows.
V-0: The duration of the first flammable combustion was within 10 seconds, and the sum of the second flammable combustion duration and the flameless combustion duration was within 30 seconds, and there were no burning fallen objects.
V-1: The duration of the first flammable combustion is more than 10 seconds within 30 seconds and the total of the second flammable combustion duration and the flameless combustion duration is more than 30 seconds and within 60 seconds, There wasn't.
V-2: The duration of the first flammable combustion is over 10 seconds within 30 seconds, and the total of the second flammable combustion duration and the flameless combustion duration is over 30 seconds within 60 seconds, there were.
The flame retardancy of Examples 1 and 2 and Comparative Examples 1 to 7 in Table 1 is represented by the following symbols.
○: V-0 level flame retardancy was exhibited.
X: It had V-1 level flame retardancy.

From the comparison between Example 1 and Comparative Examples 1 and 3, the reinforced thermoplastic resin composition of Example 1 containing a phosphate ester flame retardant of a biphenyl derivative is a comparative example containing a phosphate ester flame retardant other than a biphenyl derivative. It was found that the tensile strength was superior to the reinforced thermoplastic resin compositions 1 and 3, and the tensile strength retention after the high temperature and high humidity test was also high. In Example 1 and Comparative Examples 1 and 3, the tensile strength after the high-temperature and high-humidity test was higher than that of the non-reinforced thermoplastic resin composition of Comparative Example 8 before the high-temperature and high-humidity test. Only the reinforced thermoplastic resin composition of Example 1 was obtained.
Further, from the comparison between Example 1 and Comparative Examples 5, 6, and 7, the reinforced thermoplastic resin composition of Example 1 containing a polysiloxane rubber / polybutyl acrylate composite rubber polymer is polysiloxane rubber / poly Comparative Examples 5, 6 and 7 containing a rubbery polymer other than a butyl acrylate composite rubbery polymer are superior in flame retardancy and tensile strength before and after a high temperature and high humidity test, and particularly high in high temperature. It was found that the tensile strength retention after the wet test was high.
Furthermore, from the comparison between Example 2 and Comparative Examples 2 and 4, the reinforced thermoplastic resin composition of Example 2 containing a phosphoric ester-based flame retardant of a biphenyl derivative and a glycidyl ether unit-containing polymer is other than the biphenyl derivative. The tensile strength is superior to the reinforced thermoplastic resin composition of Comparative Examples 2 and 4 containing a phosphate ester flame retardant and a glycidyl ether unit-containing polymer. Particularly, the tensile strength retention rate after a high temperature and high humidity test is high. It was. Therefore, excellent durability under high temperature and high humidity can be obtained only by using a phosphate ester flame retardant of a biphenyl derivative, but by using a phosphate ester flame retardant of a glycidyl ether unit-containing polymer and a biphenyl derivative. It is clear that the synergistic effect is even better.

Claims (4)

Polycarbonate resin (A) 50-90 mass%, graft copolymer (B) 10-50 mass% (however, the sum total of (A) component and (B) component is 100 mass%), and polycarbonate 0.1 to 50 parts by mass of the inorganic filler (D) and the phosphate ester-based difficulty represented by the following formula (I) with respect to a total of 100 parts by mass of the resin (A) and the graft copolymer (B) Containing 0.1 to 40 parts by mass of a flame retardant (E),
The graft copolymer (B) comprises an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide compound monomer (b) unit in the presence of a rubber-like polymer (B1) of a silicone-acrylic composite rubber. A reinforced thermoplastic resin composition, which is obtained by graft polymerization of a graft polymer (B2) having styrene.

(Wherein R ¹ and R ² each independently represents a hydrogen atom or a methyl group, and n represents an integer of 1 to 5)   The reinforced thermoplastic resin composition according to claim 1, comprising a polymer (F) having a glycidyl ether unit.   The reinforced thermoplastic resin composition according to claim 1 or 2, wherein the inorganic filler (D) is carbon fiber.   A molded article, wherein the reinforced thermoplastic resin composition according to any one of claims 1 to 3 is molded.