HK1171242B - Reinforced thermoplastic resin composition and molded article - Google Patents

Description

Reinforced thermoplastic resin composition and molded article

Technical Field

The present invention relates to a reinforced thermoplastic resin composition and a molded article used as a material for a case of a notebook-size personal computer, a liquid crystal projector, a portable device, or the like.

The present application claims priority based on japanese application No. 2009-218504 at 24/9/2009, the contents of which are incorporated herein by reference.

Background

As materials for electronic device housings of notebook-size personal computers, liquid crystal projectors, portable devices, and the like, thermoplastic resin compositions such as ABS resins, polycarbonate resins, ABS resins, and the like, or reinforced thermoplastic resin compositions in which the thermoplastic resin compositions are reinforced with inorganic fillers are widely used. Generally, as a method for manufacturing a housing, a method of molding the resin composition by injection molding capable of freely forming a shape to some extent is employed.

In recent years, electronic devices are required to be further lightweight and thin, and to be able to sufficiently withstand an impact or load in a state of being packed in a leather bag or the like. To meet this requirement, it is necessary for the resin used in the housing to have not only high rigidity and impact resistance but also high impact resistance when the product is dropped.

Among them, it is known that the impact resistance when the product is dropped has a high correlation with the surface impact strength measured in the ball drop test of UL1950 standard and the correlation with Izod impact strength or Charpy impact strength is low. Therefore, the resin used for the case is required to have high surface impact strength, not high Izod impact strength or Charpy impact strength.

Among resin materials for electronic device cases used in the past, ABS resins and polycarbonate resins/ABS resins that are not reinforced with inorganic fillers have low rigidity and cannot meet the recent demand for thinner electronic device cases.

In addition, although a glass fiber reinforced resin composition is sometimes used as a resin material for an electronic device case, the balance between rigidity and mass is insufficient.

Therefore, as a material for an electronic device case, a thermoplastic resin composition reinforced with carbon fibers has been studied.

However, although conventional carbon fiber-reinforced thermoplastic resin compositions have high rigidity and are lightweight, they have a disadvantage that they are brittle and easily cracked as a material for a housing.

In order to overcome the above-mentioned drawbacks, patent document 1 proposes a carbon fiber surface-treated with a polyamide, which contains an aromatic polycarbonate resin, and has a carboxyl group, a carboxylic anhydride group, an epoxy group and a carboxyl groupA lubricant of at least 1 functional group selected from oxazoline groups.

Patent document 1 describes: carbon fibers surface-treated with polyamide dissolved in methanol were used, but high impact resistance (Izod impact strength) could not be achieved only with this. In addition, the carbon fiber of patent document 1 does not improve the surface impact strength. Further, the resin composition described in patent document 1 has a disadvantage that the amount of gas generated during molding is large because it contains a lubricant.

Further, as a means different from patent document 1, patent document 2 proposes a carbon fiber-reinforced polycarbonate resin composition containing a polycarbonate resin, a rubber-containing polymer, and carbon fibers bundled with a polyamide-based bundling agent. As the rubber-containing polymer in patent document 2, a (meth) acrylate having an alkyl group with 1 to 18 carbon atoms, an MBS resin mainly composed of butadiene and styrene, or a MAS resin composed of a methacrylate, an acrylate and styrene is used. As the polyamide sizing agent, nylon 3, nylon 4, nylon 6, nylon 66, and the like are used.

However, the carbon fiber-reinforced polycarbonate resin composition described in patent document 2 cannot improve the surface impact strength.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2001-240738

Patent document 2: japanese patent laid-open publication No. 60-88062

Disclosure of Invention

Problems to be solved by the invention

The present invention aims to provide a reinforced thermoplastic resin composition which has excellent moldability and generates little gas during molding, and which can improve the rigidity of the molded article obtained and the impact resistance (surface impact strength by a ball drop test) of the article when dropped.

Further, the present invention has an object to provide a molded article having high rigidity and high impact resistance when the article is dropped.

Means for solving the problems

The present invention includes the following aspects.

[1] A reinforced thermoplastic resin composition characterized by containing: 50 to 90 mass% of a polycarbonate resin (A), 10 to 50 mass% of a graft copolymer mixture (B) (wherein the total of the components (A) and (B) is 100 mass%), and 6 to 22 parts by mass of an inorganic filler (D) surface-treated with a water-soluble polyamide based on 100 parts by mass of the total of the polycarbonate resin (A) and the graft copolymer mixture (B); the graft copolymer mixture (B) comprises a graft copolymer (B') in which a graft polymer (B2) having an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide compound monomer (B) unit is graft-polymerized with a rubbery polymer (B1).

[2] The reinforced thermoplastic resin composition as described in [1], which further comprises a phosphate-based flame retardant (E).

[3] The reinforced thermoplastic resin composition as described in [2], wherein the phosphate-based flame retardant (E) has a mass average molecular weight of 326 to 800.

[4] The reinforced thermoplastic resin composition as described in any one of [1] to [3], wherein the inorganic filler (D) surface-treated with a water-soluble polyamide is a carbon fiber surface-treated with a water-soluble polyamide.

[5] A molded article, which is obtained by molding the reinforced thermoplastic resin composition as described in any one of [1] to [4 ].

ADVANTAGEOUS EFFECTS OF INVENTION

The reinforced thermoplastic resin composition of the present invention has excellent moldability, generates little gas during molding, and can improve the rigidity of the resulting molded article and the impact resistance (surface impact strength by a ball drop test) of the article when dropped.

The molded article of the present invention has high rigidity and high impact resistance when the article is dropped.

Detailed Description

Reinforced thermoplastic resin composition "

The reinforced thermoplastic resin composition of the present invention contains, as essential components, a polycarbonate resin (a), a graft copolymer mixture (B), and an inorganic filler (D) surface-treated with a water-soluble polyamide.

In the present specification, a component composed of the polycarbonate resin (a) and the graft copolymer mixture (B) is referred to as a resin main component (C).

< polycarbonate resin (A) >

The polycarbonate resin (A) is a resin obtained from a dihydroxydiarylalkane, and may be optionally branched.

The polycarbonate resin (a) is produced by a known method. For example, the polycarbonate resin is produced by a melt polymerization method in which a dihydroxy or polyhydroxy compound is reacted with phosgene or a diester of carbonic acid. In addition, recycled polycarbonate resins from CD and the like may also be used.

As the dihydroxydiarylalkane, for example, dihydroxydiarylalkane having an alkyl group at the ortho-position with respect to the hydroxyl group can be used. Preferred specific examples of the dihydroxydiarylalkanes include 4, 4-dihydroxy-2, 2-diphenylpropane (i.e., bisphenol A), tetramethylbisphenol A, and bis- (4-hydroxyphenyl) -p-diisopropylbenzene.

The branched polycarbonate is produced by substituting, for example, 0.2 to 2 mol% of a dihydroxy compound constituting a polycarbonate resin with a polyhydroxy compound. Specific examples of the polyhydric compound include phloroglucinol, 4, 6-dimethyl-2, 4, 6-tris- (4-hydroxyphenyl) -heptene, 4, 6-dimethyl-2, 4, 6-tris- (4-hydroxyphenyl) -heptane, 1, 3, 5-tris- (4-hydroxyphenyl) -benzene, and the like.

The polycarbonate resin (A) may be used alone in 1 kind, or may be used in a mixture of 2 or more kinds.

The viscosity average molecular weight (Mv) of the polycarbonate resin (A) is preferably 15,000 to 35,000. If 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 if 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, since it is particularly excellent in balance between mechanical strength, surface impact strength in a ball drop test, and fluidity.

[ content of polycarbonate resin (A) ]

The content of the polycarbonate resin (a) in the resin main component (C) is 50 to 90 mass%, preferably 80 to 90 mass% (wherein the total of the component (a) and the component (B) is 100 mass%). If 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 if it exceeds 90% by mass, the moldability of the reinforced thermoplastic resin composition is lowered.

< graft copolymer mixture (B) >

The graft copolymer mixture (B) is a reaction product obtained by graft polymerizing the aromatic vinyl compound monomer (a) units and the vinyl cyan compound monomer (B) units with the rubbery polymer (B1). The graft copolymer mixture (B) comprises a graft copolymer (B') in which a graft polymer (B2) having an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide compound monomer (B) unit is graft-polymerized with a rubbery polymer (B1), and a polymer (B ") having an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide compound monomer (B) unit but not having a rubbery polymer (B1).

[ acetone-insoluble fraction and acetone-soluble fraction of graft copolymer mixture (B) ]

The graft copolymer mixture (B) comprises an "acetone insoluble fraction" insoluble in acetone and an "acetone soluble fraction" soluble in acetone.

The acetone-insoluble fraction contains a graft copolymer (B') in which a graft polymer (B2) having an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide compound monomer (B) unit is graft-polymerized with a rubbery polymer (B1).

The acetone-soluble component contains a polymer (B ") having an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide compound monomer (B) unit but not having the rubbery polymer (B1). The polymer (B ") was a polymer having the same monomer composition as the monomer constituting the graft polymer (B2), and was not graft-polymerized with the rubber polymer (B1).

[ rubbery Polymer (B1) ]

Examples of the rubbery polymer (B1) in the graft copolymer mixture (B) include butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, isoprene rubber, chloroprene rubber, butyl rubber, ethylene-propylene-non-conjugated diene rubber, epichlorohydrin rubber, diene-acrylic composite rubber, silicone (polysiloxane) -acrylic composite rubber, and the like. Among these, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, acrylic rubber, diene-acrylic composite rubber, and silicone-acrylic composite rubber are preferable because the molded article obtained from the reinforced thermoplastic resin composition has good plating properties.

The diene component of the diene-acrylic composite rubber contains 50 mass% or more of a butadiene unit, and specifically, is a butadiene rubber, a styrene-butadiene rubber, an acrylonitrile-butadiene rubber, or the like.

The acrylic rubber component in the diene-acrylic composite rubber is obtained by polymerizing (f) an alkyl (meth) acrylate and (g) a polyfunctional monomer.

In the present specification, "(meth) acrylate" means one or both of an acrylate having a hydrogen atom bonded to the α -position and a methacrylate having a methyl group bonded to the α -position.

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; alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate, and n-dodecyl methacrylate. These can be used alone in 1, can also be more than 2 combination use.

Examples of the polyfunctional monomer (g) include allyl methacrylate, ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1, 3-butanediol dimethacrylate, 1, 4-butanediol dimethacrylate, triallyl cyanurate, triallyl isocyanurate, and the like. These can be used alone in 1, can also be more than 2 combination use.

Examples of the composite structure of the diene-acrylic composite rubber include a core-shell structure in which the periphery of the core layer of the diene rubber is covered with the alkyl (meth) acrylate rubber, a core-shell structure in which the periphery of the core layer of the alkyl (meth) acrylate rubber is covered with the diene rubber, a structure in which the diene rubber and the alkyl (meth) acrylate rubber are complexed with each other, and a copolymer structure in which the diene monomer and the alkyl (meth) acrylate monomer are randomly arranged.

The silicone component of the silicone-acrylic composite rubber contains a polyorganosiloxane as a main component, and among these, a polyorganosiloxane containing a vinyl-polymerizable functional group is preferable. The acrylic rubber component in the silicone-acrylic composite rubber is the same as the acrylic rubber component in the diene-acrylic composite rubber.

Examples of the composite structure of the silicone-acrylic composite rubber include a core-shell structure in which the periphery of the core layer of the polyorganosiloxane rubber is covered with the alkyl (meth) acrylate rubber, a core-shell structure in which the periphery of the core layer of the alkyl (meth) acrylate rubber is covered with the polyorganosiloxane rubber, a structure in which the polyorganosiloxane rubber and the alkyl (meth) acrylate rubber are complexed with each other, and a structure in which a segment of the polyorganosiloxane and a segment of the alkyl (meth) acrylate are bonded to each other linearly and sterically to form a network rubber structure.

The rubber polymer (B1) is prepared, for example, by subjecting a monomer forming the rubber polymer (B1) to emulsion polymerization with a radical polymerization initiator. The particle size of the rubbery polymer (B1) can be easily controlled by the preparation method using the emulsion polymerization method.

The average particle diameter of the rubber polymer (B1) is preferably 0.1 to 0.6. mu.m, because it can further improve the impact resistance of the reinforced thermoplastic resin composition.

The content of the rubber polymer (B1) is preferably 5 to 25% by mass based on 100% by mass of the resin main component (C). When the content of the rubber polymer (B1) is 5% by mass or more, the impact resistance of the reinforced thermoplastic resin composition can be further improved, and when it is 25% by mass or less, the moldability becomes higher and the appearance of the molded article becomes good.

[ graft Polymer (B2) ]

The graft polymer (B2) is a polymer moiety having, as essential components, the aromatic vinyl compound monomer (a) unit and the vinyl cyanide compound monomer (B) unit in the graft copolymer (B'), and having, as optional components, the monomer (c) unit copolymerizable therewith. The composition ratio is not particularly limited, and since the balance between impact resistance and moldability is excellent, it is preferable that the aromatic vinyl compound monomer (a) unit is 50 to 90% by mass, the vinyl cyanide compound monomer (b) unit is 10 to 50% by mass, and the monomer (c) unit is 0 to 40% by mass (wherein the total of (a), (b), and (c) is 100% by mass).

Examples of the aromatic alkenyl compound monomer (a) include styrene, α -methylstyrene, and vinyltoluene, with styrene being preferred.

Examples of the vinyl cyanide compound monomer (b) include acrylonitrile and methacrylonitrile, and acrylonitrile is preferred.

Examples of the monomer (c) copolymerizable with these monomers 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, and maleimide compounds such as N-phenylmaleimide.

The graft copolymer mixture (B) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

[ Polymer (B ") ]

The polymer (B ") is a polymer having an aromatic vinyl compound monomer (a) unit and a vinyl cyanide compound monomer (B) unit as essential components, and may have a monomer (c) unit copolymerizable therewith as an optional component. The polymer (B ") is produced simultaneously when the rubber polymer (B1) is graft-polymerized with units of the aromatic vinyl compound monomer (a) and units of the vinyl cyanide compound monomer (B).

The graft copolymer mixture (B) preferably contains 70 to 99 mass% of acetone-insoluble matter, and a 0.2g/dl N, N-dimethylformamide solution as acetone-soluble matter has a reduced viscosity of 0.3 to 0.7dl/g as measured at 25 ℃. If the acetone insoluble content is 70 mass% or more, the molding appearance and moldability of the reinforced thermoplastic resin composition are further improved, while if 99 mass% or less, the tear strength of the reinforced thermoplastic resin composition is improved.

Further, if the above reduced viscosity of the acetone-soluble fraction is 0.3dl/g or more, the tear strength of the reinforced thermoplastic resin composition is improved, and if it is 0.7dl/g or less, the molding appearance and moldability of the reinforced thermoplastic resin composition are further improved.

The method for measuring acetone solubility is as follows.

2.5g of the graft copolymer mixture was immersed in 90ml of acetone, heated at 65 ℃ for 3 hours, and then centrifuged at 1500rpm for 30 minutes using a centrifuge. Then, the supernatant was removed, and the residue was dried at 65 ℃ for 12 hours in a vacuum dryer, followed by precision weighing of the dried sample. The content (%) of the acetone-soluble component in the graft copolymer mixture can be determined from the mass difference ([ 2.5g of the graft copolymer mixture ] - [ mass of the dried sample ]).

The reduced viscosity was measured at 25 ℃ in a 0.2g/dl N, N-dimethylformamide solution.

[ method for producing graft copolymer mixture (B) ]

The graft copolymer mixture (B) is obtained by graft-polymerizing the aromatic vinyl compound monomer (a), the vinyl cyan compound monomer (B), and if necessary, another monomer (c) with the rubbery polymer (B1).

The polymerization method of the graft copolymer mixture (B) is not limited, and the emulsion polymerization method is preferred. In the graft polymerization, various chain transfer agents may be added to adjust the molecular weight and the graft ratio of the graft copolymer mixture (B).

[ content of graft copolymer mixture (B) ]

The content of the graft copolymer mixture (B) in the resin main component (C) is 10 to 50% by mass, preferably 10 to 20% by mass (wherein the total of the component (a) and the component (B) is 100% by mass). If the content of the graft copolymer mixture (B) in the resin main component (C) is less than 10% by mass, moldability of the reinforced thermoplastic resin composition is insufficient, and if it exceeds 50% by mass, flame retardancy of the reinforced thermoplastic resin composition is lowered.

< inorganic Filler (D) surface-treated with Water-soluble Polyamide >

The inorganic filler (D) surface-treated with a water-soluble polyamide is obtained by performing a surface treatment in which the surface of an untreated inorganic filler is coated with a water-soluble polyamide.

Examples of the untreated inorganic filler include inorganic fibers such as glass fibers and carbon fibers, metal-coated inorganic fibers, wollastonite, talc, mica, glass flakes, glass beads, potassium titanate, calcium carbonate, magnesium carbonate, carbon black, ケツチエンブラツク and other inorganic substances, and fibers and powders of metals such as iron, copper, zinc, aluminum, alloys thereof and oxides thereof. A preferred form of the untreated inorganic filler is a fibrous inorganic filler, and among these, a carbon fiber having high rigidity is preferably obtained by blending a small amount of the inorganic filler. Among the carbon fibers, chopped fibers are more preferable.

The inorganic fillers (D) may be used alone in 1 kind or in combination of 2 or more kinds.

Examples of the water-soluble polyamide include a polyamide having a tertiary amine in the main chain or in a side chain, and a polyamide having a polyalkylene glycol component in the main chain.

In order to obtain a polyamide having a tertiary amine, a monomer containing a tertiary amine in the main chain (for example, aminoethylpiperazine, bisaminopropylpiperazine, etc.) and a monomer containing a tertiary amine in the side chain (for example, α -dimethylamino ∈ -caprolactam, etc.) can be used.

More preferably, a surfactant is further added to the water-soluble polyamide. Examples of the surfactant include a betaine type surfactant.

Examples of such water-soluble polyamides are commercially available as "KP 2007", "KP 2021A" manufactured by Songbu oil & fat pharmacy, Ltd., "AQ ナイロン" manufactured by east レフアインケミカル Co., Ltd.

The content of the inorganic filler (D) surface-treated with a water-soluble polyamide is 6 to 22 parts by mass, preferably 6 to 20 parts by mass, per 100 parts by mass of the resin main component (C). If the content of the inorganic filler (D) surface-treated with a water-soluble polyamide is less than 6 parts by mass, the rigidity of the reinforced thermoplastic resin composition cannot be sufficiently improved, and if it exceeds 22 parts by mass, the moldability of the reinforced thermoplastic resin composition is lowered.

< impact resistance improver (F) >

The reinforced thermoplastic resin composition of the present invention may contain a polyester resin as the impact resistance improver (F). The polyester resin mainly contains an aromatic dicarboxylic acid unit having 8 to 22 carbon atoms and an alkylene glycol unit or cycloalkylene glycol unit having 2 to 22 carbon atoms, and the total of these structural units is 50 mass% or more. The polyester resin may contain, as a constituent unit, an aliphatic dicarboxylic acid such as adipic acid or sebacic acid, or a polyalkylene glycol such as polyethylene glycol or polytetramethylene glycol.

Preferred polyester resins include polyethylene terephthalate, polybutylene terephthalate-1, 4-butanediol, and polybutylene naphthalate. These polyester resins may be used alone in 1 kind, or 2 or more kinds may be used in combination.

The content of the impact resistance improver (F) in the reinforced thermoplastic resin composition is preferably 1 to 10 parts by mass, more preferably 3 to 7 parts by mass, per 100 parts by mass of the resin main component (C). When the content of the impact resistance improver (F) is 1 part by mass or more, the impact resistance of the reinforced thermoplastic resin composition can be sufficiently improved, and when it is 10 parts by mass or less, the moldability of the reinforced thermoplastic resin composition can be ensured.

< surface appearance improver (G) >

The reinforced thermoplastic resin composition of the present invention may contain a glycidyl ether unit-containing polymer as the surface appearance improver (G). Examples of the glycidyl ether unit-containing polymer include glycidyl ether type epoxy resins obtained by the reaction of a compound having a hydroxyl group and epichlorohydrin.

Examples of the glycidyl ether-type epoxy resin include high molecular weight products such as bisphenol-type epoxy resins, novolak-type epoxy resins, polyglycidyl ethers of aliphatic polyols, biphenyl-type epoxy resins, and the like, that is, resins having a polymer having a repeating unit represented by the following formula (1) (for example, epoxy group-containing phenoxy resins).

[ solution 1]

(m represents an integer of 1 or more.)

Examples of the bisphenol epoxy resin include bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol AD epoxy resin, and epoxy resin having a structure of bisphenol a and bisphenol F.

Examples of the novolak type epoxy resin include phenol novolak type epoxy resins, cresol novolak type epoxy resins, and the like.

Examples of the polyglycidyl ether of an aliphatic polyhydric alcohol include alkylene glycol diglycidyl ether (e.g., ethylene glycol diglycidyl ether), polyoxyalkylene glycol diglycidyl ether (e.g., diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, etc.), and glycerol triglycidyl ether.

These glycidyl ether type epoxy resins may be used alone in 1 kind, or 2 or more kinds may be used in combination.

Preferred polymers containing glycidyl ether units are bisphenol a type epoxy resins, bisphenol F type epoxy resins, epoxy resins having a structure of bisphenol a and bisphenol F, phenol novolac type epoxy resins, cresol novolac type epoxy resins, epoxy group-containing phenoxy resins. If these preferred polymers are used, the surface appearance is further improved.

As the glycidyl ether unit-containing polymer, a polymer which is liquid at room temperature (20 ℃), a polymer which is semisolid, or a polymer which is solid can be used, and a polymer which is solid is preferable in view of workability in extrusion processing and the like.

Examples of the glycidyl ether unit-containing polymers are commercially available in "jER" series manufactured by ジヤパンエポキシレジン, "エポト - ト" series manufactured by Tokyo chemical Co., Ltd "," フエノト - ト "series," AER "series manufactured by Asahi chemical Co., Ltd" ケミカルズ ", and" エピクロン "series manufactured by Tokyo インキ chemical industry Co., Ltd.

The content of the surface appearance improver (G) in the reinforced thermoplastic resin composition is preferably 1 to 12 parts by mass, more preferably 3 to 9 parts by mass, per 100 parts by mass of the resin main component (C). When the content of the surface appearance improver (G) is 1 part by mass or more, the surface appearance of a molded article obtained from the reinforced thermoplastic resin composition can be sufficiently improved, and when it is 12 parts by mass or less, the moldability of the reinforced thermoplastic resin composition can be ensured.

< phosphoric acid ester-based flame retardant (E) >

The reinforced thermoplastic resin composition of the present invention may contain a phosphate-based flame retardant (E).

The phosphate-based flame retardant is a compound represented by the following formula (2).

[ solution 2]

(R¹、R²、R³、R⁴Each independently a hydrogen atom or an organic group. However, R¹，R²，R³，R⁴Not all are hydrogen atoms. A is an organic group having a valence of 2 or more, p represents 0 or 1, q represents an integer of 1 or more, and r represents an integer of 0 or more. )

Examples of the organic group include a substituted alkyl group (e.g., methyl, ethyl, butyl, octyl, etc.), a cycloalkyl group (e.g., cyclohexyl, etc.), and an aryl group (e.g., phenyl, alkyl-substituted phenyl, etc.). In addition, the number of substituents at the time of substitution is not limited. Examples of the substituted organic group include an alkoxy group, an alkylthio group, an aryloxy group, and an arylthio group. Further, these substituents may be combined (for example, an arylalkoxyalkyl group), or may be combined with each other by an oxygen atom, a nitrogen atom, a sulfur atom, or the like (for example, an arylsulfonylalryl group).

The organic group having a valence of 2 or more means a functional group having a valence of 2 or more obtained by removing 2 or more hydrogen atoms bonded to a carbon atom from the organic group. Examples thereof include alkylene groups and (substituted) phenylene groups. The position of the hydrogen atom removed from the carbon atom is arbitrary.

Specific examples of the phosphate-based flame retardant (E) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, octyl diphenyl phosphate, diphenyl-2-ethylcresyl phosphate, tri (isopropylphenyl) phosphate, and レゾルシニル diphenyl phosphate.

In addition, there may be mentioned polyphosphoric acid esters such as bisphenol a-bis (di (toluene) phosphate), phenylene bis (diphenyl phosphate), phenylene bis (di (toluene) phosphate) and phenylene bis (di (xylene) phosphate) as bisphenol a diphosphate, hydroquinone diphosphate, resorcinol diphosphate and trihydroxybenzene triphosphate.

The phosphoric ester flame retardant (E) may be used alone in 1 kind, or may be used in combination of 2 or more kinds.

Among the above-mentioned specific examples, preferred phosphate-based flame retardants (E) are trixylenyl phosphate, phenylenebis (diphenyl phosphate), phenylenebis (dixylenyl phosphate), phenylenebis (ditoluene phosphate), and bisphenol a-bis (ditoluene phosphate), and more preferably phenylenebis (diphenyl phosphate) and phenylenebis (dixylenyl phosphate).

In the phosphate-based flame retardant (E), the polyphosphate ester is obtained by dehydration condensation of various diphenols such as polynuclear phenols (e.g., bisphenol a) and orthophosphoric acid. Examples of the diphenol include hydroquinone, resorcinol, dihydroxyphenyl methane, dihydroxyphenyl dimethyl methane, dihydroxybiphenyl, p' -dihydroxydiphenyl sulfone, and dihydroxynaphthalene.

The mass average molecular weight of the phosphate flame retardant (E) is preferably 326 or more, and more preferably 550 or more. When the mass average molecular weight is 326 or more, good flame retardancy can be exhibited, and when 550 or more of the phosphate-based flame retardant is used, moldability becomes higher, generation of gas during molding becomes less, and a molded article having excellent appearance can be obtained. The upper limit of the mass average molecular weight of the phosphate-based flame retardant is preferably 800 or less in view of the flame retardancy of the reinforced thermoplastic resin composition to be obtained. More preferably 690 or less.

Phosphoric ester-based flame retardants (E) are commercially available, for example, in "FP" series manufactured by asahi electric and chemical industries, in "クロニテツクス" series manufactured by kaki フアインテクノ (strain), in "レオフオス" series manufactured by ケムチユラジヤパン (strain), in "CR" series manufactured by yaba chemical industries, and in "PX" series.

The content of the phosphate-based flame retardant (E) is preferably 1 to 40 parts by mass, more preferably 1 to 25 parts by mass, based on 100 parts by mass of the resin main component (C). When the content of the phosphate-based flame retardant (E) is 1 part by mass or more, high surface impact strength can be sufficiently obtained, and when it is 40 parts by mass or less, heat resistance and flame retardancy can be sufficiently ensured. Further, if the content of the phosphate-based flame retardant (E) is in the above range, the surface impact strength in the falling ball test can be further improved by the synergistic effect with the inorganic filler surface-treated with the water-soluble polyamide.

< other flame retardants >

In the reinforced thermoplastic resin composition of the present invention, a known non-halogen flame retardant may be blended in addition to the phosphate-based flame retardant (E) and used in combination with the phosphate-based flame retardant (E). Examples of the non-halogen flame retardant include inorganic flame retardants such as red phosphorus and aluminum hydroxide.

As the red phosphorus flame retardant, a product stabilized by coating with a thermosetting resin or a thermosetting resin and a metal hydroxide is used. Since the red phosphorus-based flame retardant alone has an ignition property, it can be blended 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 auxiliary >

The reinforced thermoplastic resin composition of the present invention may contain a flame retardant aid (H) for preventing dripping during combustion. Examples of the flame retardant aid include polytetrafluoroethylene, tetrafluoroethylene-containing compounds, and silicone polymers.

When polytetrafluoroethylene or a tetrafluoroethylene-containing compound is blended as the flame retardant auxiliary, the blending amount thereof is preferably 0.5 parts by mass or less with respect to 100 parts by mass of the resin main component (C) from the viewpoint of surface appearance.

< 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, as required.

< production method >

The reinforced thermoplastic resin composition of the present invention is obtained by mixing the polycarbonate resin (a), the graft copolymer mixture (B), the inorganic filler (D) surface-treated with a water-soluble polyamide, and, if necessary, other components such as the phosphate-based flame retardant (E) using a mixing apparatus (e.g., henschel mixer, tumbler mixer, or natta mixer). It is also possible to use a kneading apparatus (e.g., a single-screw extruder, a twin-screw extruder, a Banbury mixer, a co-kneader, etc.) for kneading.

As described above, the reinforced thermoplastic resin composition of the present invention comprising the polycarbonate resin (A), the graft copolymer mixture (B) and the inorganic filler (D) surface-treated with a water-soluble polyamide is excellent in moldability and can improve the impact resistance (surface impact strength in the falling ball test) when the article is dropped.

Further, the reinforced thermoplastic resin composition of the present invention can contain no lubricant as an essential component, and therefore, gas generation during molding is small. Further, since the resin material is contained, the obtained molded article has excellent rigidity.

Shaped article "

The molded article of the present invention is obtained by molding the reinforced thermoplastic resin composition.

Examples of the molding method of the reinforced thermoplastic resin composition include injection molding, injection compression molding, extrusion molding, blow molding, vacuum molding, air-pressure molding, calender molding, and inflation molding. Among these, injection molding and injection compression molding are preferable because they are excellent in mass productivity and can give a molded article with high dimensional accuracy.

The molded article of the present invention can be applied to, for example, housings of personal computers (including notebook type), projectors (including liquid crystal projectors), televisions, printers, facsimiles, copiers, audio devices, game machines, cameras (including video cameras, digital cameras, and the like), image devices such as videos, musical instruments, mobile devices (electronic notebooks, Personal Digital Assistants (PDAs), and the like), lighting devices, communication devices such as telephones (including mobile phones), and the like, game devices such as fishing tackle and slingshot articles, products for vehicles, products for furniture, sanitary products, products for building materials, and the like. Among these applications, the present invention is suitable for a case of an electronic component such as a notebook-size personal computer or a portable device, in particular, since the effects of the present invention are exhibited.

Examples

The following specifically illustrates embodiments. The present invention is not limited to these examples. In addition, "part" and "%" described below mean "part by mass" and "% by mass", respectively.

In the examples below, the following ingredients were used.

[ polycarbonate resin (A) ]

As the polycarbonate resin (a), "ノバレツクス 7021 PJ" manufactured by mitsubishi エンジニアリングプラスチツクス (ltd.) was used.

[ production of graft copolymer mixture (B1-1) ]

To 100 parts (as solids) of a polybutadiene latex having a solid content of 35% and an average particle diameter of 0.08. mu.m, 2 parts (as solids) of a copolymer latex having an average particle diameter of 0.08. mu.m and comprising 85% of n-butyl acrylate units and 15% of methacrylic acid units were added under stirring. Subsequently, the stirring was continued for 30 minutes to obtain an enlarged butadiene-based rubbery polymer latex having an average particle diameter of 0.28. mu.m.

The resulting enlarged butadiene rubber polymer latex was charged into a reactor, and further added with 100 parts of distilled water, 4 parts of wood rosin emulsifier, 0.4 part of デモ - ル N (trade name, product of kao corporation, formalin condensate of naphthalene sulfonic acid), 0.04 part of sodium hydroxide, and 0.7 part of dextrose. Then, while the temperature was increased under stirring, 0.1 part of ferrous sulfate, 0.4 part of sodium pyrophosphate, and 0.06 part of sodium hydrosulfite were added at a time of an internal temperature of 60 ℃, and then a mixture containing the following components was continuously dropped over 90 minutes, followed by holding for 1 hour and cooling.

30 portions of acrylonitrile

Styrene 70 parts

0.4 part of cumene hydroperoxide

1 part of tert-dodecyl mercaptan

The thus-obtained graft copolymer mixture latex was coagulated with dilute sulfuric acid, washed, filtered and dried to obtain a dry powder of the graft copolymer mixture (B1-1).

The acetone-soluble fraction of the graft copolymer mixture (B1-1) was 27%. Further, the acetone-soluble fraction had a reduced viscosity of 0.3 dl/g.

The method for measuring acetone solubility is as follows.

2.5g of the graft copolymer mixture was immersed in 90ml of acetone, heated at 65 ℃ for 3 hours, and then centrifuged at 1500rpm for 30 minutes using a centrifuge. Then, the supernatant was removed, and the residue was dried at 65 ℃ for 12 hours in a vacuum dryer, followed by precision weighing of the dried sample. The content (%) of the acetone-soluble component in the graft copolymer mixture can be determined from the mass difference ([ 2.5g of the graft copolymer mixture ] - [ mass of the dried sample ]).

The reduced viscosity was measured at 25 ℃ in a 0.2g/dl solution of N, N-dimethylformamide.

[ production of graft copolymer mixture (B1-2) ]

The raw materials were charged into a reactor in the following proportions and polymerized for 4 hours at 50 ℃ under stirring under nitrogen substitution to obtain a rubber latex.

100 parts (in terms of solid content) of the thus-obtained rubber latex was charged into a separate reactor, and 280 parts of ion-exchanged water was added thereto to dilute the latex, followed by heating to 70 ℃.

In addition, 0.7 part of benzoyl peroxide was dissolved in 100 parts of a monomer mixture consisting of acrylonitrile/styrene (mass ratio) 29/71, and after nitrogen substitution, the monomer mixture was fed into a reactor containing the rubber latex by a quantitative pump at a rate of 30 parts/hour. After all the monomers were added, the temperature in the reactor was raised to 80 ℃ and stirring was continued for 30 minutes to obtain a graft copolymer mixture latex. The polymerization rate was 99%.

The above graft copolymer mixture latex was charged with aluminum chloride (AlCl) in an amount of 3 times the amount of the whole latex while stirring₃.6H₂O) 0.15% aqueous solution (90 ℃ C.) was poured into a coagulation vessel to coagulate the solution. After the entire amount of the latex was added, the temperature in the coagulation tank was raised to 93 ℃ and the mixture was left as it was for 5 minutes. After cooling, the resultant mixture was subjected to liquid removal and washing with a centrifuge, and then dried to obtain a dry powder of the graft copolymer mixture (B1-2).

The acetone-soluble fraction of the graft copolymer mixture (B1-2) was 21%. Further, the acetone-soluble fraction had a reduced viscosity of 0.70 dl/g.

[ production of graft copolymer mixture (B1-3) ]

A graft copolymer mixture (B1-3) comprising a polybutadiene/polybutyl acrylate composite rubber as a rubbery polymer was obtained by the following method.

To 20 parts (as solids) of a polybutadiene latex having a solid content of 35% and an average particle diameter of 0.08. mu.m, 0.4 part (as solids) of a copolymer latex having an average particle diameter of 0.10. mu.m and comprising 82% of n-butyl acrylate units and 18% of methacrylic acid units was added under stirring. Then, the stirring was continued for 30 minutes to obtain an enlarged diene rubber latex having an average particle diameter of 0.36. mu.m.

The obtained enlarged diene rubber latex was charged in an amount of 20 parts (in terms of solid content) into a reactor, and a monomer mixture of 1 part of non-homogenized potassium rosinate, 150 parts of ion-exchanged water and the following composition was added thereto to replace nitrogen, followed by heating to 50 ℃. Further, a solution prepared by dissolving 0.0002 parts of ferrous sulfate, 0.0006 parts of disodium ethylenediaminetetraacetate, and 0.25 parts of rongalite in 10 parts of ion-exchanged water was added to the reactor to react.

80 portions of n-butyl acrylate

0.32 part of allyl methacrylate

Ethylene glycol dimethacrylate 0.16 part

The internal temperature at the end of the reaction was 75 ℃ and further increased to 80 ℃ to continue the reaction for 1 hour, thereby obtaining a composite rubber of an enlarged diene rubber and a polybutyl acrylate rubber. The polymerization rate was 98.8%.

Then, 50 parts (in terms of solid content) of a composite rubber latex of an enlarged diene rubber and a polybutyl acrylate rubber was charged into a reactor, and 140 parts of ion-exchanged water was added thereto to dilute the latex, and the temperature was raised to 70 ℃.

Separately, 0.35 part of benzoyl peroxide was dissolved in 50 parts of a monomer mixture composed of acrylonitrile/styrene (mass ratio) of 29/71, and nitrogen substitution was performed. This monomer mixture was added to the reactor containing the above-mentioned rubber latex at a rate of 15 parts/hour using a metering pump. After all the monomers were added, the temperature in the reactor was raised to 80 ℃ and stirring was continued for 30 minutes to obtain a graft copolymer mixture latex. The polymerization rate was 99%.

The graft copolymer mixture latex was put into a coagulation vessel containing a 0.5% aqueous solution (90 ℃) of sulfuric acid in an amount of 3 times the total amount of the latex while stirring, and coagulated. After the entire amount of the latex was added, the temperature in the coagulation tank was raised to 93 ℃ and the mixture was left as it was for 5 minutes. After cooling, the resultant mixture was subjected to liquid removal and washing with a centrifugal separator, and then dried to obtain a dry powder of the graft copolymer mixture (B1-3).

The acetone-soluble fraction of the graft copolymer mixture (B1-3) was 20%. Further, the acetone-soluble fraction had a reduced viscosity of 0.7 dl/g.

[ production of graft copolymer mixture (B1-4) ]

A graft copolymer mixture (B1-4) comprising a silicone rubber/polybutyl acrylate composite 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-based mixture. To this, 300 parts of distilled water in which 0.67 part of sodium dodecylbenzenesulfonate was dissolved was added, and after stirring at 10000 rpm/2 minutes using a homomixer, the resulting mixture was passed into a homogenizer at a pressure of 30MPa for 1 time to obtain a stable premixed organosiloxane latex.

In addition, 2 parts of dodecylbenzenesulfonic acid and 98 parts of distilled water were poured into a reactor equipped with a reagent-pouring vessel, a cooling tube, a jacket heater and a stirring device to prepare a 2% dodecylbenzenesulfonic acid aqueous solution. The aqueous solution was heated to 85 ℃, and the premixed organosiloxane latex was added dropwise over 4 hours, and after completion of the addition, the temperature was maintained for 1 hour, followed by cooling.

The reaction solution was left 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 ℃ for 30 minutes to determine the solid content concentration, which was 17.3%.

Next, 119.5 parts of polyorganosiloxane latex (L-1), 0.8 part of sodium polyoxyethylene alkylphenyl ether sulfate, and 203 parts of distilled water were charged into a reactor equipped with a reagent injection vessel, a cooling tube, a jacket heater, and a stirring device, and mixed. Then, a mixture composed of 53.2 parts of n-butyl acrylate, 0.21 part of allyl methacrylate, 0.11 part of 1, 3-butanediol dimethacrylate and 0.13 part of t-butyl hydroperoxide was added. Nitrogen substitution of the atmosphere was performed by passing a nitrogen stream into the reactor, and the temperature was raised to 60 ℃. When the temperature inside the reactor reached 60 ℃, an aqueous solution in which 0.0001 part of ferrous sulfate, 0.0003 part of disodium ethylenediaminetetraacetate, and 0.24 part of rongalite were dissolved in 10 parts of distilled water was added to initiate radical polymerization. The liquid temperature rose to 78 ℃ due to the polymerization of the acrylate component. This state was maintained for 1 hour, and polymerization of the acrylate component was terminated to obtain a composite rubber latex of polyorganosiloxane and butyl acrylate rubber.

After the temperature of the liquid in the reactor was decreased to 60 ℃, an aqueous solution prepared by dissolving 0.4 part of rongalite in 10 parts of distilled water was added. Then, a mixture of 11.1 parts of acrylonitrile, 33.2 parts of styrene and 0.2 part of t-butyl hydroperoxide was added dropwise over about 1 hour to polymerize the product. After the dropwise addition was completed and the mixture was kept for 1 hour, an aqueous solution prepared by dissolving 0.0002 part of ferrous sulfate, 0.0006 part of disodium ethylenediaminetetraacetate, and 0.25 part of rongalite in 10 parts of distilled water was added. Then, a mixture of 7.4 parts of acrylonitrile, 22.2 parts of styrene and 0.1 part of t-butyl hydroperoxide was added dropwise over about 40 minutes to carry out polymerization. After the dropping was completed and kept for 1 hour, cooling was conducted to obtain a latex of a graft copolymer mixture in which an acrylonitrile-styrene copolymer was grafted with a composite rubber composed of polyorganosiloxane and butyl acrylate rubber.

Then, 150 parts of an aqueous solution in which calcium acetate was dissolved at a ratio of 5% was heated to 60 ℃ and stirred. 100 parts of a latex of the graft copolymer mixture was gradually dropped into the calcium acetate aqueous solution to coagulate it. The obtained coagulated product was separated, washed and dried to obtain a dry powder of a graft copolymer mixture (B1-4).

The acetone-soluble fraction of the graft copolymer mixture (B1-4) was 26%. Further, the acetone-soluble fraction had a reduced viscosity of 0.60 dl/g.

[ impact resistance improver (F) ]

As the impact resistance improver (F), a polybutylene terephthalate resin NOVADURAN 5020S manufactured by Mitsubishi エンジニアリングプラスチツクス (Ltd.) was used.

[ inorganic Filler (D) ]

As the inorganic filler (D-1), chopped carbon fiber (manufactured by Mitsubishi レイヨン, Inc.) and "TR 06 NE" (surface treatment agent: water-soluble polyamide) were used.

As the inorganic filler (D-2), carbon fiber chopped fibers (manufactured by Toho テナツクス Co., Ltd.) "HTA-C6-U" (surface treatment agent: polyurethane) was used.

As the inorganic filler (D-3), carbon fiber chopped fibers made of Toho テナツクス (strain), "HTA-C6N" (surface treatment agent: polyamide dissolved in methanol) were used.

[ phosphoric acid ester-based flame retardant (E) ]

As the phosphate flame retardant (E-1), "PX-200" (mass-average molecular weight 686) manufactured by Dai eight chemical Co., Ltd. was used.

As the phosphate-based flame retardant (E-2), "CR-733S" (mass-average molecular weight 574) manufactured by Dai Kabushiki Kaisha was used.

As the phosphate-based flame retardant (E-3), "TPP" (mass-average molecular weight 326) manufactured by Dai eight chemical Co., Ltd.

As the phosphate-based flame retardant (E-4), "BAPP" (mass average molecular weight 692) manufactured by kaipin フアインテクノ (strain) was used.

In the case of flame-retarding with the phosphate-based flame retardant (E), Polytetrafluoroethylene (PTFE) is added as the flame-retarding aid (H).

[ other ingredients ]

In example 8 and comparative example 5 described below, a glycidyl ether unit-containing polymer, "1256" manufactured by ジヤパンエポキシレジン (strain) was blended as the surface appearance improver (G).

The reinforced thermoplastic resin compositions were obtained by blending the above components as shown in tables 1 to 4. The resulting reinforced thermoplastic resin composition was evaluated for surface impact strength, Charpy impact strength, flexural modulus, flame retardancy, and moldability by the following methods. The evaluation results are shown in tables 1 to 4.

[ surface impact Strength ]

A falling ball impact test was carried out using a test piece (100 mm. times.100 mm. times.1 mm in thickness) prepared by injection molding. In this test, the ultimate failure height when a 500g steel ball was used was examined using a test machine of the UL1956 vertical ball drop test method.

[ Charpy impact Strength ]

The Charpy impact strength was determined according to ISO 179.

[ flexural modulus of elasticity ]

The flexural modulus was determined according to ISO 178.

[ flame retardancy ]

The reinforced thermoplastic resin composition was molded to prepare a test piece (width 12.7mm, length 127mm, thickness 1.0mm), and a flame test was performed according to UL 94. For the resin compositions of examples 1 to 17 and comparative examples 1 to 7 containing the phosphate ester-based flame retardant (E), a vertical burning test was applied, and for the resin compositions of examples 18 to 19 and comparative examples 8 to 12 not containing the phosphate ester-based flame retardant (E), a horizontal burning test was applied to evaluate flame retardancy.

(1) Vertical burning test

The lower end of the vertically supported test piece was brought into contact with the burner flame for 10 seconds, and then the burner flame was moved away from the test piece. After the flame had extinguished, it was again exposed to the burner flame and the same operation was carried out. Then, the presence or absence of the combustion drop was determined by the duration of the flaming combustion after the 1 st flame contact was completed, the sum of the duration of the flaming combustion and the duration of the flameless combustion in the 2 nd flame contact, and the presence or absence of the combustion drop. The standards for each grade in UL94 are outlined below.

V-0: the duration of the flame combustion at the 1 st time is within 10 seconds, and the sum of the duration of the flame combustion at the 2 nd time and the duration of the flameless combustion is within 30 seconds, and no combustion drop occurs.

V-1: the duration of the flame combustion at the 1 st time is more than 10 seconds and less than 30 seconds, and the sum of the duration of the flame combustion at the 2 nd time and the duration of the flameless combustion is more than 30 seconds and less than 60 seconds, and no combustion drop is generated.

V-2: the duration of the flame combustion at the 1 st stage is more than 10 seconds and less than 30 seconds, and the sum of the duration of the flame combustion at the 2 nd stage and the duration of the flameless combustion is more than 30 seconds and less than 60 seconds, and there are combustion drops.

The flame retardancy of examples 1 to 17 and comparative examples 1 to 7 in tables 1 to 3 is shown by the following symbols.

Very good: has flame retardancy of a V-0 level.

O: has flame retardancy of V-1 level.

And (delta): has flame retardancy of V-2 level.

X: does not have flame retardancy at the V-2 level.

(2) Horizontal burning test

The end of the above test piece supported horizontally was brought into contact with the burner flame, held for 30 seconds, and then the burner flame was moved away from the test piece. After the completion of the flame contact, the combustion time between the standards (75mm) marked on the test piece in advance was measured, and the combustion speed was determined from the measurement result. The standards in UL94 are outlined below.

HB: the flame is extinguished and the combustion speed is 75 mm/min or less after the completion of the flame application.

The flame retardancy of examples 18 to 19 and comparative examples 8 to 12 in tables 2 and 4 are shown by the following symbols.

O: has flame retardancy of HB level.

X: flame retardancy of HB level was not exhibited.

[ formability ]

A liquid crystal display cover (thickness 1mm) of a4 size notebook-size personal computer was molded by an injection molding machine (Japan Steel works J350E, pressure vessel of 350 tons) under the following molding conditions. Moldability was evaluated by the presence or absence of insufficient injection (unfilled portion) and the presence or absence of gas scorch at the time of molding.

O: there are no unfilled portions.

And (delta): some find unfilled parts.

X: no filling, or gas scorch was found.

● Molding conditions

The molding conditions of the reinforced thermoplastic resin composition of the present invention are as follows, molding temperature: 280 ℃, injection speed: 99% and the mold temperature: 80 ℃. However, the molding conditions of the reinforced thermoplastic resin composition containing the phosphate-based flame retardant are as follows: 260 ℃, injection rate: 99% and the mold temperature: 80 ℃.

[ Table 1]

[ Table 2]

[ Table 3]

[ Table 4]

As is clear from the comparison between example 1 and comparative example 1, example 2 and comparative example 2, example 5 and comparative example 3, example 7 and comparative example 5, example 9 and comparative example 6, example 18 and comparative example 9, and example 19 and comparative example 10, the reinforced thermoplastic resin composition containing the carbon fiber chopped fibers (D) surface-treated with the water-soluble polyamide is superior in the surface impact strength by the falling ball test to the reinforced thermoplastic resin composition containing the carbon fiber chopped fibers surface-treated with a material other than the water-soluble polyamide.

Further, as is clear from comparison of example 2 with comparative example 7, and example 19 with comparative example 11, the reinforced thermoplastic resin composition containing carbon fiber chopped fibers surface-treated with a water-soluble polyamide has higher surface impact strength by the falling ball test than the reinforced thermoplastic resin composition containing carbon fiber chopped fibers surface-treated with a polyamide dissolved in methanol.

The reinforced thermoplastic resin compositions of examples 2, 13 and 14 in which the mass average molecular weight of the phosphate-based flame retardant (E) was 686 or less had higher flame retardancy than the reinforced thermoplastic resin composition of example 15 in which the mass average molecular weight of the phosphate-based flame retardant (E) exceeded 686.

The reinforced thermoplastic resin composition of comparative example 4, which contains the polycarbonate resin (A), the graft copolymer mixture (B) and the inorganic filler (D) surface-treated with a water-soluble polyamide, has low moldability, but the content of the inorganic filler (D) surface-treated with a water-soluble polyamide exceeds 22 parts.

The reinforced thermoplastic resin composition of comparative example 12, which contained the polycarbonate resin (A), the graft copolymer mixture (B) and the inorganic filler (D) surface-treated with a water-soluble polyamide, had a low moldability, but contained the polycarbonate resin (A) in an amount exceeding 90 parts.

Further, in examples 1 and comparative examples 1 and 3, examples 2 and 9 and comparative examples 4 and 6, example 3 and comparative examples 2, 5 and 7, example 18 and comparative example 9, and example 19 and comparative examples 10, 11 and 12, Charpy impact strength was the same value, but the impact strength of the surface by the ball drop test was different. Further, when examples 3 and 9 were compared with comparative example 3, the face impact strength by the ball drop test decreased as the Charpy impact strength increased, and when example 18 was compared with comparative examples 2 and 4, the face impact strength by the ball drop test increased as the Charpy impact strength increased.

Therefore, the correlation between the Charpy impact strength and the surface impact strength in the ball drop test was low. Further, since Charpy impact strength has a high correlation with Izod impact strength, it is found that the correlation between Izod impact strength and surface impact strength by the ball drop test is also low.

Industrial applicability of the invention

The reinforced thermoplastic resin composition of the present invention is excellent in moldability, generates little gas during molding, gives a molded article having high rigidity, and can improve impact resistance (surface impact strength in a falling ball test) when the article is dropped.

The molded article of the present invention has high rigidity, high impact resistance when the article is dropped, and high industrial applicability.

Claims (4)

1. A reinforced thermoplastic resin composition characterized by containing:

50 to 90 mass% of a polycarbonate resin (A),

10 to 50 mass% of a graft copolymer mixture (B), wherein the total of the component (A) and the component (B) is 100 mass%, and

6 to 22 parts by mass of a carbon fiber surface-treated with a water-soluble polyamide per 100 parts by mass of the total of the polycarbonate resin (A) and the graft copolymer mixture (B);

the graft copolymer mixture (B) comprises a graft copolymer (B') in which a graft polymer (B2) having an aromatic alkenyl compound monomer (a) unit and a vinyl cyanide compound monomer (B) unit is graft-polymerized with a rubbery polymer (B1).

2. The reinforced thermoplastic resin composition according to claim 1, further comprising a phosphate-based flame retardant (E).

3. The reinforced thermoplastic resin composition according to claim 2, wherein the phosphate-based flame retardant (E) has a mass average molecular weight of 326 to 800 inclusive.

4. A molded article obtained by molding the reinforced thermoplastic resin composition according to any one of claims 1 to 3.