Reinforced thermoplastic resin composition and molded article

Abstract

A reinforced thermoplastic resin composition comprising specific amounts of: a main resin component (C) comprising 50 to 100% by weight of a polycarbonate resin (A) and 0 to 50% by weight of a graft copolymer (B) obtained by polymerizing an aromatic alkenyl compound monomer (a) and a vinyl cyanide compound monomer (b) in the presence of a rubber polymer (B1); a grass fiber (D); a glycidyl ether unit-containing polymer (E) containing glycidyl ether units and having a weight average molecular weight of 3,800 to 60,000; a phosphoric acid ester-based flame retardant (F); and an organomodified siloxane (G).

Claims

1. A reinforced thermoplastic resin composition comprising: a main resin component (C) comprising 50 to 95% by weight of a polycarbonate resin (A) and 5 to 50% by weight of a graft copolymer (B) obtained by polymerizing an aromatic alkenyl compound monomer (a) and a vinyl cyanide compound monomer (b) in the presence of an ethylene-propylene-nonconjugated diene rubber (B1), provided that a total amount of the polycarbonate resin (A) and the graft copolymer (B) is 100% by weight; a glass fiber (D); a glycidyl ether unit-containing polymer (E) containing glycidyl ether units and having a weight average molecular weight of 3,800 to 60,000, provided that the graft copolymer (B) is excluded from the glycidyl ether unit-containing polymer (E); a phosphoric acid ester-based flame retardant (F); and an organomodified siloxane (G), which is a compound in which an organomodified siloxane is chemically bonded with a polyolefin or a polyamide, or a mixture of an organomodified siloxane with a polyolefin or a polyamide, wherein: the amount of the glass fiber (D) is 10 to 50% by weight, based on the total weight of the main resin component (C), the glass fiber (D), the glycidyl ether unit-containing polymer (E), the phosphoric acid ester-based flame-retardant (F), and the organomodified siloxane (G), the total weight being 100% by weight, the amount of the glycidyl ether unit-containing polymer (E) is 1 to 10 parts by weight, relative to 100 parts by weight of the main resin component (C), the amount of the phosphoric acid ester-based flame retardant (F) is 1 to 30 parts by weight, relative to 100 parts by weight of the main resin component (C), and the amount of the organomodified siloxane (G) is 1 to 5 parts by weight, relative to 100 parts by weight of the main resin component (C).

2. A molded article obtainable by molding the reinforced thermoplastic resin composition of claim 1.

3. The reinforced thermoplastic resin composition according to claim 1, which further comprises a flame retardant auxiliary agent (H).

4. The reinforced thermoplastic resin composition according to claim 1, wherein polycarbonate resin (A) has a viscosity average molecular weight between 15,000 and 35,000.

5. The reinforced thermoplastic resin composition according to claim 1, wherein the amount of graph co-polymer (B) is between 5 and 50 wt %, provided that the total amount of polycarbonate resin (A) and graph polymer (B) is 100 wt %.

6. The reinforced thermoplastic resin composition according to claim 1, wherein glass fiber (D) has a cross-section having a major axis and a minor axis and a ratio of major axis length to minor axis length of 1:1 to 6:1.

7. The reinforced thermoplastic resin composition according to claim 1, wherein the glycidyl ether unit-containing polymer (E) includes an epoxy group containing phenoxyresin.

8. The reinforced thermoplastic resin composition according to claim 1, wherein phosphoric acid ester-based flame retardant (F) includes phenylene-bis(dixylyl phosphate).

9. The reinforced thermoplastic resin composition according to claim 1, wherein the organomodified siloxane is a compound of organomodified siloxane and polyolefin.

10. The reinforced thermoplastic resin composition according to claim 3, wherein polycarbonate resin (A) has a viscosity average molecular weight between 15,000 and 35,000.

11. The reinforced thermoplastic resin composition according to claim 3, wherein the glycidyl ether unit-containing polymer (E) includes an epoxy group containing phenoxyresin.

12. The reinforced thermoplastic resin composition according to claim 3, wherein phosphoric acid ester-based flame retardant (F) includes phenylene-bis(dixylyl phosphate).

13. The reinforced thermoplastic resin composition according to claim 3, wherein the organomodified siloxane is a compound of organomodified siloxane and polyolefin.

14. The molded article obtainable by molding the reinforced thermoplastic resin composition of claim 1, wherein polycarbonate resin (A) has a viscosity average molecular weight between 15,000 and 35,000.

15. The molded article obtainable by molding the reinforced thermoplastic resin composition of claim 1, wherein glass fiber (D) has a cross-section having a major axis and a minor axis and a ratio of major axis length to minor axis length of 1:1 to 6:1.

16. The molded article obtainable by molding the reinforced thermoplastic resin composition of claim 1, wherein the glycidyl ether unit- containing polymer (E) includes an epoxy group containing phenoxyresin.

17. The molded article obtainable by molding the reinforced thermoplastic resin composition of claim 1, wherein the organomodified siloxane is a compound of organomodified siloxane and polyolefin.

Description

EXAMPLES

(1) Hereinbelow, specific examples are shown. The present invention is in no way limited by these examples. In addition, in the following description, the units “parts” and “%” refer to “parts by weight” and “% by weight”, respectively.

(2) <Measurement Method and Evaluation Method>

(3) [Acetone-Soluble Fraction]

(4) 2.5 g of a graft copolymer was immersed in 90 ml of acetone, heated at 65° C. for 3 hours, and then centrifuged at 1,500 rpm for 30 minutes by using a centrifugal separator. Thereafter, the supernatant liquid was removed. The residue was dried at 65° C. for 12 hours in a vacuum drier, and the resulting sample after drying was precisely weighed. From the weight difference between before and after this process (namely, [2.5 g of graft copolymer]−[sample weight after drying]), the content (%) of the acetone-soluble fraction relative to the graft copolymer was determined. The reduced viscosity of the acetone-soluble fraction was measured in a 0.2 g/dl N,N-dimethylformamide solution at 25° C.

(5) [Gel Content]

(6) The EPDM-containing crosslinked latex was coagulated with dilute sulfuric acid, and the coagulated material was washed with water and dried to produce solids. 1 g of the solids were collected, and the collected solids were immersed and kept in 200 ml of toluene for 40 hours. The resulting was filtered through a 200-mesh stainless wire net, followed by drying the residue. The gel content (%) was determined from the weight of the dried residue.

(7) [Average Particle Diameter]

(8) The average particle diameter of the EPDM-containing crosslinked latex was measured by a particle size distribution analyzer (“CAPA-500”, manufactured by Horiba, Ltd.).

(9) [Evaluation of Charpy Impact Strength]

(10) The Charpy impact strength was measured in accordance with ISO 179.

(11) [Evaluation of Flexural Strength and Flexural Modulus]

(12) The flexural strength and flexural modulus were measured in accordance with ISO 178. Here, each of the flexural strength and the flexural modulus is an index of the mechanical strength.

(13) [Sliding Property (Coefficient of Dynamic Friction)]

(14) According to JIS K 7218 A method (ring-on-ring method), the coefficient of dynamic friction was measured using an EM type friction tester (“EFM-iii”, manufactured by Orientec Co., Ltd.) by a method in which hollow cylindrical test pieces (inner diameter: 20 mm, outer diameter: 25.6 mm) are attached to upper and lower portions of the tester, and the test pieces are rubbed together under a load of 4.0 kg at a test speed of 100 mm/sec.

(15) [Appearance]

(16) The appearance of the molded article was visually observed, and evaluated in accordance with the following criteria.

(17) ∘ (Good): No flow mark was observed.

(18) x (Poor): Flow marks were observed.

(19) [Moldability]

(20) A liquid crystal display cover for a laptop personal computer having a thickness of 1.0 mm was formed by molding with an injection molding machine (“J350E” equipped with a 350 t accumulator, manufactured by The Japan Steel Works, LTD.) under the molding conditions in which the molding temperature was 290° C., the injection rate was 99%, and the mold temperature was 85° C. The moldability was evaluated based on the occurrence of short shot (unfilled portions) and the occurrence of sink marks or corrosion by gas during the molding.

(21) ⊚ (Excellent): None of unfilled portion, sink marks and corrosion by gas was observed.

(22) ∘ (Good): Unfilled portions were partially observed.

(23) x (Poor): Either one or both of unfilled portions and corrosion by gas was observed.

(24) <Ingredients>

(25) [Polycarbonate Resin (A)]

(26) The “Novarex (registered trademark) 7021PJ” manufactured by Mitsubishi Engineering-Plastics Corporation was used as the polycarbonate resin (A-1) (viscosity average molecular weight (Mv): 18,800).

(27) [Production of Graft Copolymer (B-1)]

(28) 2 parts (in terms of solids content) of a copolymer latex having an average particle size of 0.08 μm composed of 85% of an n-butyl acrylate unit and 15% of a methacrylic acid unit were added, with stirring, to 100 parts (in terms of solids content) of a polybutadiene latex having an average particle size of 0.08 μm at a solid content concentration of 35%. Subsequently, the mixture was kept stirred for 30 minutes, thereby yielding an enlarged butadiene-based rubber polymer (B1-1) latex having an average particle size of 0.28 μm.

(29) The yielded enlarged butadiene-based rubber polymer (B1-1) latex was placed in a reaction vessel, to which 100 parts of distilled water, 4 parts of a wood rosin emulsifier, 0.4 parts of “Demol (registered trademark) N” (naphthalene sulfonate formaldehyde condensate, manufactured by Kao Corporation), 0.04 parts of sodium hydroxide, and 0.7 parts of dextrose were further added. Subsequently, the mixture was heated under stirring. When the internal temperature reached 60° C., 0.1 part of ferrous sulfate, 0.4 parts of sodium pyrophosphate, and 0.06 parts of sodium dithionite were added. Then, a mixture containing the following components was continuously added dropwise over 90 minutes. The resultant product was allowed to stand for 1 hour and then was cooled down.

(30) TABLE-US-00001 Acrylonitrile 30 parts Styrene 70 parts Cumene hydroperoxide 0.4 parts tert-dodecylmercaptan 1 part

(31) The thus yielded graft copolymer (B-1) latex was coagulated with dilute sulfuric acid. The coagulated product was then washed, filtered, and dried, thereby yielding a graft copolymer (B-1) in the form of a dried powder.

(32) The acetone-soluble fraction of this graft copolymer (B-1) was 27%. In addition, the reduced viscosity of this acetone-soluble fraction was 0.3 dl/g.

(33) [Production of Graft Copolymer (B-2)]

(34) Raw materials at the following proportions were charged in a reaction vessel and polymerized under stirring with nitrogen purge at 50° C. for 4 hours, thereby yielding a rubber polymer (B1-2) latex.

(35) TABLE-US-00002 n-butyl acrylate 98 parts 1,3-butylene glycol dimethacrylate 1 part Allyl methacrylate 1 part Sodium dioctylsulfosuccinate 2.0 parts Deionized water 300 parts Potassium persulfate 0.3 parts Disodium phosphate dodecahydrate 0.5 parts Sodium hydrogen phosphate dodecahydrate 0.3 parts

(36) 100 parts (in terms of solids content) of the thus yielded rubber polymer (B1-2) latex was charged in another reaction vessel and diluted by adding 280 parts of ion exchanged water thereto, and the resulting diluted product was heated to 70° C.

(37) Separately, 0.7 parts of benzoyl peroxide was dissolved in 100 parts of a monomer mixture composed of acrylonitrile/styrene=29/71 (weight ratio), and the reaction vessel was purged with nitrogen. Then, this monomer mixture was added at a rate of 30 parts/hour by a metering pump into the reaction vessel which contained the above-mentioned rubber polymer (B1-2) latex. After addition of all the monomers, the temperature inside the reaction vessel was raised to 80° C., and the mixture was kept stirred for 30 minutes, thereby yielding a graft copolymer (B-2) latex. The polymerization ratio was 99%.

(38) The above graft copolymer (B-2) latex was charged into a coagulation bath which contained a 0.15% aqueous solution of aluminum chloride (AlCl.sub.3.6H.sub.2O) in an amount that is three-fold the total amount of the latex, under stirring to cause the coagulation. After addition of all the latex, the temperature inside the coagulation bath was raised to 93° C., and the mixture was allowed to stand for 5 minutes. The resultant was cooled, and then liquid was removed therefrom by using a centrifugal separator. The resulting product was washed and then dried, thereby yielding a graft copolymer (B-2) in the form of a dried powder.

(39) The acetone-soluble fraction of this graft copolymer (B-2) was 21%. In addition, the reduced viscosity of this acetone-soluble fraction was 0.70 dl/g.

(40) [Production of Graft Copolymer (B-3)]

(41) 0.4 parts (in terms of solids content) of a copolymer latex having an average particle size of 0.08 μm composed of 82% of an n-butyl acrylate unit and 18% of a methacrylic acid unit were added, with stirring, to 20 parts (in terms of solids content) of a polybutadiene latex having an average particle size of 0.08 μm at a solids content concentration of 35%. Subsequently, the stirring of the mixture was continued for further 30 minutes, thereby yielding an enlarged diene-based rubber latex having an average particle size of 0.36 μm.

(42) 20 parts (in terms of solids content) of the thus yielded enlarged diene-based rubber latex were placed in a reaction vessel, to which 1 part of disproportionated potassium rosinate, 150 parts of ion exchanged water, and a monomer mixture having the following composition were added. The reaction vessel was purged with nitrogen, and the temperature inside the reaction vessel was raised to 50° C.

(43) TABLE-US-00003 n-butyl acrylate   80 parts Allyl methacrylate 0.32 parts Ethylene glycol dimethacrylate 0.16 parts

(44) Furthermore, a solution of 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 into the reaction vessel, to effect a reaction. The internal temperature at the completion of the reaction was 75° C. The solution was further heated up to 80° C., and the reaction was continued further for 1 hour, thereby yielding a rubber polymer (B1-3) composed of a composite rubber of an enlarged diene-based rubber and a polybutyl acrylate-based rubber. The polymerization rate was 98.8%.

(45) Subsequently, 50 parts (in terms of solids content) of the rubber polymer (B1-3) latex were placed in a reaction vessel, which was then diluted by adding 140 parts of ion exchanged water thereto. The resulting diluted solution was heated to 70° C.

(46) Separately, 0.35 parts of benzoyl peroxide were dissolved in 50 parts of a monomer mixture composed of acrylonitrile/styrene=29/71 (weight ratio), and the container was purged with nitrogen. This monomer mixture was added at a rate of 15 parts/hour by a metering pump into the reaction vessel containing the above-mentioned rubber polymer (B1-3) latex. After addition of all the monomers, the temperature inside the reaction vessel was raised to 80° C., and the mixture was kept stirred for 30 minutes, thereby yielding a graft copolymer (B-3) latex. The polymerization ratio was 99%.

(47) The above graft copolymer latex was charged into a coagulation bath containing a 0.5% aqueous solution of sulfuric acid (90° C.) in an amount that is three-fold the total amount of the latex, under stirring to effect coagulation. After addition of all the latex, the temperature inside the coagulation bath was raised to 93° C., and the mixture was allowed to stand for 5 minutes. The resultant was cooled, and then liquid was removed therefrom by using a centrifugal separator. The resulting product was washed and then dried, thereby yielding a graft copolymer (B-3) in the form of a dried powder.

(48) The acetone-soluble fraction of this graft copolymer (B-3) was 20%. The reduced viscosity of this acetone-soluble fraction was 0.7 dl/g.

(49) [Production of Graft Copolymer (B-4)]

(50) 96 parts of octamethyltetracyclosiloxane, 2 parts of γ-methacryloxypropyldimethoxymethylsilane, and 2 parts of ethyl orthosilicate were mixed to yield 100 parts of a siloxane-based mixture. 300 parts of distilled water having 0.67 parts of sodium dodecylbenzene sulfonate dissolved therein were added to this mixture. The resulting mixture was stirred by a homomixer at 10000 rpm for 2 minutes, and was then homogenized once at a pressure of 30 MPa by a homogenizer, thereby yielding a stable premixed organosiloxane latex.

(51) In addition, 2 parts of dodecylbenzenesulfonate and 98 parts of distilled water were charged in a reaction vessel equipped with a reagent injection container, a cooling tube, a jacket heater and a stirring device, whereby an aqueous solution of 2% dodecylbenzenesulfonate was prepared. While heating this aqueous solution to 85° C., the premixed organosiloxane latex was dropwise added thereto over 4 hours. After the completion of the dropwise addition, the solution was kept at that temperature for 1 hour, and was then cooled down. The reaction solution was allowed to stand at room temperature for 48 hours and was then neutralized with an aqueous solution of sodium hydroxide, thereby yielding a polyorganosiloxane latex (L-1). A portion of the polyorganosiloxane latex (L-1) was dried at 170° C. for 30 minutes to obtain the solids content concentration. The thus obtained solids content concentration was 17.3%.

(52) Subsequently, 119.5 parts of the polyorganosiloxane latex (L-1) and 0.8 parts of sodium polyoxyethylene alkyl phenyl ether sulfate were charged in a reaction vessel equipped with a reagent injection container, a cooling tube, a jacket heater, and a stirring device. Thereto were added 203 parts of distilled water and the resultant was stirred. Then, a mixture composed of 53.2 parts of n-butyl acrylate, 0.21 parts of allyl methacrylate, 0.11 parts of 1,3-butylene glycol dimethacrylate, and 0.13 parts of tertiary butyl hydroperoxide was added thereto. A nitrogen gas was flown through this reaction vessel so as to substitute the inside atmosphere with nitrogen, and the temperature was raised to 60° C. When the internal temperature of the reaction vessel reached 60° C., an aqueous solution of 0.0001 part of ferrous sulfate, 0.0003 parts of disodium ethylenediaminetetraacetate, and 0.24 parts of Rongalite in 10 parts of distilled water was added to initiate a radical polymerization. Due to the polymerization of the acrylate components, the temperature of the solution increased to 78° C. This state was maintained for 1 hour to complete the polymerization of the acrylate components, thereby yielding a rubbery polymer (B1-4) latex composed of a composite rubber of polyorganosiloxane and a butyl acrylate rubber.

(53) After the solution temperature inside the reaction vessel decreased to 60° C., an aqueous solution of 0.4 parts of Rongalite in 10 parts of distilled water was added. Subsequently, a mixed solution including 11.1 parts of acrylonitrile, 33.2 parts of styrene, and 0.2 parts of tertiary butyl hydroperoxide was dropwise added thereto over about 1 hour to effect polymerization. After the completion of the dropwise addition, the resulting mixture was allowed to stand for 1 hour, followed by addition of an aqueous solution of 0.0002 parts of ferrous sulfate, 0.0006 parts of disodium ethylenediaminetetraacetate, and 0.25 parts of Rongalite in 10 parts of distilled water. Subsequently, a mixed solution including 7.4 parts of acrylonitrile, 22.2 parts of styrene, and 0.1 part of tertiary butyl hydroperoxide was dropwise added thereto over about 40 minutes to effect polymerization. After the completion of the dropwise addition, the resulting mixture was allowed to stand for 1 hour, and was then cooled, thereby yielding a graft copolymer (B-4) latex.

(54) Subsequently, 150 parts of a 5% aqueous solution of calcium acetate was heated to 60° C. and stirred. 100 parts of the graft copolymer (B-4) latex was gradually dropwise added into this aqueous solution of calcium acetate to effect coagulation. The resulting coagulated product was separated, washed, and then dried, thereby yielding a graft copolymer (B-4) in the form of a dried powder.

(55) The acetone-soluble fraction of this graft copolymer (B-4) was 26%. The reduced viscosity of this acetone-soluble fraction was 0.60 dl/g.

(56) [Production of EPDM-Containing Crosslinked Latex (a)]

(57) 100 Parts of an EPDM (“EPT3012P” manufactured by Mitsui Chemicals Inc.; the ratio of ethylene unit: 82 mol %, the ratio of nonconjugated diene (5-ethylidene-2-norbornene) unit: 1 mol %) were dissolved in 566 parts of n-hexane. Then, 10 parts of an acid-modified polyethylene (“Hi-wax (registered trademark) 2203A”, manufactured by Mitsui Chemicals, Inc.) were added to the resulting solution, followed by the addition of 4.5 parts of oleic acid, and these were dissolved completely. Separately, 0.5 parts of ethylene glycol were added to an aqueous solution obtained by dissolving 0.9 parts of potassium hydroxide in 700 parts of water, and the resulting was kept at 60° C. Thereto was gradually added the EPDM solution prepared above, thereby emulsifying the resulting mixture, followed by stirring with a homomixer. Then, the solvent and a part of the water were distilled off, thereby obtaining a latex having an average particle size of 0.4 to 0.6 μm. To the obtained latex were added 1.5 parts of divinylbenzene and 1.0 part of di-tert-butylperoxytrimethylcyclohexane, relative to 100 parts of the EPDM, and a reaction was carried out for 1 hour at 120° C., thereby obtaining an EPDM-containing crosslinked latex (a). With respect to the obtained EPDM-containing crosslinked latex (a), the acid-modified polyethylene content, the gel content and the average particle size are shown in Table 1.

(58) [Production of EPDM-Containing Crosslinked Latex (b)]

(59) An EPDM-containing crosslinked latex (b) was obtained in the same manner as in the production of the EPDM-containing crosslinked latex (a) except that the amount of the di-tert-butylperoxytrimethylcyclohexane was changed from 1.0 part to 2.0 parts. With respect to the obtained EPDM-containing crosslinked latex (b), the acid-modified polyethylene content, the gel content and the average particle size are shown in Table 1.

(60) [Production of EPDM-Containing Crosslinked Latex (c)]

(61) An EPDM-containing crosslinked latex (c) was obtained in the same manner as in the production of the EPDM-containing crosslinked latex (a) except that the amount of the di-tert-butylperoxytrimethylcyclohexane was changed from 1.0 part to 3.0 parts. With respect to the obtained EPDM-containing crosslinked latex (c), the acid-modified polyethylene content, the gel content and the average particle size are shown in Table 1.

(62) [Production of EPDM-Containing Crosslinked Latex (d)]

(63) An EPDM-containing crosslinked latex (d) was obtained in the same manner as in the production of the EPDM-containing crosslinked latex (a) except that the acid-modified polyethylene was not added. With respect to the obtained EPDM-containing crosslinked latex (d), the acid-modified polyethylene content, the gel content and the average particle size are shown in Table 1.

(64) [Production of EPDM-Containing Crosslinked Latex (e)]

(65) An EPDM-containing crosslinked latex (e) was obtained in the same manner as in the production of the EPDM-containing crosslinked latex (a) except that the amount of the acid-modified polyethylene was changed from 10 parts to 25 parts. With respect to the obtained EPDM-containing crosslinked latex (e), the acid-modified polyethylene content, the gel content and the average particle size are shown in Table 1.

(66) TABLE-US-00004 TABLE 1 Amount of acid- Average EPDM-containing modified particle crosslinked latex polyethylene(*) Gel content (%) diameter (μm) (a) 10 69 0.57 (b) 10 13 0.53 (c) 10 98 0.55 (d) 0 73 0.52 (e) 25 71 0.48 (*)Amount (parts) relative to 100 parts of EPDM

(67) [Production of Graft Copolymer (B-5)]

(68) Into a stainless steel polymerizer vessel equipped with a stirrer were added 70 parts of the EPDM-containing crosslinked latex (a), 170 parts of water, 0.01 part of sodium hydroxide, 0.45 parts of sodium pyrophosphate, 0.01 part of ferrous sulfate, 0.57 parts of dextrose, and the polymerization was performed at a constant polymerization temperature of 80° C. while continuously adding 9 parts of acrylonitrile, 21 parts of styrene, 1.0 part of cumene hydroperoxide over 150 minutes and while, at the same time, continuously adding 0.45 parts of sodium pyrophosphate, 0.01 part of ferrous sulfate, 0.56 parts of dextrose, 1.0 part of sodium oleate, 30 parts of water over 180 minutes, thereby obtaining a graft polymer (B-5) latex. The polymerization ratio was 93%, and the amount of precipitated solids was 0.25%.

(69) An antioxidant was added to the graft copolymer (B-5) latex, and the resulting was coagulated with sulfuric acid, followed by washing, dehydration and drying, to thereby obtain a powder of the graft copolymer (B-5).

(70) The acetone-soluble fraction of this graft copolymer (B-5) was 4%. The reduced viscosity of this acetone-soluble fraction was 0.30 dl/g.

(71) [Production of Graft Copolymer (B-6)]

(72) A graft polymer (B-6) latex was obtained in the same manner as in the preparation of the graft copolymer (B-5) except that the EPDM-containing crosslinked latex (b) was used instead of the EPDM-containing crosslinked latex (a). The polymerization ratio was 90%, and the amount of precipitated solids was 0.22%.

(73) Further, a powder of the graft copolymer (B-6) was obtained in the same manner as in the preparation of the graft copolymer (B-5).

(74) The acetone-soluble fraction of this graft copolymer (B-6) was 4%. The reduced viscosity of this acetone-soluble fraction was 0.29 dl/g.

(75) [Production of Graft Copolymer (B-7)]

(76) A graft polymer (B-7) latex was obtained in the same manner as in the preparation of the graft copolymer (B-5) except that the EPDM-containing crosslinked latex (c) was used instead of the EPDM-containing crosslinked latex (a). The polymerization ratio was 92%, and the amount of precipitated solids was 0.31%.

(77) Further, a powder of the graft copolymer (B-7) was obtained in the same manner as in the preparation of the graft copolymer (B-5).

(78) The acetone-soluble fraction of this graft copolymer (B-7) was 4%. The reduced viscosity of this acetone-soluble fraction was 0.30 dl/g.

(79) [Production of Graft Copolymer (B-8)]

(80) A graft polymer (B-8) latex was obtained in the same manner as in the preparation of the graft copolymer (B-5) except that the EPDM-containing crosslinked latex (d) was used instead of the EPDM-containing crosslinked latex (a). The polymerization ratio was 92%, and the amount of precipitated solids was 0.52%.

(81) Further, a powder of the graft copolymer (B-8) was obtained in the same manner as in the preparation of the graft copolymer (B-5).

(82) The acetone-soluble fraction of this graft copolymer (B-8) was 4%. The reduced viscosity of this acetone-soluble fraction was 0.29 dl/g.

(83) [Production of Graft Copolymer (B-9)]

(84) A graft polymer (B-9) latex was obtained in the same manner as in the preparation of the graft copolymer (B-5) except that the EPDM-containing crosslinked latex (e) was used instead of the EPDM-containing crosslinked latex (a). The polymerization ratio was 93%, and the amount of precipitated solids was 0.24%.

(85) Further, a powder of the graft copolymer (B-9) was obtained in the same manner as in the preparation of the graft copolymer (B-5).

(86) The acetone-soluble fraction of this graft copolymer (B-9) was 4%. The reduced viscosity of this acetone-soluble fraction was 0.29 dl/g.

(87) [Glass Fiber (D)]

(88) The “CSG 3PA-820” (surface treatment agent: water-soluble polyurethane, the ratio represented by [major axis]/[minor axis]=4) which was chopped glass fibers and manufactured by Nitto Boseki Co., Ltd. was used as a glass fiber (D-1).

(89) The “CSH 3PA-870” (surface treatment agent: water-soluble polyurethane, the ratio represented by [major axis]/[minor axis]=2) which was chopped glass fibers and manufactured by Nitto Boseki Co., Ltd. was used as a glass fiber (D-2).

(90) The “CS3PE-937” (surface treatment agent: water-soluble epoxy resin, the ratio represented by [major axis]/[minor axis]=1) which was chopped glass fibers and manufactured by Nitto Boseki Co., Ltd. was used as a glass fiber (D-3).

(91) The “CS3PE-455” (surface treatment agent: water-soluble polyurethane, the ratio represented by [major axis]/[minor axis]=1) which was chopped glass fibers and manufactured by Nitto Boseki Co., Ltd. was used as a glass fiber (D-4).

(92) [Glycidyl Ether Unit-Containing Polymer (E)]

(93) An epoxy group-containing phenoxy resin (“jER (registered trademark) 4250” (weight average molecular weight: 60,000) manufactured by Mitsubishi Chemical Co., Ltd.) was used as a glycidyl ether unit-containing polymer (E-1).

(94) An epoxy group-containing phenoxy resin (“jER (registered trademark) 1256” (weight average molecular weight: 50,000) manufactured by Mitsubishi Chemical Co., Ltd.) was used as a glycidyl ether unit-containing polymer (E-2).

(95) A bisphenol A type epoxy resin (“jER (registered trademark) 1010” (weight average molecular weight: 5,500) manufactured by Mitsubishi Chemical Co., Ltd.) was used as a glycidyl ether unit-containing polymer (E-3).

(96) A bisphenol A type epoxy resin (“jER (registered trademark) 1009” (weight average molecular weight: 3,800) manufactured by Mitsubishi Chemical Co., Ltd.) was used as a glycidyl ether unit-containing polymer (E-4).

(97) A bisphenol A type epoxy resin (“jER (registered trademark) 1004” (weight average molecular weight: 1,650) manufactured by Mitsubishi Chemical Co., Ltd.) was used as a glycidyl ether unit-containing polymer (E-5).

(98) [Production of Glycidyl Ether Unit-Containing Polymer (E-6)]

(99) Into a separable flask having a capacity of 500 ml and equipped with a stirrer, a thermometer, a nitrogen inlet and a cooling tube were charged 82.42 parts of a bisphenol A type epoxy resin (epoxy equivalent: 467 g/eq), 6.3 parts of a bisphenol A type liquid epoxy resin (epoxy equivalent weight: 210 g/eq, hydrolyzable chlorine: 1.79%), 13.95 parts of bisphenol A, 19.6 parts of p-cumylphenol, 7.5 parts of a polyester resin (“GV-335”, manufactured by Japan U-pica Co., Ltd.; acid value: 30 KOHmg/g) and 30 parts of xylene, and the resulting mixture was heated to raise the temperature thereof under a nitrogen atmosphere.

(100) When the internal temperature of the reaction system had reached 80° C., 0.18 part of 5% aqueous lithium chloride solution were added, followed by further heating to raise the temperature. When the internal temperature of the reaction system had reached 130° C., the reaction system was depressurized to withdraw xylene and water from the system. The reaction was performed while maintaining the reaction temperature at 160° C. for 1 hour, whereafter the internal pressure of the reaction system was returned to the atmospheric pressure by introducing nitrogen into the reaction system. When 7 hours have passed since the reaction temperature had reached 160° C., 20.25 parts of a high molecular weight bisphenol A epoxy resin (epoxy equivalent: 2,700 g/eq) were added and the resulting mixture was stirred for 1 hour. Then, 100 parts of a polyester resin (“GV-730” manufactured by Japan U-pica Co., Ltd.; acid value: 3 KOHmg/g) was added, and a reaction was performed at 180° C. for 10 hours, to thereby obtain a high molecular weight epoxy resin. For measuring the molecular weight of the obtained high molecular weight epoxy resin by GPC, it was attempted to dissolve 0.1 g of a sample thereof in 10 ml of tetrahydrofuran, to find that about 0.05 g of the sample were insoluble. The resulting was filtered through a 5C filter paper, and the filtrate was subjected to a molecular weight measurement by GPC. As a result, the weight average molecular weight was found to be 70,200.

(101) [Phosphoric Acid Ester-Based Flame Retardant (F)]

(102) Phenylene-bis(dixylylphosphate) (“PX-200”, manufactured by Daihachi Chemical Industry Co., Ltd.; weight average molecular weight: 686, catalogue value) was used as a phosphoric acid ester-based flame retardant (F-1).

(103) Phenylene-bis(dixylylphosphate) (“CR-733S”, manufactured by Daihachi Chemical Industry Co., Ltd.; weight average molecular weight: 574, catalogue value) was used as a phosphoric acid ester-based flame retardant (F-2).

(104) Triphenylphosphate (“TPP”, manufactured by Daihachi Chemical Industry Co., Ltd.; weight average molecular weight: 326, catalogue value) was used as a phosphoric acid ester-based flame retardant (F-3).

(105) Bisphenol-A bis(diphenyl phosphate) (“BAPP”, manufactured by Ajinomoto Fine-Techno Co., Inc.; weight average molecular weight: 692, catalogue value) was used as a phosphoric acid ester-based flame retardant (F-4).

(106) [Organomodified Siloxane Compound (G)]

(107) As organomodified siloxane (G-1), “TEGOMER (registered trademark) AntiScratch 100” (a compound of an organomodified siloxane and a polyolefin) manufactured by Evonik Industries Co., Ltd. was used.

(108) As organomodified siloxane (G-2), “TEGOMER (registered trademark) AntiScratch 200” (a compound of an organomodified siloxane and a polyamide) manufactured by Evonik Industries Co., Ltd. was used.

(109) [Flame Retardant Auxiliary Agent (H)]

(110) Polytetrafluoroethylene (PTFE) was used as a flame retardant auxiliary agent (H-1).

(111) [Other Components]

(112) As a sliding property-imparting material other than the organomodified siloxane (G), the following compounds were used.

(113) Silicone oil: “SH-200-100CS” manufactured by Dow Corning Toray Co., Ltd.

(114) Low molecular weight PTFE: “Lubron (registered trademark) L-5F” manufactured by Daikin Industries, Ltd.

(115) Acid-modified polyethylene: “High-Wax (registered trademark) 2203A” manufactured by Mitsui Chemicals, Inc.

Examples 1 to 25, Comparative Examples 1 to 10

(116) The components described above were mixed at the ratios as indicated in Table 2 et seq. to obtain reinforced thermoplastic resin compositions. Each of the obtained reinforced thermoplastic resin compositions was formed into a molded article for evaluation. In the table, each of the amounts of the components (E) to (H) and the other components is an amount relative to 100 parts of the component (C). With respect to the obtained molded article, the Charpy impact strength, the flexural strength, the flexural modulus, the sliding property, and the appearance were evaluated. The evaluation results are shown in Table 2 et seq.

(117) TABLE-US-00005 TABLE 2 Example No. 1 2 3 4 5 6 7 Reinforced C A % 50 50 50 50 50 50 50 Thermoplastic B-1 % 50 Resin B-2 % 50 Composition B-3 % 50 B-4 % 50 B-5 % 50 50 B-6 % B-7 % 50 B-8 % B-9 % E-1 Part 3 E-2 Part 3 3 3 3 3 3 E-3 Part E-4 Part E-5 Part E-6 Part F-1 Part 3 3 3 3 3 3 3 F-2 Part F-3 Part F-4 Part G-1 Part 1 1 1 1 1 1 1 G-2 Part Silicone oil Part Low molecular weight PTFE Part Acid-modified polyethylene Part H-1 Part 0.5 0.5 0.5 0.5 0.5 0.5 0.5 D-1 Part D-2 Part D-3 Part D-4 Part 46.1 46.1 46.1 46.1 46.1 46.1 46.1 Amount ratio relative to % 30 30 30 30 30 30 30 the amount of reinforced thermoplastic resin composition Charpy Impact Strength kJ/m.sup.2 8 8 8 9 10 10 9 Flexural Strength MPa 168 173 178 176 163 163 142 Flexural Modulus MPa 7900 7800 7800 7900 7800 7800 7600 Sliding Property (coefficient of — 0.188 0.188 0.189 0.188 0.160 0.160 0.159 dynamic friction) Appearance — ◯ ◯ ◯ ◯ ◯ ◯ ◯ Moldability — ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯

(118) TABLE-US-00006 TABLE 3 Example No. 8 9 10 11 12 13 14 Reinforced C A % 50 50 50 50 50 50 50 Thermoplastic B-1 % Resin B-2 % Composition B-3 % B-4 % B-5 % 50 50 50 50 50 50 50 B-6 % B-7 % B-8 % B-9 % E-1 Part E-2 Part 3 3 3 3 3 E-3 Part 3 E-4 Part 3 E-5 Part E-6 Part F-1 Part 3 3 3 3 F-2 Part 3 F-3 Part 3 F-4 Part 3 G-1 Part 1 1 1 1 1 1 G-2 Part 1 Silicone oil Part Low molecular weight PTFE Part Acid-modified polyethylene Part H-1 Part 0.5 0.5 0.5 0.5 0.5 0.5 0.5 D-1 Part D-2 Part D-3 Part 46.1 D-4 Part 46.1 46.1 46.1 46.1 46.1 46.1 Amount ratio relative to the % 30 30 30 30 30 30 30 amount of reinforced thermoplastic resin composition Charpy Impact Strength kJ/m.sup.2 9 8 11 11 10 10 8 Flexural Strength MPa 150 150 163 164 160 167 150 Flexural Modulus MPa 7700 7700 7800 7800 7800 7800 7800 Sliding Property (coefficient of — 0.159 0.158 0.158 0.159 0.159 0.176 0.160 dynamic friction) Appearance — ◯ ◯ ◯ ◯ ◯ ◯ ◯ Moldability — ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ⊚

(119) TABLE-US-00007 TABLE 4 Example No. 15 16 17 18 19 20 21 Reinforced C A % 50 50 95 100 50 50 50 Thermoplastic B-1 % Resin B-2 % Composition B-3 % B-4 % B-5 % 50 50 5 50 50 50 B-6 % B-7 % B-8 % B-9 % E-1 Part E-2 Part 3 3 3 3 3 1 8 E-3 Part E-4 Part E-5 Part E-6 Part F-1 Part 3 3 23 25 1 3 3 F-2 Part 3 F-3 Part F-4 Part G-1 Part 1 1 1 1 1 1 1 G-2 Part Silicone oil Part Low molecular weight PTFE Part Acid-modified polyethylene Part H-1 Part 0.5 0.5 0.5 0.5 0.5 0.5 0.5 D-1 Part 46.1 D-2 Part 46.1 D-3 Part D-4 Part 105.9 134.5 11.9 45.2 48.2 Amount ratio relative to the % 30 30 45 50 10 30 30 amount of reinforced thermoplastic resin composition Charpy Impact Strength kJ/m.sup.2 10 10 13 11 11 8 12 Flexural Strength MPa 161 159 210 208 165 136 203 Flexural Modulus MPa 7900 8000 13000 13200 7700 7700 7800 Sliding Property (coefficient of — 0.160 0.160 0.188 0.190 0.159 0.160 0.161 dynamic friction) Appearance — ◯ ◯ ◯ ◯ ◯ ◯ ◯ Moldability — ⊚ ⊚ ⊚ ◯ ⊚ ⊚ ⊚

(120) TABLE-US-00008 TABLE 5 Example No. 22 23 24 25 Reinforced C A % 50 50 50 50 Thermoplastic B-1 % Resin B-2 % Composition B-3 % B-4 % B-5 % 50 50 50 50 B-6 % B-7 % B-8 % B-9 % E-1 Part E-2 Part 10 3 3 3 E-3 Part E-4 Part E-5 Part E-6 Part F-1 Part 3 3 3 3 F-2 Part F-3 Part F-4 Part G-1 Part 1 2 4 5 G-2 Part Silicone oil Part Low molecular weight PTFE Part Acid-modified polyethylene Part H-1 Part 0.5 0.5 0.5 0.5 D-1 Part D-2 Part D-3 Part D-4 Part 48.9 46.5 47.4 47.8 Amount ratio relative to the % 30 30 30 30 amount of reinforced thermoplastic resin composition Charpy Impact Strength kJ/m.sup.2 13 10 10 9 Flexural Strength MPa 202 151 150 140 Flexural Modulus MPa 7700 7600 7600 7600 Sliding Property (coefficient of — 0.160 0.112 0.096 0.090 dynamic friction) Appearance — ◯ ◯ ◯ ◯ Moldability — ◯ ⊚ ⊚ ◯

(121) TABLE-US-00009 TABLE 6 Comparative Example No. 1 2 3 4 5 Reinforced C A % 50 50 50 50 50 Thermoplastic B-1 % Resin B-2 % Composition B-3 % B-4 % 50 50 B-5 % 50 50 50 B-6 % B-7 % B-8 % B-9 % E-1 Part 3 3 E-2 Part 3 E-3 Part E-4 Part E-5 Part 3 E-6 Part 3 F-1 Part 3 3 3 3 3 F-2 Part F-3 Part F-4 Part G-1 Part 1 1 1 G-2 Part Silicone oil Part 1 Low molecular weight PTFE Part Acid-modified polyethylene Part H-1 Part 0.5 0.5 0.5 0.5 0.5 D-1 Part D-2 Part D-3 Part D-4 Part 45.6 44.8 46.1 46.1 46.1 Amount ratio relative to the % 30 30 30 30 30 amount of reinforced thermoplastic resin composition Charpy Impact Strength kJ/m.sup.2 7 6 7 10 10 Flexural Strength MPa 148 126 122 140 164 Flexural Modulus MPa 7400 7700 7800 7600 7800 Sliding Property (coefficient of — 0.296 0.224 0.160 0.159 0.264 dynamic friction) Appearance — ◯ ◯ ◯ ◯ ◯ Moldability — ⊚ ⊚ ⊚ X ⊚

(122) TABLE-US-00010 TABLE 7 Comparative Example No. 6 7 8 9 10 Reinforced C A % 50 50 45 50 50 Thermoplastic B-1 % Resin B-2 % Composition B-3 % B-4 % 50 50 B-5 % 55 50 50 B-6 % B-7 % B-8 % B-9 % E-1 Part 3 3 3 11 3 E-2 Part E-3 Part E-4 Part E-5 Part E-6 Part F-1 Part 3 3 3 3 F-2 Part F-3 Part F-4 Part G-1 Part 1 1 1 G-2 Part Silicone oil Part Low molecular weight PTFE Part 1 Acid-modified polyethylene Part 1 H-1 Part 0.5 0.5 0.5 0.5 0.5 D-1 Part D-2 Part D-3 Part D-4 Part 46.1 46.1 46.1 49.9 44.8 Amount ratio relative to the % 30 30 30 30 30 amount of reinforced thermoplastic resin composition Charpy Impact Strength kJ/m.sup.2 9 9 6 13 12 Flexural Strength MPa 163 146 136 201 166 Flexural Modulus MPa 7800 7900 7500 7600 7800 Sliding Property (coefficient of — 0.208 0.192 0.164 0.161 0.161 dynamic friction) Appearance — ◯ ◯ ◯ ◯ ◯ Moldability — ⊚ ⊚ ⊚ X X

(123) From the comparison between Example 4 and Comparative Examples 1, 5, 6 and 7, it can be seen that the reinforced thermoplastic resin composition of the present invention is superior in the sliding property of the molded article to the reinforced thermoplastic resin compositions containing no organomodified siloxane compound (G).

(124) From the comparison between Example 5 and Comparative Example 2, it can be seen that the reinforced thermoplastic resin composition of the present invention is superior in the impact resistance or mechanical strength of the molded article to the reinforced thermoplastic resin composition containing no glycidyl ether unit-containing polymer (E).

(125) From the comparison between Example 5 and Comparative Example 3, it can be seen that the reinforced thermoplastic resin composition of the present invention is superior in the impact resistance or mechanical strength of the molded article to the reinforced thermoplastic resin composition containing a glycidyl ether unit-containing polymer (E) having a weight average molecular weight of less than 3,800.

(126) From the comparison between Example 5 and Comparative Example 4, it can be seen that the reinforced thermoplastic resin composition of the present invention is superior in the moldability to the reinforced thermoplastic resin composition containing a glycidyl ether unit-containing polymer (E) having a weight average molecular weight of higher than 60,000.

(127) From the comparison between Example 5 and Comparative Example 8, it can be seen that the reinforced thermoplastic resin composition of the present invention is superior in the impact resistance of the molded article to the reinforced thermoplastic resin composition in which the amount of the polycarbonate resin (A) in the main resin component (C) is less than 50% by weight.

(128) From the comparison between Example 5 and Comparative Example 9, it can be seen that the reinforced thermoplastic resin composition of the present invention is superior in the moldability to the reinforced thermoplastic resin composition in which the amount of the glycidyl ether unit-containing polymer (E) is larger than 10 parts, relative to 100 parts of the main resin component (C).

(129) From the comparison between Example 5 and Comparative Example 10, it can be seen that the reinforced thermoplastic resin composition of the present invention is superior in the moldability to the reinforced thermoplastic resin composition containing no phosphoric acid ester-based flame retardant (F).

INDUSTRIAL APPLICABILITY

(130) The reinforced thermoplastic resin compositions of the present invention is especially useful as materials for the housings of mobile devices such as laptop personal computers, tablet personal computers, mobile phones including smart phones, digital cameras, digital video cameras, or the like.