JP3474251B2 - Fiber reinforced thermoplastic resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fiber-reinforced thermoplastic resin composition. More specifically, it has excellent rigidity and dimensional accuracy,
The present invention also relates to a fiber-reinforced thermoplastic resin composition having excellent impact resistance. [0002] Aromatic polycarbonate resins are known as excellent engineering plastics.
Polycarbonate resin compositions reinforced with fibrous fillers to further improve heat resistance and rigidity and to reduce molding shrinkage and thermal expansion coefficient have been put on the market, and are used in a wide range of fields including precision parts. However, polycarbonate resin reinforced with fibrous filler has a problem that its impact resistance is inferior to non-reinforced polycarbonate resin, especially for molded products for thin-walled enclosures, etc. Is strongly desired. [0003] Various proposals have been made to improve the impact resistance of fiber reinforced polycarbonate resins. For example,
There is a method of blending polyethylene (JP-A-57-94040) or a rubber component (JP-B-53-12946). However, the effect of improving the impact resistance by these methods is not yet sufficient, and further improvement is desired. [0004] An object of the present invention is to provide a fiber-reinforced thermoplastic resin composition having excellent dimensional accuracy and mechanical properties, and particularly good impact resistance. The present inventors have conducted intensive studies to achieve the above object, and as a result, the aromatic polycarbonate resin composition containing carbon fibers and / or metal-coated carbon fibers has a carboxyl group. When a specific composite rubber-based graft polymer of olefin-based wax or olefin-based polymer, polyorganosiloxane rubber, and polyalkyl (meth) acrylate rubber is blended, a fiber-reinforced thermoplastic resin composition meeting the above-mentioned object can be obtained. Heading, the present invention has been reached. SUMMARY OF THE INVENTION [0006] The present invention relates to a method for satisfying L / D ≧ 3.
It is selected from olefin-based waxes and olefin-based polymers having a carboxylic anhydride group and / or a carboxyl group in 100 parts by weight of an aromatic polycarbonate resin composition containing 1 to 60% by weight of carbon fiber and / or metal-coated carbon fiber. At least one compound 0.0
One or more vinyl monomers in a composite rubber having a structure in which 5 to 30 parts by weight, a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are entangled with each other so as not to be separated. Is a composite rubber-based graft copolymer obtained by graft polymerization or a mixture of the composite rubber-based graft copolymer and a vinyl copolymer 0.5
The present invention relates to a fiber-reinforced thermoplastic resin composition containing up to 30 parts by weight. The aromatic polycarbonate resin used in the present invention is produced by reacting a dihydric phenol with a carbonate precursor by a solution method or a melting method. Examples of the dihydric phenol include 2,2-bis (4-hydroxyphenyl) propane (commonly known as bisphenol A) and bis (4-
Hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 2,2
-(4-hydroxy-3-methylphenyl) propane,
Bis (4-hydroxyphenyl) sulfone and the like can be mentioned. Preferred dihydric phenols are bis (4-hydroxyphenyl) alkanes, especially bisphenol A
Is preferred. Examples of the carbonate precursor include carbonyl halides, carbonate esters, and haloformates, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformates of dihydric phenols, and mixtures thereof. In producing the aromatic polycarbonate resin, the dihydric phenol may be used alone or in combination of two or more. In addition, a suitable molecular weight regulator, a branching agent, a catalyst for accelerating the reaction, and the like can also be used. Although the molecular weight of the aromatic polycarbonate resin is not specified, if the molecular weight is too low, the impact resistance decreases, and if the molecular weight is too high, the moldability decreases, so that the viscosity average molecular weight is 10,000 to 50,000. Are preferred, and those of 15,000 to 30,000 are particularly preferred. Also, two or more aromatic polycarbonate resins may be mixed. The carbon fiber and / or metal used in the present invention
The coated carbon fiber is not particularly limited as long as L / D ≧ 3 (L: fiber length, D: fiber diameter) and generally used for reinforcing an aromatic polycarbonate resin. L /
When D is less than 3, the effect of improving the mechanical properties is insufficient, which is not preferable . Diameter is preferably has 3 to 30 .mu.m, to use a fiber length in the range of usually 0.01～8Mm. The diameter of the whiskers is preferably 0.01 to 5 μm, and the fiber length is 1 to 100 μm. The carbon fibers and / or metal-coated carbon fibers are preferably subjected to a surface treatment or a surface oxidation treatment with a silane coupling agent, a titanate coupling agent, an aluminate coupling agent or the like. Further, olefin resin, styrene resin, acrylic resin, polyester resin, epoxy resin, those that have been subjected to a bunching treatment with a urethane resin, and the like, particularly those that have been bunched with an epoxy resin or a urethane resin are particularly preferable. . If the addition amount of the carbon fiber and / or the metal-coated carbon fiber is too small, the reinforcing effect is small, and if it is too large, the effect of improving the impact resistance of the composition cannot be obtained, so that the aromatic polycarbonate resin and the carbon fiber and / or It is usually 1 to 60% by weight, and preferably 3 to 50% by weight, based on 100% by weight of the metal-coated carbon fibers in total. The olefin wax or olefin polymer having a carboxylic anhydride group and / or a carboxyl group (hereinafter simply referred to as having a carboxyl group) used in the present invention is an olefin wax or an olefin polymer. Is a wax or a polymer obtained by oxidizing or acid-treating . [0012] [0013] [0014] Ca Rubo olefin wax and olefin polymer having a cyclohexyl group may be used alone or in combination, the amount of the aromatic polycarbonate resin and carbon
0.05 to 30 parts by weight, preferably 0.1 to 1 part by weight, based on 100 parts by weight of the fiber and / or the metal-coated carbon fiber in total.
5 parts by weight. If the amount is less than 0.05 part by weight, the effect of improving the impact resistance is small. Absent. The composite rubber-based graft copolymer used in the present invention is a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are entangled with each other so that they cannot be separated. It is a composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl monomers or a mixture of such a composite rubber-based polymer and a vinyl-based polymer. If the particle size of the composite rubber used here is too small, the impact resistance of the obtained resin composition will decrease, and if it is too large, the surface appearance of the molded article of the obtained resin composition will deteriorate. Therefore, the average particle diameter of the composite rubber is preferably 0.08 to 0.6 μm. In order to obtain a composite rubber-based graft copolymer, first, various cyclic organosiloxanes having three or more ring members, for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and the like, are crosslinked with a crosslinking agent and / or a graft. The latex of the polyorganosiloxane rubber is prepared by emulsion polymerization using a cross-linking agent, and then the latex of the polyorganosiloxane rubber is impregnated with an alkyl (meth) acrylate monomer, a crosslinking agent and / or a graft cross-linking agent, and then polymerized. It is obtained by doing. The alkyl (meth) acrylate monomer used herein includes, for example, alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, hexyl methacrylate,
Examples thereof include alkyl methacrylates such as ethylhexyl methacrylate, and n-butyl acrylate is particularly preferable. Examples of the vinyl monomer to be graft-polymerized on the composite rubber include aromatic vinyl compounds such as styrene and α-methylstyrene, vinyl cyanide compounds such as acrylonitrile and methacrylonitrile, methyl methacrylate, and 2-ethylhexyl. Examples thereof include methacrylates such as methacrylate, and acrylates such as methyl acrylate, ethyl acrylate, and butyl acrylate. These may be used alone or in combination of two or more. The ratio of the composite rubber to the vinyl monomer in the composite rubber-based graft copolymer is preferably 30 to 95% by weight of the composite rubber and 70 to 5% by weight of the vinyl monomer based on the weight of the graft copolymer. , Composite rubber 40-9
0% by weight and 60 to 10% by weight of a vinyl monomer are particularly preferred. If the amount of the vinyl monomer is less than 5% by weight, the graft copolymer in the resin composition tends to be poorly dispersed, and if the amount exceeds 70% by weight, the effect of improving the impact strength is undesirably reduced. . Further, a mixture of the above-mentioned composite rubber-based graft copolymer and a vinyl-based polymer may be used. In this case, the vinyl-based copolymer may be a vinyl-based monomer to be graft-polymerized as described above. At least one monomer selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers and (meth) acrylate monomers,
Those obtained by copolymerizing 0% by weight and 30 to 0% by weight of a vinyl monomer copolymerizable therewith, for example, ethylene and vinyl acetate, are used. Two or more of these vinyl monomers may be used in combination. Preferred examples of such a composite rubber-based graft copolymer or a mixture of the composite rubber-based graft copolymer and a vinyl-based monomer include a composite rubber-based graft copolymer described in JP-A-1-230664 or A mixture of the graft copolymer and a vinyl monomer is exemplified. Among them, preferred are those commercially available from Mitsubishi Rayon Co., Ltd. under the trade name Metablen S-2001. The compounding amount of the composite rubber-based graft copolymer is as follows:
The aromatic polycarbonate resin and carbon fiber and / or
0.5 with respect to 100 parts by weight in total with metal-coated carbon fiber
-30 parts by weight, preferably 1-20 parts by weight. If the compounding amount is less than 0.5 part by weight, the effect of improving the impact resistance is small, and if it exceeds 30 parts by weight, the extrudability and the mechanical strength, dimensional stability and heat resistance of the obtained molded product are reduced. Not preferred. The resin composition of the present invention contains optional additives such as a flame retardant, a flame retardant aid, a heat stabilizer, an antioxidant, a light stabilizer, a mold release agent, a flow modifier, a colorant, and a lubricant. If necessary, a foaming agent and the like may be added in an effective expression amount. Further, other reinforcing materials and fillers such as glass flakes, glass beads, talc, mica, wollastonite, calcium carbonate, carbon black, metal powder, metal flakes and the like can be used in combination. Further, another thermoplastic resin, an elastic body, or the like may be added. The resin composition of the present invention can be produced by any method. For example, tumblers, V-type blenders, Nauta mixers, Banbury mixers,
It can be manufactured by mixing with a kneading roll and an extruder.
The resin composition thus obtained is molded by various known methods, for example, an injection molding method, an extrusion molding method and the like. The present invention will be further described below with reference to examples. The evaluation was performed by the following method. Impact value: A
STM D-256 (with Izod notch, thickness 3.
2 mm). Flexural modulus: measured according to ASTM D-790. Examples 1 to 5 and Comparative Examples 1 to 9 After the polycarbonate resin, reinforcing fibers and additives shown in Table 1 were dry-blended in the proportions shown in Table 1, a single screw extruder with a screw diameter of 30 mm and a vent was used. Nakatanani Machinery Co., Ltd.
Manufactured by VSK-30] at a cylinder temperature of 290 ° C., pellets are obtained by strand cutting, and the obtained pellets are dried at 120 ° C. for 5 hours by a hot-air circulating drier, followed by an injection molding machine [Toshiba Machine Co., Ltd. Co., Ltd .: IS
[−150EN5Y], an impact test piece and a bending test piece were obtained at a cylinder temperature of 300 ° C. and a mold temperature of 100 ° C. Table 1 shows the evaluation results. The symbols for resins, fibers and additives in Table 1 are as follows. In addition, parts by weight indicating the amount of the additive to be added indicate the ratio to the total of 100 parts by weight of the resin and the fiber. PC: polycarbonate resin [Panlite L-1225 manufactured by Teijin Chemicals Ltd.] GF: chopped glass fiber [ECS03T-511 / P manufactured by Nippon Electric Glass Co., Ltd., diameter 13 μm, length 3 mm] CF: carbon fiber [Toho rayon Vesfight H manufactured by
TA-C6-U, diameter 7 μm, length 6 mm] NiCF: nickel-coated carbon fiber [Vesfight MCHTA-C6-US (I) manufactured by Toho Rayon Co., Ltd .;
7.5 μm in diameter and 6 mm in length] W-1: an olefin wax having a carboxyl group [Diacarna-30, manufactured by Mitsubishi Kasei Corporation, acid value 7]
5 mgKOH / g] W-2: an olefin wax having a carboxyl group [Mitsui Petrochemical Co., Ltd. wax acid treatment type 22]
03A, acid value 30 mg KOH / g] W-3: an olefin polymer having a carboxyl group [Exzero VA-1803 manufactured by Exxon Chemical Co., Ltd.
Maleic anhydride content 0.65% by weight] W-4: Olefin wax having no carboxyl group [High wax 200 manufactured by Mitsui Petrochemical Co., Ltd.]
P] W-5: an olefin polymer having no carboxyl group [HIZEX powder 2 manufactured by Mitsui Petrochemical Co., Ltd.]
100JP] R-1: Composite rubber-based graft copolymer [METABLEN S-2001 manufactured by Mitsubishi Rayon Co., Ltd.] R-2: MBS resin [Kaneace B-56 manufactured by Kanegafuchi Chemical Industry Co., Ltd.] R-3: Acrylic -Based copolymer [H manufactured by Kureha Chemical Industry Co., Ltd.
IA-15] [Table 1] The composition of the present invention has excellent rigidity, dimensional accuracy and impact resistance of fiber-reinforced aromatic polycarbonate resin, and is suitable for a wide range of industrial fields including housing for electric appliances. It is suitable in the field, and its industrial effect is remarkable.

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 51:00) (56) References JP-A-59-27947 (JP, A) JP-A-64-79257 (JP, A) JP-A Heisei 5-302025 (JP, A) JP-A-56-45944 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 69/00 C08K ⁷ /00-7/28

Claims (1)

(57) [Claims 1] Carbon fiber and / or metal core with L / D ≧ 3
At least one compound selected from an olefin wax and an olefin polymer having a carboxylic acid anhydride group and / or a carboxyl group in 100 parts by weight of an aromatic polycarbonate resin composition containing 1 to 60% by weight of carbon fibers. 0.05 to 30 parts by weight, a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component having a structure in which they are entangled with each other so that they cannot be separated from each other. Rubber-based thermoplastic resin composition obtained by blending 0.5 to 30 parts by weight of a composite rubber-based graft copolymer obtained by graft-polymerizing a polymer or a mixture of the composite rubber-based graft copolymer and a vinyl-based copolymer object.