JPH07238213A - Fiber-reinforced thermoplastic resin composition - Google Patents

Abstract

PURPOSE:To obtain a fiber-reinforced polycarbonate resin composition having excellent dimensional accuracy and excellent mechanical properties and especially excellent in impact resistance despite of containing a reinforcing fiber. CONSTITUTION:This fiber-reinforced thermoplastic resin composition is prepared by blending a reinforcing fiber-containing aromatic polycarbonate resin composition, one or more kinds of compounds selected from olefinic waxes and olefinic polymers respectively having carboxylic acid anhydride groups and/or carboxyl groups and a composite rubber-based graft copolymer synthesized by graftpolymerizing one or more kinds of vinyl monomers on a composite rubber having a structure in which a polyorganosiloxane rubber component and a polyalkyl (meth)acrylate rubber component are entangled with each other not so as to be separated from each other or a mixture of the composite rubber- based graft copolymer and a vinyl copolymer.

Description

Detailed Description of the Invention

[0001]

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,
A polycarbonate resin composition reinforced with a fibrous filler has been put on the market in order to further improve heat resistance and rigidity, and to reduce the molding shrinkage rate and the thermal expansion coefficient, and is used in a wide range of fields including precision parts. However, the polycarbonate resin reinforced with the fibrous filler has a problem that the impact resistance is inferior to that of the non-reinforced polycarbonate resin, and particularly in a molded product for a thin-walled case, the rigidity and the impact resistance are compatible with each other. Is strongly requested.

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 impact resistance by these methods is not yet sufficient, and further improvement is desired.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a fiber reinforced thermoplastic resin composition having excellent dimensional accuracy and mechanical properties and particularly good impact resistance.

The present inventor has conducted extensive studies in order to achieve the above object, and as a result, an aromatic polycarbonate resin composition containing reinforcing fibers was added to an olefin wax having a carboxyl group or an olefin polymer and a polyorganosiloxane. The present inventors have found that a fiber-reinforced thermoplastic resin composition that meets the above purpose can be obtained by blending a specific composite rubber-based graft polymer of rubber and polyalkyl (meth) acrylate rubber, and arrived at the present invention.

[0006]

According to the present invention, 100 parts by weight of an aromatic polycarbonate resin composition containing 1 to 60% by weight of reinforcing fibers having L / D ≧ 3 contains a carboxylic acid anhydride group and / or a carboxyl group. 0.05 to 30 parts by weight of at least one compound selected from the olefin wax and the olefin polymer having the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are intertwined with each other so that they cannot be separated. A composite rubber-based graft copolymer obtained by graft-polymerizing one or two or more vinyl-based monomers to the composite rubber included therein, or a mixture of the composite rubber-based graft copolymer and the vinyl-based copolymer 0 The present invention relates to a fiber reinforced thermoplastic resin composition containing 5 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 called 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,
Examples thereof include bis (4-hydroxyphenyl) sulfone. The preferred dihydric phenol is bis (4-hydroxyphenyl) alkane, especially bisphenol A.
Is preferred.

Further, examples of the carbonate precursor include carbonyl halide, carbonate ester, haloformate and the like, and specific examples thereof include phosgene, diphenyl carbonate, dihaloformate of dihydric phenol and a mixture thereof. In producing the aromatic polycarbonate resin, the dihydric phenol may be used alone or in combination of two or more kinds. Further, an appropriate molecular weight regulator, branching agent, catalyst for accelerating the reaction and the like can also be used. The molecular weight of the aromatic polycarbonate resin is not specified. However, if the molecular weight is too low, the impact resistance will decrease, and if it is too high, the molding processability will decrease. Therefore, it is represented by a viscosity average molecular weight of 10,000 to 50,000. Those having 15,000 to 30,000 are particularly preferable. Also, two or more aromatic polycarbonate resins may be mixed.

The reinforcing fibers used in the present invention have L / D ≧ 3.
(L: fiber length, D: fiber diameter) are not particularly limited as long as they are generally used for reinforcing an aromatic polycarbonate resin. If L / D is less than 3, the effect of improving mechanical properties is insufficient, which is not preferable. Examples of such reinforcing fibers include chopped glass fibers, milled glass fibers, carbon fibers, metal-coated carbon fibers, metal fibers, aramid fibers, and aluminum borate whiskers, whiskers such as potassium titanate whiskers, and these are used in combination of two or more. You can also do it. Preferred reinforcing fibers are chopped glass fibers, milled glass fibers, carbon fibers, and metal-coated carbon fibers, those having a diameter of 3 to 30 μm are preferable, and those having a fiber length of usually 0.01 to 8 mm are used. The whiskers preferably have a diameter of 0.01 to 5 μm and a fiber length of 1 to 100 μm.

Such reinforcing fibers are silane coupling agents,
Those subjected to surface treatment or surface oxidation treatment with a titanate coupling agent, an aluminate coupling agent or the like are preferable. In addition, olefin resin, styrene resin,
Those that have been subjected to a focusing treatment with an acrylic resin, a polyester resin, an epoxy resin, a urethane resin or the like are preferable, and those that have been subjected to a focusing treatment with an epoxy resin or a urethane resin are particularly preferable. If the addition amount of the reinforcing 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. Therefore, the addition amount is usually 1% based on 100% by weight of the total amount of the aromatic polycarbonate resin and the reinforcing fiber. -60% by weight, preferably 3-50% by weight.

The olefin wax or olefin polymer having a carboxylic acid 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. It is a wax or a polymer obtained by subjecting a wax to an oxidation treatment or an acid treatment. Preferred examples of the olefin wax having a carboxyl group include the following formulas.

[0012]

[Chemical 1]

[0013]

[Chemical 2]

[In the formula, n is an integer of 12 to 20. ]
I can give you one. Two or more kinds of olefin waxes and olefin polymers having a carboxyl group may be used in combination, and the amount thereof is 0.05 to 3 with respect to 100 parts by weight of the total amount of the aromatic polycarbonate resin and the reinforcing fiber.
It is 0 part by weight, preferably 0.1 to 15 parts by weight. When the amount is less than 0.05 parts by weight, the effect of improving impact resistance is small, and when the amount is more than 30 parts by weight, extrudability, mechanical strength, dimensional stability and heat resistance of a molded article are deteriorated, which is preferable. Absent.

The composite rubber-based graft copolymer used in the present invention is a composite rubber having a structure in which the polyorganosiloxane rubber component and the polyalkyl (meth) acrylate rubber component are intertwined with each other so that they cannot be separated. A composite rubber-based graft copolymer obtained by graft-polymerizing one or more vinyl-based 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 resulting resin composition will decrease, and if it is too large, the surface appearance of the molded article of the resulting resin composition will deteriorate. Therefore, the average particle diameter of the composite rubber is preferably 0.08 to 0.6 μm. To obtain a composite rubber-based graft copolymer, first, various cyclic organosiloxanes having three or more membered rings, such as hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, etc., and a crosslinking agent and / or a grafting agent. A polyorganosiloxane rubber latex is prepared by emulsion polymerization using a crossing agent, and then the poly (organosiloxane) rubber latex is impregnated with an alkyl (meth) acrylate monomer, a cross-linking agent and / or a graft crossing agent and then polymerized. It is obtained by doing.

Examples of the alkyl (meth) acrylate monomer used here include alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate and 2-ethylhexyl acrylate, hexyl methacrylate and 2-.
Examples thereof include alkyl methacrylates such as ethylhexyl methacrylate, and n-butyl acrylate is particularly preferable.

Examples of the vinyl-based 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 methacrylic acid esters such as methacrylate, acrylic acid esters 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-based 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-based monomer, based on the weight of the graft copolymer. , Composite rubber 40-9
0% by weight and 60 to 10% by weight of vinyl monomer are particularly preferable. If the amount of the vinyl-based monomer is less than 5% by weight, poor dispersion of the present graft copolymer in the resin composition tends to occur, and if it exceeds 70% by weight, the effect of improving impact strength tends to be low, such being undesirable. .

Further, a mixture of the above composite rubber-based graft copolymer and a vinyl-based polymer may be used, in which case the vinyl-based copolymer is the above-mentioned vinyl-based monomer to be graft-polymerized. 70 to 10 of one or more monomers selected from the group consisting of aromatic vinyl monomers, vinyl cyanide monomers and (meth) acrylic acid ester monomers similar to
What is obtained by copolymerizing 0% by weight with 30 to 0% by weight of a vinyl-based monomer copolymerizable therewith, for example, ethylene or vinyl acetate is used. Two or more kinds 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 the composite rubber-based graft copolymer described in JP-A 1-230664 or A mixture of the graft copolymer and a vinyl monomer can be used. Among them, the one commercially available from Mitsubishi Rayon Co., Ltd. under the trade name of METABLEN S-2001 is preferable.

The compounding amount of the composite rubber-based graft copolymer is
Total 1 of the aromatic polycarbonate resin and the reinforcing fiber
0.5 to 30 parts by weight, preferably 1 to 100 parts by weight
20 parts by weight. If the blending amount is less than 0.5 parts by weight, the impact resistance improving effect is small, and if it exceeds 30 parts by weight, the extrudability and the mechanical strength, dimensional stability and heat resistance of the resulting molded article are deteriorated. Not preferable.

The resin composition of the present invention contains optional additives such as flame retardants, flame retardant aids, heat stabilizers, antioxidants, light stabilizers, release agents, flow modifiers, colorants, and lubricants. If desired, a foaming agent or the like may be added in an effective expression amount thereof. 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 together. Further, other thermoplastic resins, elastic bodies, etc. may be added.

The resin composition of the present invention can be produced by any method. For example, tumbler, V type blender, Nauter mixer, Banbury mixer,
It can be manufactured by mixing with a kneading roll or an extruder.
The resin composition thus obtained is molded by various known methods such as injection molding and extrusion molding.

[0023]

EXAMPLES The present invention will be further described with reference to the following 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 8 and Comparative Examples 1 to 9] The polycarbonate resin shown in Table 1, the reinforcing fiber and the additives were dry blended in the proportions shown in Table 1, and then the screw diameter was 30 m.
Single-screw extruder with vent for m [Nakatani Machinery Co., Ltd .: VS
K-30] at a cylinder temperature of 290 ° C. and melt-kneaded to obtain pellets by strand cutting, and the obtained pellets are dried at 120 ° C. for 5 hours by a hot air circulation dryer, and then an injection molding machine [Toshiba Machine Co., Ltd. ): IS-150
EN5Y] cylinder temperature 300 ℃, mold temperature 1
Impact test pieces and bending test pieces were obtained at 00 ° C. The evaluation results are shown in Table 1.

The symbols for resins, fibers and additives in Table 1 are as follows. Further, the parts by weight showing the amount of addition of the additive shows the ratio to 100 parts by weight of the total of the resin and the fibers. 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 Co., Ltd.
TA-C6-U, diameter 7 μm, length 6 mm] NiCF: nickel-coated carbon fiber [Besfight MCHTA-C6-US (I) manufactured by Toho Rayon Co., Ltd.,
Diameter 7.5 μm, length 6 mm] W-1: Olefin wax having carboxyl group [Diacarna-30 manufactured by Mitsubishi Kasei Co., Ltd., acid value 7]
5 mgKOH / g] W-2: olefin wax having 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 [Egzero VA-1803 manufactured by Exxon Chemical Co., Ltd.,
Amount of maleic anhydride 0.65% by weight] W-4: Olefin wax having no carboxyl group [High Wax 200 manufactured by Mitsui Petrochemical Co., Ltd.]
P] W-5: olefin polymer having no carboxyl group [Hi-Zex Powder 2 manufactured by Mitsui Petrochemical Co., Ltd.]
100JP] R-1: Composite rubber-based graft copolymer [Metablene 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]

[0026]

[Table 1]

[0027]

INDUSTRIAL APPLICABILITY The composition of the present invention has the excellent rigidity, dimensional accuracy and impact resistance of the fiber reinforced aromatic polycarbonate resin, and is suitable for a wide range of industrial fields including housings for electric appliances. And the industrial effect that it produces is exceptional.

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Claims (1)

[Claims] 1. 1 to 60% by weight of reinforcing fiber having 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 the aromatic polycarbonate resin composition contained 0.05
˜30 parts by weight, a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are intertwined with each other so that they cannot be separated from each other. Graft-polymerized composite rubber-based graft copolymer or mixture of the composite rubber-based graft copolymer and vinyl-based copolymer 0.5 to
A fiber-reinforced thermoplastic resin composition containing 30 parts by weight.