JP3585147B2 - Polycarbonate resin composition - Google Patents

Description

【００３５】
【表２】

【００３６】
【発明の効果】
本発明のポリカーボネート樹脂組成物は、離型性、流動性、寸法安定性および機械的強度に優れている。成形加工性、寸法安定性等が不足するとして従来困難であった薄肉成形品用途においても、本発明のポリカーボネート樹脂組成物を用いる事で不都合を生じる事なく成形加工が可能であり、優れた寸法安定性および機械的強度を得る事が出来る。
【００３７】
【図面の簡単な説明】
【図１】正面図
本発明の実施例にて用いられた成形品の正面図である。１〜６は、反りの測定場所である。
【図２】断面図
（ａ）は、図１のＡ−Ａ部の断面図である。
（ｂ）は、図１のＢ−Ｂ部の断面図である。
（ｃ）は、図１のＣ−Ｃ部の断面図である。[0001]
The present invention relates to a polycarbonate resin composition. More specifically, the present invention relates to a polycarbonate resin composition containing a flake-like inorganic filler, a fibrous filler, and a polyethylene wax and having excellent releasability, fluidity, dimensional stability, and mechanical strength (impact resistance, rigidity). It is.
[0002]
[Prior art]
Polycarbonate resins are widely used as engineering plastics having excellent toughness, transparency, impact resistance and electrical properties. In addition, a reinforced polycarbonate resin composition containing glass fibers and / or glass beads for the purpose of further improving mechanical strength and dimensional stability utilizing the above characteristics has been proposed (JP-A-57-12815). ing.
[0003]
[Problems to be solved by the invention]
However, polycarbonate resin reinforced with glass fiber or glass beads improves mechanical strength and dimensional stability, but improves mechanical strength, dimensional stability, and mold release and fluidity during injection molding. However, there is a need for a material that is more excellent in fluidity, releasability, mechanical strength, and dimensional stability.
[0004]
Further, when trying to improve the mold release property of the reinforced polycarbonate resin, there is a problem that the balance between the mechanical strength and the dimensional stability of a thin molded product is inferior.
[0005]
[Means for Solving the Problems]
The present inventors have, as a result of various investigations to solve the problems described above, fluidity can be formulated specific flake-like filler, a fibrous filler Oyobipo triethylene wax, releasability, mechanical It has been found that a polycarbonate resin composition having excellent mechanical strength and dimensional stability can be obtained, and the present invention has been completed.
[0006]
That is, in the present invention, 1.5 parts by weight of polyethylene wax is added to 100 parts by weight of a mixture comprising 50 to 95% by weight of a polycarbonate resin, 5 to 50% by weight of a flake-like inorganic filler, and 0 to 25% by weight of a fibrous filler. An object of the present invention is to provide a polycarbonate resin composition containing not more than 3 parts by weight .
[0007]
Hereinafter, the present invention will be described in detail.
The polycarbonate resin used in the present invention is a polymer obtained by a phosgene method of reacting various dihydroxydiaryl compounds with phosgene, or a transesterification method of reacting a dihydroxydiaryl compound with a carbonate such as diphenyl carbonate. A typical example is a polycarbonate resin produced from 2,2-bis (4-hydroxyphenyl) propane (commonly called bisphenol A).
[0008]
Examples of the dihydroxydiaryl compound include bisphenol A, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, 2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxyphenyl-3-methylphenyl) propane, 1,1-bis (4-hydroxy-3) -Tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis ( Bis (hydroxyaryl) alkanes such as 4-hydroxy-3,5-dichlorophenyl) propane, 1,1- Bis (hydroxyaryl) cycloalkanes such as 1,4- (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3 Dihydroxy diaryl ethers such as 3,3'-dimethyldiphenyl ether, dihydroxy diaryl sulfides such as 4,4'-dihydroxy diphenyl sulfide, 4,4'-dihydroxy diphenyl sulphoxide, 4,4'-dihydroxy-3,3 ' Dihydroxydiarylsulfoxides such as dimethyldiphenylsulfoxide, dihydroxydiaryls such as 4,4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfone Sulfone, and the like.
[0009]
These may be used alone or as a mixture of two or more kinds. In addition, piperazine, dipiperidyl hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, and the like may be used in combination.
[0010]
Further, the above dihydroxyaryl compound and a phenol compound having three or more valences as shown below may be mixed and used.
Phloroglucin, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene, 2,4,6-dimethyl-2,4,6-tri- (4 -Hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) -benzol, 1,1,1-tri- (4-hydroxyphenyl) -ethane and 2,2-bis- [4 4- (4,4'-dihydroxydiphenyl) -cyclohexyl] -propane and the like.
[0011]
The viscosity average molecular weight of the polycarbonate resin is not particularly limited, but is usually 10,000 to 100,000, preferably 15,000 to 35,000 from the viewpoint of moldability and strength. In producing such a polycarbonate resin, a molecular weight regulator, a catalyst and the like can be used as required.
[0012]
The amount of the polycarbonate resin used is 50 to 95% by weight. If the polycarbonate resin content is less than 50% by weight, the moldability deteriorates, and if it exceeds 95% by weight, the dimensional stability and the rigidity are inferior. A more preferred range is 70-90% by weight.
[0013]
Examples of the flake-like inorganic filler used in the present invention include flake-like glass, talc, mica, clay, and carbon.The size of such a filler is not particularly limited. From the viewpoint of dimensional stability, it is preferable that the average particle diameter is 10 to 600 μm and the average shape ratio (major axis / thickness) is 2 to 120.
[0014]
The shape of the flake-like inorganic filler is determined by dissolving the obtained polycarbonate resin composition or molded product in methylene chloride, separating the flake-like filler from the polycarbonate resin, and observing with an optical microscope or using an image analyzer. You can do it.
[0015]
Further, the surface treatment of the flake-like inorganic filler is not limited at all, and is not limited to treatment, but is treated with a silane-based (such as aminosilane) chemical and converged with an epoxy-based (urethane-based) chemical. It may be something. In particular, those treated with a silane-based surface treatment agent and converged with urethane are desirable.
[0016]
The used amount of the flake-like inorganic filler is 5 to 50% by weight. If the amount of the flake-like inorganic filler is less than 5% by weight, rigidity and dimensional stability are poor, and if it exceeds 50% by weight, the fluidity is poor, which is not preferable. More preferably, it is in the range of 10 to 30% by weight.
[0017]
Examples of the fibrous filler used in the present invention include fibrous fillers such as glass, carbon, and aromatic polyamide, and metal fillers such as stainless steel, aluminum, copper, iron, and nickel.
[0018]
The size is not particularly limited, but is preferably 0.2 to 20 μm in average diameter and 10 μm to 10 mm in fiber length from the viewpoint of rigidity and dimensional stability of the molded product.
[0019]
The shape of the fibrous filler should be determined by dissolving the obtained polycarbonate resin composition or molded article in methylene chloride, separating the fibrous filler from the polycarbonate resin, and observing with an optical microscope or using an image analyzer. Can be done.
[0020]
The surface treatment of the fibrous filler is not limited at all, and is not limited to treatment, but is treated with a silane-based (such as aminosilane) chemical and converged with an epoxy-based (urethane-based) chemical. But it's fine. In particular, those treated with a silane-based surface treatment agent and converged with urethane are desirable.
[0021]
The amount of the fibrous filler used is 0 to 25% by weight. If the amount of the fibrous filler exceeds 25% by weight, the dimensional stability is inferior. More preferably, it is in the range of 0 to 15% by weight.
[0022]
The molecular weight of the polyethylene wax used in the present invention is not particularly limited, but is preferably about 1,000 to 8,000.
[0023]
The amount of polyethylene wax used is more than 1.5 parts by weight and not more than 3 parts by weight . If the polyethylene wax content is less than 1.5 parts by weight , the releasability and impact resistance are poor, and if it exceeds 3 parts by weight, the thermal stability is poor, which is not preferable.
[0024]
The method of mixing the polycarbonate resin, the flake-like inorganic filler, the fibrous filler, and the polyethylene wax is not particularly limited, and is mixed by an arbitrary mixer such as a tumbler, a ribbon blender, a high-speed mixer, or melt-kneaded by an extruder. Is raised.
[0025]
At the time of mixing, other additives such as an antioxidant [2,6-di-t-butyl-4-methylphenol, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, if necessary, 2,2-methylenebis- (4-ethyl-6-t-methylphenol), 4,4'-thiobis- (6-t-butyl-3-methylphenol), dilaurylthiodipropionate, tris (di- Nonylphenyl) phosphite and the like are exemplified. And ultraviolet absorbers (pt-butylphenyl salicylate, 2,2'-dihydroxy-4-methoxybenzophenone, 2- (2'-hydroxy-4'-n-octoxyphenyl) benzotriazole, and the like. . ], A lubricant [paraffin wax, stearic acid, hardened oil, stearamide, methylenebisstearamide, ethylenebisstearamide, n-butylstearate, ketone wax, octyl alcohol, lauryl alcohol, hydroxystearic acid triglyceride, etc. are exemplified. You. And a fluidity improver [triphenyl phosphate and the like. ], A decomposition inhibitor for a polycarbonate resin, a release agent [natural beeswax, synthetic beeswax, monohydric alcohol and monovalent fatty acid ester (eg, stearyl stearate), partial ester of polyhydric alcohol (eg, glycerol monoester, glycerol diester) , Saturated esters of polyhydric alcohols (eg, glycerol triester, pentaerythritol tetrastearate), flame retardants [tetrabromobisphenol A], etc., and other thermoplastic resins [eg, polymethyl methacrylate, polyamide, polyphenylene ether, polyacetal. , Polyvinyl chloride, polybutylene terephthalate, polyethylene terephthalate, styrene resin (ABS resin, styrene-acrylonitrile copolymer, polystyrene, etc.)] and the like as required Rukoto can.
[0026]
Examples of a method for molding the polycarbonate resin composition of the present invention include a conventional injection molding method and an injection / compression molding method.
[0027]
【Example】
Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. In the examples, “parts” and “%” mean parts by weight and% by weight, respectively, unless otherwise specified.
[0028]
Examples and Comparative Examples Polycarbonate resin having a viscosity average molecular weight of 21,000 (Calibur 200-13 manufactured by Sumitomo Dow), flake-like inorganic filler (REFG-302 manufactured by Nippon Glass Fiber Co., Ltd.), glass fiber (CS03MA409C manufactured by Asahi Fiberglass Co., Ltd.) And polyethylene wax (PE520 manufactured by Hoechst Wax Co., Ltd.) were melt-kneaded at a cylinder temperature of 280 ° C. using a twin screw extruder (KTX-37 manufactured by Kobe Steel) having a diameter of 37 mm based on the compounding ratios shown in Tables 1 and 2. To obtain a pellet. The polycarbonate and polyethylene wax were fed from the first feed of the twin screw extruder, and the flake inorganic filler and glass fiber were fed from the intermediate feed.
[0029]
For comparison, the same operation was performed using glass beads (GB731 manufactured by Toshiba Barotini Co.) or glass powder (PFE-301S manufactured by Nitto Boseki) in place of the flake-like inorganic filler described above. Got.
[0030]
After drying the pellets at 125 ° C. for 4 hours, the liquid crystal frame shown in FIG. 1 was molded using an injection molding machine (J100E-C5 manufactured by Nippon Steel Works, Ltd.) (resin temperature set at 300 ° C., injection pressure 1600 kg / cm 2). did. Twenty-four hours after the molding, the liquid crystal frame was allowed to stand on a horizontal flat plate, and the maximum warpage was measured. The measurement points are shown in FIG.
[0031]
Further, as for the releasability, a load stress at the time of molding the liquid crystal frame and at the time of extruding a molded product on an extrusion pin at the time of releasing was determined.
[0032]
For the fluidity, the flow length was determined from the pellets using a spiral flow type (10 mm width, 1 mm thickness).
[0033]
Further, a test piece was prepared from the pellet, and the flexural rigidity and the flexural strength were determined according to ASTM D-790, and the impact strength was determined according to ASTM D-256. Tables 1 and 2 show the evaluation results.
[0034]
[Table 1]

[0035]
[Table 2]

[0036]
【The invention's effect】
The polycarbonate resin composition of the present invention is excellent in releasability, fluidity, dimensional stability and mechanical strength. Molding workability, dimensional stability, etc. are insufficient, so even in thin molded products that have been difficult in the past, molding can be performed without inconvenience by using the polycarbonate resin composition of the present invention, and excellent dimensions can be obtained. Stability and mechanical strength can be obtained.
[0037]
[Brief description of the drawings]
FIG. 1 is a front view of a molded product used in an embodiment of the present invention. Numerals 1 to 6 are measurement locations for warpage.
FIG. 2A is a cross-sectional view taken along a line AA in FIG.
(B) is sectional drawing of the BB part of FIG.
FIG. 2C is a cross-sectional view taken along the line CC of FIG. 1.

Claims (2)

To 100 parts by weight of a mixture of 50 to 95% by weight of a polycarbonate resin, 5 to 50% by weight of a flake-like inorganic filler and 0 to 25% by weight of a fibrous filler, more than 1.5 parts by weight of polyethylene wax and 3 parts by weight or less A polycarbonate resin composition comprising: The polycarbonate resin composition according to claim 1, wherein the flake-like inorganic filler is glass flake.

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