JPH07166048A - Polycarbonate resin composition - Google Patents

Abstract

PURPOSE:To obtain a polycarbonate resin compsn. which is excellent in flowability and exhibits a reduced anisotropy in molding shrinkage. CONSTITUTION:A low-anisotropy high-stiffness glass-fiber-reinforced polycarbonate resin compsn. comprises 100 pts.wt. modified polycarbonate resin, 0.05-30 pts.wt. thermoplastic polyurethane resin, 10-100 pts.wt. glass fibers having a fiber diameter of 3-20mum and a fiber length 0.5-15mm, and 10-100 pts.wt. glass flakes having a mean thickness of 1-10mum and a flake size of 5-5,000mum. The modified polycarbonate resin is prepd. by melt mixing 100 pts.wt. polycarbonate resin, 0.01-20 pts.wt. acrylamide compd. of the formula (wherein Ar is a 6-24C arom. hydrocarbon group having at least one glycidyl group; and R is H or methyl), and 0.005-7 pts.wt. free-radical generator.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass fiber reinforced polycarbonate resin composition, and more specifically to a glass fiber reinforced polycarbonate having improved fluidity and molding shrinkage anisotropy without impairing good mechanical strength. It relates to a resin composition.

[0002]

2. Description of the Related Art Polycarbonate resin is widely used mainly in the electrical and electronic fields as an engineering plastic having not only the highest level of impact resistance among thermoplastic resins but also excellent electrical properties such as electrical insulation and dimensional stability. Has been done. Polycarbonate resins have recently been used for the purpose of weight reduction or productivity improvement in structural materials such as OA equipment in which metal materials such as aluminum die-cast or thermosetting resins such as BMC have been conventionally used. There is. Therefore, it is common practice to add an inorganic filler such as glass fiber to the polycarbonate resin composition to improve the rigidity. The present inventors previously disclosed in Japanese Patent Application No. 03-328630 to improve the affinity between the polycarbonate resin and the glass fiber by adding a specific acrylamide compound when the glass fiber reinforced polycarbonate resin is melt-kneaded. It is found that the physical properties are improved. However, the polycarbonate resin has a high melt viscosity and poor molding processability, and the glass fiber reinforced polycarbonate resin composition has a further poor flowability, so that problems such as molding defects occur when molding a product having a complicated shape. There is. Therefore, for the purpose of improving the fluidity, the present inventors in Japanese Patent Application No. 04-195179,
It has been found that adding a thermoplastic polyurethane resin to a glass fiber reinforced polycarbonate resin composition significantly improves the fluidity of the composition. However, in general, high filling of glass fibers causes fiber orientation inside the injection-molded product, and the orientation causes anisotropy in molding shrinkage and mechanical strength, causing problems such as warping of the injection-molded product. Cheap. To improve the anisotropy, a plate-like filler such as mica or talc alone or in combination with glass fiber can be considered, but the polycarbonate decomposes during melt kneading,
It also causes poor appearance and lower mechanical strength. Further, it is conceivable to use scaly glass flakes instead of mica or talc, but it was unavoidable that the mechanical strength, especially the bending strength, was significantly lowered.

[0003]

DISCLOSURE OF THE INVENTION The present invention is a glass fiber reinforced glass fiber reinforced polycarbonate resin composition which maintains good mechanical strength and has improved fluidity and molding shrinkage anisotropy. An object is to provide a polycarbonate resin composition.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have found that a polycarbonate resin, a specific acrylamide compound, a radical generator, a thermoplastic polyurethane resin, a glass fiber, and a glass. By adding flakes, a thermoplastic resin composition having excellent fluidity and reduced anisotropy in molding shrinkage was found without impairing mechanical strength, and the present invention was reached. That is, the present invention includes (A) 100 parts by weight of a polycarbonate resin, (2) 0.01 to 20 parts by weight of an acrylamide compound represented by the formula (1) (Chemical Formula 2),

[0005]

[Chemical 2] (In the formula, Ar is C ₆ having at least one glycidyl group.
To C ₂₄ aromatic hydrocarbon, R is a hydrogen atom or a methyl group), and (3) a modified polycarbonate resin 100 obtained by melt-kneading 0.005 to 7 parts by weight of a radical generator.
Parts by weight, (B) thermoplastic polyurethane resin 0.05 to 3
0 parts by weight, (C) the fiber diameter is 3 to 20 μm, and the fiber length is 0.
5 to 15 mm glass fiber 10 to 100 parts by weight, (D)
A low-anisotropic, high-rigidity glass fiber reinforced polycarbonate resin composition comprising 10 to 100 parts by weight of scaly glass flakes having an average thickness of 1 to 10 μm and a particle size of 5 to 5000 μm. In the present invention, the modified polycarbonate resin (A) is the acrylamide compound represented by the formula (1)

[0006]

[Chemical 3] (In the formula, Ar is C ₆ having at least one glycidyl group.
To C ₂₄ aromatic hydrocarbon, where R is a hydrogen atom or a methyl group) and a radical generator are melt-kneaded to produce.

The polycarbonate resin used as a constituent of the polycarbonate resin composition of the present invention is usually a reaction of a dihydric phenol with phosgene in the presence of an acid acceptor and a molecular weight modifier, or a dihydric phenol with diphenyl carbonate. It is produced by a transesterification reaction. As the dihydric phenol that can be used, bisphenols are preferable, and 2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as bisphenol A) is preferable. Further, a part or all of bisphenol A may be replaced with another dihydric phenol. Bisphenol A
Examples of dihydric phenols other than the above include compounds such as hydroquinone, 4,4′-dihydroxyphenyl, bis (4-hydroxyphenyl) alkane, and bis (4-hydroxyphenyl) cycloalkane, or 2,2-
Mention may be made of halogenated bisphenols such as bis (3,5-dibromo-4-hydroxyphenyl) propane. In addition, polycarbonate resin
It may be a homopolymer of a dihydric phenol, a copolymer of two or more kinds, or a polyblend thereof.

The acrylamide compound useful in the present invention includes, for example, at least 1 phenolic hydroxyl group.
It is easily obtained by condensing one or more aromatic hydrocarbons with N-methylol acrylamide or an alkyl ether derivative of N-methylol acrylamide with an acid catalyst and then glycidylating the phenolic hydroxyl groups. Specific acrylamide compounds include N- [4
-(2,3-Epoxypropoxy) -3,5-dimethylbenzene] acrylamide, N- [4- (2,3-epoxypropoxy) -3,5-dimethylbenzene] methacrylamide, N- [4- (2 , 3-epoxypropoxy) -3-methylbenzene] acrylamide and the like.

As the radical generator, a compound known as a radical polymerization initiator is used, and specific examples thereof include tertiary butyl peroxide and 2,5-dimethyl-2,5-di (tertiary butyl peroxy). ) Organic peroxides represented by hexane and ditertiary butyl peroxide, and azobisnitrile compounds represented by azobisisobutyronitrile and azobisisovaleronitrile.

The respective proportions of the polycarbonate resin, the acrylamide compound and the radical generator are 100 parts by weight of the polycarbonate resin, 0.01 to 20 parts by weight of the acrylamide compound and 0.005 to 7 of the radical generator.
It is preferably part by weight. Further, a part of the above acrylamide-modified polycarbonate resin may be replaced with an unmodified polycarbonate resin.

Suitable (B) thermoplastic polyurethane resins useful in the present invention are made from difunctional polyols, short chain glycols and organic diisocyanates and are substantially linear and have thermoplastic processability. As the difunctional polyol used for producing the thermoplastic polyurethane, a dibasic acid such as adipic acid, succinic acid, suberic acid, sebacic acid, pimelic acid, phthalic acid, terephthalic acid or isophthalic acid is used as a suitable short chain glycol, For example ethylene glycol, propylene glycol, butylene glycol, 1,
Polyester having a hydroxyl group at the terminal of a molecule produced by reacting with 4-butanediol, 1,6-hexanediol, etc., polycarbonate ester produced by reacting a short chain glycol with a carbonate precursor such as phosgene, lactone Examples thereof include polyesters based on ring-opening polymerization products of caprolactones, and polyethers such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, preferably polyester polyols.

The above-mentioned bifunctional polyol having a hydroxyl group and an organic diisocyanate which forms a urethane bond are ethylene diisocyanate, propylene diisocyanate, butylene diisocyanate, 4,4 '.
-Diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, tridene diisocyanate, hexamethylene diisocyanate and the like. Suitable short chain glycols having an active hydrogen containing group which reacts with isocyanate groups are ethylene glycol, propylene glycol, butylene glycol, 1,4-butanediol, 1,6-hexanediol and the like.

Commercially available thermoplastic polyurethane resins for use in the polycarbonate resin composition of the present invention include Miractolane E190 (adipate ester type), E390 (polyether type) and E manufactured by Nippon Miractolan Co., Ltd.
590 (polycaprolactone type), E990 (polycarbonate type), manufactured by Takeda Bardish Urethane Co.,
Elastran ET680, ET685 (adipate ester type) are included. The polycarbonate resin composition of the present invention comprises (A) (1) polycarbonate resin, (2)
It is composed of a mixture of an acrylamide compound, (3) a modified polycarbonate resin obtained by melt-kneading a radical generator, (B) thermoplastic polyurethane, (C) glass fibers, and (D) glass flakes. Therefore, the respective proportions in the mixture are (1) polycarbonate resin 10 in the modified polycarbonate resin (A).
0 parts by weight of (2) acrylamide compound 0.01
-20 parts by weight, preferably 0.1-10 parts by weight, (3)
Radical generator 0.005 to 7 parts by weight, preferably 0.1.
01 to 5 parts by weight, more preferably 0.03 to 1 part by weight, and (B) thermoplastic polyurethane 0.0
5 to 30 parts by weight, preferably 0.5 to 20 parts by weight, and (C) glass fiber 10 to 100 parts by weight, preferably 2
It is also used in the range of 0 to 90 parts by weight, (D) glass flakes 10 to 100 parts by weight, preferably 20 to 90 parts by weight. If the amount is out of the above range, it becomes difficult to obtain a resin composition having excellent fluidity and good mechanical properties. That is, if the (2) acrylamide compound is less than 0.01 parts by weight, or 20 parts by weight or more, there is no effect of improving the bending strength. (3) When the amount of the radical generator is less than 0.005 parts by weight, or 7 parts by weight or more, there is no effect of improving the bending strength. If the amount of the thermoplastic polyurethane resin (B) is less than 0.05 parts by weight, there is no effect of improving the fluidity, and if it is 30 parts by weight or more, the bending strength decreases. When the amount of the (C) glass fiber is less than 10 parts by weight, there is no effect of improving the bending strength and the bending elastic modulus. If it is 100 parts by weight or more, the anisotropy increases, which is not preferable. If the amount of the (D) glass flake is less than 10 parts by weight, the effect of improving anisotropy will not be obtained, and if it is 100 parts by weight or more, the effect of improving bending strength and bending elastic modulus will not be obtained.

The glass fiber reinforced polycarbonate resin composition having good fluidity of the present invention has the above-mentioned (A),
Various elastomers in addition to (B), (C) and (D)
Plasticizers, pigments, stabilizers, fillers, metal powders, etc. are appropriately used depending on the application. The method for producing the polycarbonate resin composition of the present invention is not particularly limited, and a commonly known method can be adopted. That is,
(1) Polycarbonate resin, (2) Specific acrylamide compound, (3) Melt-kneading radical generator to obtain (A) modified polycarbonate resin, (A) modified polycarbonate resin, (B) thermoplastic polyurethane resin, (C) Glass fibers and (D) glass flakes are uniformly mixed with a high-speed stirrer or the like, and then melt-kneaded with a uniaxial or multiaxial extruder having sufficient kneading capacity, or (1) polycarbonate resin, (2) Specific acrylamide compound, (3) radical generator, (B) thermoplastic polyurethane resin, (C) glass fiber, and (D) glass flakes are uniformly mixed with a high-speed stirrer or the like, and then sufficient kneading ability is obtained. It is manufactured by a method such as melt kneading with a uniaxial or multiaxial extruder having a certain property.

[0015]

EXAMPLES The present invention will now be described in detail with reference to examples, but the present invention is not limited thereto. In addition,
The physical property evaluations described in Examples and Comparative Examples were carried out according to the following methods. (1) Melt flow index (fluidity) Based on JIS-K7210. Load 2.16 kg,
Temperature 280 degrees (2) Anisotropy of mold shrinkage Mold size is 2 × 40 (TD direction) × 8 by injection molding
A flat plate of 0 (MD direction) mm was molded, the dimensions of the molded product were measured with a three-dimensional dimension measuring machine, the shrinkage ratios in the TD direction and the MD direction were calculated, and the ratio TD / MD of the molding shrinkage ratio was calculated from the value. .
The smaller the TD / MD, the smaller the anisotropy. MD direction Flow direction of molten resin (direction from side with gate to opposite side) TD direction Vertical direction to flow direction of molten resin (3) Bending test (bending strength, bending elastic modulus) Based on JIS-K7113 .

Examples 1 to 6 Polycarbonate resin (manufactured by Teijin Kasei Co., Ltd., Panlite L-1225), N- [4 as acrylamide compound
-(2,3) -epoxypropoxy) -3,5-dimethylbenzyl] acrylamide (manufactured by Kanegafuchi Chemical Co., Ltd.) and dicumyl peroxide as a radical generator were blended, and then sufficiently dried and mixed by a tumbler mixer. And then melt-kneading with a twin screw extruder having a screw diameter of 35 mm and L / D = 32 at a melting temperature of 250 ° C. and a screw rotation speed of 100 rpm to obtain a modified polycarbonate resin, and then a modified polycarbonate resin, a thermoplastic polyurethane resin ( Nippon Miractolan Co., Ltd., Miractolan E190), chopped strand glass fiber having a fiber length of 3 mm (manufactured by Nippon Electric Glass Co., Ltd., ECS03T-511 / P), and an average particle size of 600 μm and an average thickness of 4 μm. Glass flake (manufactured by Nippon Sheet Glass Co., Ltd., Micro Glass Glass Flake REF-600) A) was blended in the proportions shown in Table 1, sufficiently dried and mixed in a tumbler mixer, and then melted at a screw temperature of 35 ° C. and a screw rotation speed of 100 rpm in a twin screw extruder having a screw diameter of 35 mm and L / D = 32. A melt-mixed and extruded pellet-shaped molding material composition was obtained. The composition obtained by the above method was molded into a test piece by an injection molding machine set at 280 ° C., and each physical property was measured. The results are shown in Table 1.

Example 9 In Example 1, the thermoplastic polyurethane resin was Elastollan ET680 manufactured by Takeda Bardish Urethane Co., Ltd.
It was the same except that. Similarly, the results are shown in Table 1.

Comparative Examples 1 to 5 Comparative Examples 1 to 5 were carried out except that the compounding amounts of the polycarbonate resin, the acrylamide compound, the radical generator, the thermoplastic polyurethane resin, the glass fiber, and the glass flakes were different from those of the glass fiber reinforced polycarbonate resin composition of the present invention. Same as Examples 1 to 8. The results are shown in Table 2.

[0019]

[Table 1] Table 1

[0020]

[Table 2]

[0021]

[Table 3] Table 2

[0022]

As shown in Table 1, the glass fiber reinforced polycarbonate resin composition of the present invention has excellent flexural modulus, good fluidity and low anisotropy. Therefore, it can be used in the fields of automobiles, home appliances, industrial parts, etc., and its utility value is great.

Claims (2)

[Claims] 1. (A) (1) Polycarbonate resin 100
Parts by weight, (2) 0.01 to 20 parts by weight of the acrylamide compound represented by the formula (1) (formula 1), (In the formula, Ar is C ₆ having at least one glycidyl group.
To C ₂₄ aromatic hydrocarbon, R is a hydrogen atom or a methyl group), and (3) a modified polycarbonate resin 100 obtained by melt-kneading 0.005 to 7 parts by weight of a radical generator.
Parts by weight, (B) thermoplastic polyurethane resin 0.05 to 3
0 parts by weight, (C) the fiber diameter is 3 to 20 μm, and the fiber length is 0.
10 to 100 parts by weight of glass fiber of 5 to 15 mm,
(D) The average thickness is 1 to 10 μm and the particle size is 5 to 5000 μm.
A low-anisotropic, high-rigidity glass fiber reinforced polycarbonate resin composition comprising 10 to 100 parts by weight of scaly glass flakes of m. 2. The low anisotropy and high rigidity glass fiber reinforced polycarbonate resin composition according to claim 1, wherein the bifunctional polyol constituting the thermoplastic polyurethane resin is a polyester polyol.