JP3495197B2 - Thermoplastic resin composition - Google Patents

Description

Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent molding stability,
The present invention also relates to a thermoplastic resin composition mainly comprising a mixture of an aromatic polycarbonate resin having good appearance and surface properties of a molded article obtained and another thermoplastic composition. [0002] Conventionally, there has been known a method for improving dimensional stability and mechanical properties by blending an inorganic filler with a thermoplastic resin. However, when injection molding is performed by blending glass fibers with an aromatic polycarbonate resin, there is a problem that the resulting molded article has a poor appearance. In addition, there is a problem that a molded product obtained by injection molding with aluminum borate whisker is significantly reduced in molecular weight and further deteriorated in appearance due to foaming or the like. As a method for solving such a drawback, there is known a method of treating an inorganic filler with a silane coupling agent in advance. However, this method is expensive because the silane coupling agent is expensive and the treatment process is complicated. Because of this, the cost increased, and the effect was not sufficiently satisfactory. The present invention has excellent molding stability in which an inorganic reinforcing filler is blended with an aromatic polycarbonate resin or a composition of an aromatic polycarbonate and another thermoplastic resin,
Another object of the present invention is to provide a thermoplastic resin composition having good appearance and surface properties of a molded article obtained. The inventor of the present invention has conducted intensive studies in order to achieve the above object. As a result, when a specific amount of the compound represented by the formula (I) is used in combination with the aromatic polycarbonate in combination with the inorganic reinforcing filler, the molding stability is improved. The present inventors have found that a thermoplastic resin composition mainly containing a mixture of an aromatic polycarbonate resin and another thermoplastic composition, which is excellent and has good appearance and surface of a molded article to be obtained, has been obtained, and has led to the present invention. [0006] That is, an object of the present invention is to provide a thermoplastic resin composition containing an aromatic polycarbonate resin which is excellent in molding stability and has good appearance and surface properties of a molded article obtained. Is to provide. Other objects and advantages of the present invention will become apparent from the following description. The present invention relates to (i) -a 100 parts by weight of an aromatic polycarbonate resin or (i) -a.
b. an aromatic polycarbonate resin comprising another thermoplastic resin and having an aromatic polycarbonate content of at least 30.
(Ii) 1 to 15 parts by weight of an inorganic reinforcing filler and (iii) 0.1 to 10 parts by weight based on 100 parts by weight of the inorganic reinforcing filler.
It is a thermoplastic resin composition comprising a compound represented by the following formula (I) in parts by weight. [0008] Wherein R ¹ is an alkyl group having 1 to 40 carbon atoms or an aryl group. R ^{2 to} R ⁵ have 1 to 1 carbon atoms
10 alkyl groups or aryl groups, which may be the same or different. The aromatic polycarbonate resin used in the present invention is an aromatic polycarbonate resin derived from an aromatic dihydroxy compound and having a viscosity average molecular weight of 13,000 to 100,000, preferably 15,000 to 80,000. . Examples of the aromatic dihydroxy compound include 1,1-bis (4-hydroxy-t-butylphenyl) propane, 2,2-bis (4-hydroxyphenyl) propane, and 2,2-bis (4-hydroxyphenyl). Bis (hydroxyaryl) alkanes such as bromophenyl) propane; bis (hydroxyaryl) such as 1,1-bis (4-hydroxyphenyl) cyclopentane and 1,1-bis (4-hydroxyphenyl) cyclohexane
Dihydroxyaryl ethers such as cycloalkanes, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethylphenyl ether, 4,4'-dihydroxydiphenyl sulfide,
Dihydroxyaryl sulfides such as 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide;
4'-dihydroxydiphenyl sulfoxide, 4,4 '
Dihydroxyarylsulfoxides such as -dihydroxy-3,3'-dimethylphenylsulfoxide, 4,
Examples thereof include dihydroxyaryl sulfones such as 4'-dihydroxydiphenylsulfone and 4,4'-dihydroxy-3,3'-dimethylphenylsulfone. Of these, in particular, 2,2-bis (4-
(Hydroxyphenyl) propane (bisphenol A) is preferably used. These aromatic dihydroxy compounds can be used alone or in combination. The method for producing the aromatic polycarbonate resin is not particularly limited, and a known production method such as an interfacial polymerization method in which an aromatic dihydroxy compound is directly reacted with phosgene, or an aromatic dihydroxy compound and a carbonic acid diester are used. It can be produced by a melt polymerization method or the like in which a transesterification reaction is carried out in the presence of a catalyst in a molten state. The thermoplastic resin to be mixed with the aromatic polycarbonate resin may be any resin that can be mixed with the aromatic polycarbonate resin. Examples thereof include thermoplastic polyester resins, polyarylene ester resins, polystyrene resins, and polyethylene resins. And one or more mixtures selected from polypropylene resins, diene resins, polyamide resins, polyether resins, polysulfone resins, polyphenylene sulfide resins, and the like. The thermoplastic polyester resin is a polymer or a copolymer obtained by subjecting an aromatic dicarboxylic acid or an ester-forming derivative thereof to a diol or an ester-forming derivative thereof as a main material for a condensation reaction. As the aromatic dicarboxylic acid used here, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid and the like are preferable. As the diol, an alkylene glycol having 2 to 10 carbon atoms and an alicyclic diol having 6 to 15 carbon atoms are preferable. For example, ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, 3-methylpentanediol (2,
4) 2-Methylpentadiol (1,4), 2-ethylenehexanediol (1,3), diethylene glycol, cyclohexanedimethanol and the like. Preferred thermoplastic polyester-based resins are polyethylene terephthalate, polybutylene terephthalate, and copolymerized polyesters obtained by substituting 30% by mole or less of these acid components and / or diol components with other components. The polyarylene ester resin is a polymer or copolymer obtained by subjecting a dihydric phenol or its ester-forming derivative and an aromatic dicarboxylic acid or its ester-forming derivative to a condensation reaction as a main raw material. As the dihydric phenol used here, those described above for the aromatic polycarbonate resin are preferably used, and examples of the ester-forming derivative thereof include diesters with aliphatic or aromatic carboxylic acids. As the aromatic dicarboxylic acid, those described for the thermoplastic polyester resin are preferably used.
An interfacial polycondensation method for producing a polyarylene ester resin from a dihydric phenol or an ester-forming derivative thereof and an aromatic dicarboxylic acid or an ester-forming derivative thereof,
Any method such as a melt polycondensation method and a melt polycondensation method is employed. Examples of the polystyrene resin include general-purpose polystyrene, impact-resistant polystyrene, AS resin,
BS resin, AES resin, MBS resin, MAS resin, AA
S resin, styrene-butadiene block copolymer, styrene-maleic anhydride copolymer, and the like. Examples of the polyethylene resin include high-density polyethylene resin, low-density polyester resin, linear low-density polyethylene resin, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, and ethylene-acrylate copolymer. , Ethylene-glycidyl (meta)
Acrylate copolymers and the like can be mentioned. Examples of the polypropylene resin include a polypropylene resin, a propylene-vinyl acetate copolymer,
And propylene-vinyl chloride copolymer. Examples of the diene-based resin include monomers having a diene structure such as 1,2-polybutadiene resin and trans-1,4-polybutadiene resin alone or copolymers with monomers copolymerizable therewith. These are mixtures. Examples of the polyamide resin include, for example, a polymer comprising aminocarboxylic acid alone or a dicarboxylic acid and a diamine, or a polymer obtained by ring-opening polymerization of α, ω-caprolactam. Preferred examples of the polyether resin include a polyphenylene ether polymer and a copolymer. The shape of the inorganic reinforcing filler used in the present invention is not particularly limited, and examples thereof include fibrous, needle-like, plate-like and granular shapes. These are used according to the purpose. As the inorganic reinforcing filler, glass, alumina,
Examples include potassium titanate, aluminum borate, talc, calcium carbonate, silica and the like. The inorganic reinforcing filler is 1 part by weight based on 100 parts by weight of the (i) -a aromatic polycarbonate resin or 100 parts by weight of the composition comprising the (i) -b aromatic polycarbonate resin and another thermoplastic resin. on more than 1 5 parts by weight
The following is used. The compound represented by the above formula (I) used in the present invention is represented by the following formula: Wherein R ¹ is an alkyl group having 1 to 40 carbon atoms or an aryl group. R ^{2 to} R ⁵ have 1 to 1 carbon atoms
10 alkyl groups or aryl groups, which may be the same or different. In the formula, examples of the alkyl group for R ¹ include an alkyl group having 1 to 15 carbon atoms, preferably a hexyl group and a dodecyl group. Examples of the alkyl group of R ^{2 to} R ⁵ include an alkyl group having 1 to 5 carbon atoms, preferably a propyl group and a butyl group. Examples of the aryl group include a phenylnaphthyl group. Specific examples of the compound represented by the above formula (I) include hexylsulfonic acid tetramethylphosphonium salt, hexylsulfonic acid tetraethylphosphonium salt, hexylsulfonic acid tetrabutylphosphonium salt,
Hexylsulfonic acid tetrahexylphosphonium salt, hexylsulfonic acid tetraoctylphosphonium salt, octylsulfonic acid tetramethylphosphonium salt, octylsulfonic acid tetraethylphosphonium salt, octylsulfonic acid tetrabutylphosphonium salt, octylsulfonic acid tetrahexylphosphonium salt, octylsulfonic acid Tetraoctyl phosphonium salt, tetramethyl phosphonium decyl sulfonate, tetraethyl phosphonium decyl sulfonate, tetrabutyl phosphonium decyl sulfonate, tetrahexyl phosphonium decyl sulfonate, tetraoctyl phosphonium decyl sulfonate, tetramethyl phosphonium dodecyl sulfonate salt,
Dodecylsulfonic acid tetraethylphosphonium salt, dodecylsulfonic acid tetrabutylphosphonium salt, dodecylsulfonic acid tetrahexylphosphonium salt, dodecylsulfonic acid tetraoctylphosphonium salt, hexadecylsulfonic acid tetramethylphosphonium salt, hexadecylsulfonic acid tetraethylphosphonium salt, hexadecyl Tetrabutylphosphonium sulfonate, tetrahexylphosphonium hexadecylsulfonate, tetraoctylphosphonium hexadecylsulfonate, tetramethylphosphonium benzenesulfonate, tetraethylphosphonium benzenesulfonate, tetrabutylphosphonium benzenesulfonate, benzenesulfone Tetrahexylphosphonate, tetraoctylphosphonate benzenesulfonate Tetramethylphosphonium salt, toluenesulfonic acid tetramethylphosphonium salt, toluenesulfonic acid tetrabutylphosphonium salt, toluenesulfonic acid tetrahexylphosphonium salt, toluenesulfonic acid tetraoctylphosphonium salt, dodecylbenzenesulfonic acid tetramethylphosphonium salt And dodecylbenzenesulfonic acid tetraethylphosphonium salt, dodecylbenzenesulfonic acid tetrabutylphosphonium salt, dodecylbenzenesulfonic acid tetrahexylphosphonium salt, dodecylbenzenesulfonic acid tetraoctylphosphonium salt, and the like. By using such a compound, the moldability of the aromatic polycarbonate resin with the filler for inorganic reinforcement can be greatly improved. If the amount of the compound is too small, a sufficient effect cannot be obtained, and if the amount is too large, the effect is saturated. The amount used is usually filler 1 for inorganic reinforcement.
The optimum amount is selected from the range of 0.5 to 5 parts by weight based on 100 parts by weight of the inorganic reinforcing filler per 100 parts by weight. The composition of the present invention can be produced by mixing the above-mentioned components by any method, for example, using a tumbler, blender, Nauter mixer, Banbury mixer, kneading roll, extruder, or the like. The composition of the present invention may optionally contain other additives such as an antioxidant, an ultraviolet absorber, a lubricant, a flame retardant, an antistatic agent, a release agent, a colorant, and the like. it can. The composition of the present invention can be used in molding processability even when an inorganic reinforcing filler is blended with an aromatic polycarbonate resin or a composition of an aromatic polycarbonate resin and another thermoplastic resin. , And can be applied to any melt molding method such as injection molding, extrusion molding, compression molding, etc., especially applications that could not be used conventionally, for example, large precision machine parts And industrially excellent effects such as enabling the use of the same for large automobile parts and the like. EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. The methods for measuring and testing the physical properties of the thermoplastic resin composition in the following examples are shown below. Viscosity average molecular weight (Mv): The intrinsic viscosity [η] in a methylene chloride solution at 20 ° C. was measured and determined by the following Schnell equation. [Η] = 1.11 × 10 ⁻² × Mv ^0.82 Impact strength: A value (kgfcm / cm) measured with a notch using a 1/8 inch thick test piece. A bisphenol A type polycarbonate having a viscosity average molecular weight (Mv) of 22,500 (manufactured by Teijin Chemicals Limited)
1225) 100 parts by weight of the inorganic reinforcing filler and compound (A) shown in Table 1 were added in the amounts shown in Table 1, and 25 mmφ was added.
Using a vent-type twin-screw kneader (ZSK-25 manufactured by Werner) at a cylinder temperature of 280 ° C. to obtain pellets of a target resin composition. After drying at 120 ° C. for 5 hours, a physical property test piece was prepared at a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. using an injection molding machine (M-50B manufactured by Meiki Co., Ltd.).
Table 1 shows the viscosity average molecular weight (Mv) of the pellet and the test piece and the physical properties of the test piece. [Table 1]

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Claims (1)

(57) [Claim 1] (i) -a 100 parts by weight of an aromatic polycarbonate resin or (i) -b An aromatic polycarbonate resin comprising an aromatic polycarbonate resin and another thermoplastic resin. Composition 1 in an amount of at least 30% by weight
(Ii) 1 to 15 parts by weight of the inorganic reinforcing filler and (iii) the inorganic reinforcing filler 1
0.1 to 10 parts by weight of the following formula (I) based on 00 parts by weight
A thermoplastic resin composition comprising a compound represented by the formula: Embedded image [Wherein, R ¹ is an alkyl group having 1 to 40 carbon atoms or an aryl group. R ^{2 to} R ⁵ are an alkyl group or an aryl group having 1 to 10 carbon atoms, which may be the same or different. ]