JP3346439B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polycarbonate resin composition. More specifically, thermoplastic resin (1)
And talc, thermoplastic resin (2) and glass fiber are melt-mixed individually or simultaneously, and then have a good appearance obtained by melt-mixing with polycarbonate resin or polycarbonate resin and thermoplastic resins (1) and (2). The present invention relates to a polycarbonate resin composition capable of obtaining a molded article having excellent strength, repeated fatigue characteristics, heat resistance and the like.

[0002]

2. Description of the Related Art Polycarbonate resins are:
It is widely used as a resin having excellent mechanical strength, impact strength, and heat resistance, and is used as a polymer alloy with an appropriate thermoplastic resin to improve various properties. Further, when high rigidity and high strength are required, it is known to use various inorganic fillers such as talc and glass fiber.

[0003] However, when talc is added to the polycarbonate resin composition, the polycarbonate resin is decomposed, causing problems such as a decrease in strength due to molecular deterioration and a poor appearance. As a method of solving such a drawback, a method of treating an inorganic filler with a silane coupling agent is generally known, but the effect of talc is small and not sufficient.

Therefore, in order to improve these drawbacks,
For example, in JP-A-2-283760, a method of adding a specific acidic phosphorus compound is described.
A method of blending an organic acid is disclosed in JP-A-5-222283.
In JP-A No. 2-2, each method using a phosphite-based antioxidant has been proposed, but it is difficult to reliably suppress the adverse effects of talc even with these methods. When the amount of the organic acid or the phosphite-based antioxidant is increased to suppress the adverse effects, the adverse effects of talc can be suppressed. On the contrary, excess organic acids or phosphites can be suppressed. There is a problem in that the antioxidant has an adverse effect and causes a decrease in strength and the like.

[0005] When talc is used, the strength is improved, but its repetitive fatigue characteristics are hardly improved, and it cannot be used in a field where such characteristics are required.

On the other hand, when glass fiber is blended, strength and repeated fatigue characteristics are improved, but with respect to the surface appearance, poor appearance occurs due to floating of the glass fiber, and the fiber length and fiber diameter of the glass fiber are reduced. In fact, satisfactory results have not been obtained even if the molding conditions are changed or the molding conditions are changed.

[0007]

Means for Solving the Problems The present inventors have intensively studied a polycarbonate resin composition which can improve the above-mentioned drawbacks and can obtain a molded article excellent in appearance, strength, repeated fatigue characteristics, heat resistance and the like. As a result, the thermoplastic resin (1) and talc, the thermoplastic resin (2) and the glass fiber were melt-mixed individually or simultaneously, and then mixed with the polycarbonate resin or the polycarbonate resin and the thermoplastic resins (1) and (2). It has been found that by melt-mixing, the decomposition of the polycarbonate resin by talc is suppressed, and a molded article having high strength, excellent repetitive fatigue properties and good appearance can be obtained.

That is, according to the present invention, when blending talc and glass fiber with a polycarbonate resin, the thermoplastic resin (1) and talc, and the thermoplastic resin (2) and glass fiber are melt-mixed separately or simultaneously, The present invention relates to a polycarbonate resin composition characterized by melt-mixing the obtained mixture with a polycarbonate resin or a polycarbonate resin and thermoplastic resins (1) and (2). The resin composition of the present invention can provide a molded article having high strength, excellent repetitive fatigue characteristics, and good appearance.

The polycarbonate resin used in the present invention is a thermoplastic aromatic polycarbonate polymer which may be obtained by reacting an aromatic dihydroxy compound or a small amount thereof with a phosgene or carbonic acid diester. Or it is a copolymer.

One example of the aromatic dihydroxy compound is 2,2.
2-bis (4-hydroxyphenyl) propane (= bisphenol A), 2,2-bis (3,5-dibromo-4)
-Hydroxyphenyl) propane (= tetrabromobisphenol A), bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane,
2,2-bis (4-hydroxyphenyl) butane, 2,
2-bis (4-hydroxyphenyl) octane, 2,2
-Bis (4-hydroxy-3-methylphenyl) propane, 1,1-bis (3-t-butyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-
3,5-dimethylphenyl) propane, 2,2-bis (3-bromo-4-hydroxyphenyl) propane,
2,2-bis (3,5-dichloro-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-cyclohexyl-4-hydroxyphenyl) ) Propane, 1,
Bis (hydroxyaryl) alkanes exemplified by 1-bis (4-hydroxyphenyl-1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, etc .; 1,1-bis (4-hydroxyphenyl) cyclopentane, 1 Bis (hydroxyaryl) cycloalkanes exemplified by 1,1-bis (4-hydroxyphenyl) cyclohexane and the like; exemplified by 4,4'-dihydroxydiphenylether 4,4'-dihydroxy-3,3'-dimethyldiphenylether and the like Dihydroxy diaryl ethers; dihydroxy diaryl sulfides exemplified by 4,4'-dihydroxy diphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyl diphenyl sulfide; 4,4'-dihydroxy diphenyl sulphoxide; 4,4 ' Dihydroxy -3,
Dihydroxydiarylsulfoxides exemplified by 3′-dimethyldiphenylsulfoxide and the like; dihydroxydiarylsulfones exemplified by 4,4′-dihydroxydiphenylsulfone and 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone; Hydroquinone, resorcin, 4,4'-dihydroxydiphenyl and the like can be mentioned. These aromatic dihydroxy compounds may be used alone or in combination of two or more. Among them, 2,2-bis (4-hydroxyphenyl) propane is particularly preferably used. In order to obtain a branched aromatic polycarbonate resin, phloroglysin, 2,
6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -3-heptene, 4,6-dimethyl-2,4,6
-Tri (4-hydroxyphenyl) -2-heptene,
1,3,5-tri (2-hydroxyphenyl) benzol, 1,1,1-tri (4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol , Α, α ′, α ″ -tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene and the like;
And 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol, 5,7-dichlorisatin bisphenol, 5-bromoisatin bisphenol and the like.

In the case of the phosgene method polycarbonate, a terminal terminator or a molecular weight regulator may be used. Examples of the terminal terminator or the molecular weight regulator include compounds having a monovalent phenolic hydroxyl group.
-In addition to butylphenol, tribromophenol and the like,
Examples include long-chain alkyl phenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, alkyl ether phenols and the like.
The polycarbonate resin used in the present invention may be one kind or a mixture of two or more kinds.

In the present invention, the thermoplastic resin (1) which is previously melt-mixed with talc may be any resin which can be generally blended with a polycarbonate resin. Examples of such thermoplastic resins include, for example, thermoplastic polyester resins, polystyrene resins, polyarylene ester resins, polyolefin resins, diene resins, polyamide resins, polyether resins, polysulfone resins, and polyphenylene resins. One or a mixture of two or more selected from the above.

As for the thermoplastic resin (2) to be melt-mixed with the glass fiber in advance, a polycarbonate resin itself can be used in addition to the above thermoplastic resins.

The thermoplastic polyester resin in the present invention is a polymer obtained by reacting an aromatic dicarboxylic acid or a diester thereof with a glycol or an alkylene oxide by a known method, and specifically, terephthalic acid or terephthalic acid. Acid dimethyl, naphthalenedicarboxylic acid, dimethyl naphthalenedicarboxylate as a main component of the aromatic dicarboxylic acid, and polyethylene terephthalate, polytetramethylene terephthalate (Ethylene glycol, butanediol, cyclohexane dimethanol or ethylene oxide) Polybutylene terephthalate), polyethylene naphthalate, polytetramethylene naphthalate (polybutylene naphthalate), and the like. The polyester resin may be a copolymer, for example, a copolymer of cyclohexane dimethanol with terephthalic acid and isophthalic acid, a copolymer of cyclohexane dimethanol and a copolymer of ethylene glycol and terephthalic acid, and the like. .

The thermoplastic polyester resin has an intrinsic viscosity (intrinsic viscosity) of 0.4 or more, usually 0.5 to 1 in a mixed solvent of phenol and tetrachloroethylene mixed at a weight ratio of 6 to 4 at 30 ° C. .5 are preferred,
If it is less than 0.4, the impact resistance and chemical resistance are not sufficiently improved, which is not preferable.

The polystyrene resin in the present invention includes polystyrene (PS resin), ABS resin, AES resin, MBS resin, MAS resin, AAS resin, and styrene resin.
Butadiene block copolymer, styrene-maleic anhydride copolymer and the like are desirable.

The polyarylene ester resin is a polymer or copolymer obtained by subjecting an aromatic dihydroxy compound or a derivative thereof to a condensation reaction with an aromatic dicarboxylic acid or a derivative thereof as a main raw material. As the aromatic dihydroxy compound used herein, those described for the above polycarbonate resin are preferably used, and the derivative of the aromatic dihydroxy compound is a diester of the above aromatic dihydroxy compound with a fatty acid or an aromatic carboxylic acid. As the aromatic dicarboxylic acid, those described for the thermoplastic polyester resin are preferably used.

Examples of the polyolefin resin include high-density polyethylene resin, low-density polyethylene resin, linear low-density polyethylene resin, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-acrylate copolymer, Desirable are ethylene-glycidyl (meth) acrylate copolymer, polypropylene, propylene-vinyl acetate copolymer, propylene-vinyl chloride copolymer and the like.

Examples of the diene resin include 1,2-polybutadiene resin, trans-1,4-polybutadiene resin, and the like. Is a mixture of

The polyamide resin is preferably an aminocarboxylic acid compound alone or a copolymer of a dicarboxylic acid compound and a diamine compound, or a polymer obtained by ring-opening polymerization of α, ω-caprolactam.

As the polyether resin used in the present invention, a polyphenylene ether resin is desirable.

Among these thermoplastic resins, compatibility and mechanical strength when blended with a polycarbonate resin,
From the viewpoint of physical properties such as chemical resistance, a thermoplastic polyester resin is particularly preferred. Among the polyester resins, polyethylene terephthalate and polybutylene terephthalate are particularly preferably used.

As the talc used in the present invention, commercially available talc can be used. The talc contains silicic acid and magnesium oxide as main components, and contains aluminum oxide, calcium oxide and iron oxide as trace components. Is also good.
Talc that has been treated in advance with a surface treatment agent such as a silane coupling agent can also be used.

In the present invention, the mixing ratio of the thermoplastic resin (1) and talc is 95 to 60% by weight of the thermoplastic resin (1).
Talc is 5 to 40% by weight, and if the talc is less than 5% by weight, a sufficient effect of addition cannot be obtained.
If it exceeds 0% by weight, the moldability (extrudability) deteriorates, which is not preferable.

As the glass fiber, a commercially available glass fiber can be used. For example, chopped strands having a fiber diameter of 2 to 30 μm and a fiber length of 3 to 10 mm can be mentioned.

In the present invention, the mixing ratio of the thermoplastic resin (2) and the glass fiber is 5 to 40% by weight of the glass fiber with respect to 95 to 60% by weight of the thermoplastic resin (2). When the amount is less than 40%, a sufficient effect cannot be obtained. On the other hand, when the amount exceeds 40% by weight, fluidity is insufficient, and moldability (extrudability) is deteriorated.

[0027] The composition of the present invention further comprises,
Other additives that impart desired properties may be added. For example, impact modifiers, flame retardants, antioxidants, heat stabilizers, antistatic agents, plasticizers, release agents, lubricants, compatibilizers, foaming agents,
Reinforcing agents such as carbon fiber and ceramic whiskers, fillers,
Dyes and pigments may be used alone or in combination of two or more.

In the present invention, a known method can be used as a method for melt-mixing the thermoplastic resin and talc, or the thermoplastic resin and glass fiber individually or simultaneously, and then melt-mixing the polycarbonate resin. In such a method, for example, an extruder having two or more material supply ports is used to previously transfer the thermoplastic resin (1) and talc or the thermoplastic resin (2) and glass fiber from the first material supply port. Melt and mix through the second material supply port, polycarbonate resin or polycarbonate resin and thermoplastic resin (1), (2)
And then melt-mixing and extruding into pets. The thermoplastic resin (1) and talc, or the thermoplastic resin (2) and glass fiber are melt-mixed and extruded into pellets respectively, or the thermoplastic resin (1) and talc, the thermoplastic resin (2) and Glass fibers are simultaneously supplied, melt-mixed, extruded, and pelletized. A method in which these pellets and a polycarbonate resin or a polycarbonate resin and thermoplastic resins (1) and (2) are supplied, melt-mixed and extruded into pets. And the like. As the extruder, a single-screw or twin-screw extruder can be suitably used.

The molded article of the present invention having high strength, excellent repetitive fatigue properties and good appearance can be obtained by molding using the final composition obtained by the above-mentioned method using a usual molding machine. Can be

[0030]

The present invention will be described below in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples.

The raw materials used in each example are as follows. A: Polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd., Iupilon S-2000; molecular weight 25,000)

B: Polyethylene terephthalate resin (manufactured by Mitsubishi Rayon Co., Ltd., Dianite MA-523V)

C: polybutylene terephthalate resin (Duranex 600F, manufactured by Polyplastics Co., Ltd.)
P)

D: Talc (Enstal, manufactured by Hayashi Kasei Co., Ltd.)

G: Chopped strand glass fiber (diameter 13 μm) (ECS03T, manufactured by NEC Corporation)
531P)

G-PC: glass fiber (diameter 13 μm) 30
% Reinforced polycarbonate resin (Mitsubishi Gas Chemical Co., Ltd.)
Iupilon GS2030M)

G-PBT: glass fiber (diameter 13 μm) 3
0% reinforced polybutylene terephthalate resin (Duranex X3300, manufactured by Polyplastics Co., Ltd.)

REFERENCE EXAMPLE 1 Polybutylene terephthalate resin (C) (70% by weight) and talc (D) (30% by weight) were mixed in a tumbler to form a mixture having a diameter of 3%.
Using a 0 mm twin screw vented extruder, barrel temperature 250
C. to obtain pellets (hereinafter referred to as D-PBT).
Abbreviated as -1).

Reference Example 2 80% by weight of polybutylene terephthalate resin (C)
Pellets were obtained in the same manner as in Reference Example 1 except that talc (D) was changed to 20% by weight. (Hereinafter, this is abbreviated as D-PBT-2).

Reference Example 3 60% by weight of polybutylene terephthalate resin (C)
Pellets were obtained in the same manner as in Reference Example 1, except that talc (D) was changed to 40% by weight. (Hereinafter, this is abbreviated as D-PBT-3).

Reference Example 4 15% by weight of talc (D) and 15% by weight of glass fiber (G)
A pellet was obtained in the same manner as in Reference Example 1 except for using (hereinafter, abbreviated as DG-PBT).

REFERENCE EXAMPLE 5 The same procedures as in Reference Example 1 were carried out except that 15% by weight of polybutylene terephthalate resin (C) and 55% by weight of polyethylene terephthalate resin (B) were used as the thermoplastic resin, and the barrel temperature was 270 ° C. To obtain a pellet (hereinafter, D
-Abbreviated as PET).

Examples 1 to 7 The thermoplastic resin and talc previously described in each of the above Reference Examples were used.
Alternatively, a pellet obtained by melt-mixing a thermoplastic resin, talc and glass fiber, and a pellet obtained by previously melt-mixing a commercially available glass fiber and a thermoplastic resin (G
-PC, G-PBT) were mixed in a tumbler with a polycarbonate resin and a thermoplastic resin at the ratios shown in Table 1, and each was mixed using a uniaxial vented extruder having a diameter of 40 mm.
Extruded at a barrel temperature of 270 ° C. to obtain pellets. The pellet was dried at 120 ° C. for 5 hours or more in a hot air drier, and then injection molded at a resin temperature of 270 ° C. and a mold temperature of 90 ° C. to obtain a test piece for measuring physical properties. Tables 1 and 2 show the physical properties and appearance (surface roughness).

Comparative Examples 1 to 5 Polycarbonate resin, thermoplastic resin, talc, glass fiber, and pellets obtained by previously melting and mixing the thermoplastic resin with talc or glass fiber at the ratios shown in Table 3 were used. , Mixed in a tumbler all at once, each 40m in diameter
m using a single screw vented extruder, barrel temperature 270 ° C
To obtain pellets. After drying the pellets at 120 ° C. for 5 hours or more in a hot air drier,
Injection molding was performed at 70 ° C. and a mold temperature of 90 ° C. to obtain a test piece for measuring physical properties. Table 3 shows the physical property values and appearance (surface roughness).

The measurement of each physical property was as follows. Tensile strength; measured based on ASTM D-638. Flexural strength: measured according to ASTM D-790. Deflection temperature under load; measured based on ASTM D-648. Repeat fatigue properties: Measured based on ASTM D-671-B. Surface roughness: measured using a 100 mm diameter disk. (In the table, Rmax represents the maximum height, and Rz represents the ten-point average roughness.) (Note) In the table, "actual" represents an example, and "ratio" represents a comparative example.

[Table 1]

[Table 2]

[Table 3]

[0046]

Industrial Applicability The fat composition of the present invention has excellent mechanical strength as shown by an alloy of a polycarbonate resin and another thermoplastic resin, and is a molded article having a high strength, excellent repetitive fatigue characteristics and good appearance. Has a good appearance because it is obtained,
It is useful as a molding material requiring high strength, good repeated fatigue properties, high heat resistance, and the like.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 101/00 C08L 101/00 (72) Inventor Kazuo Okazaki 5-6-1 Higashi-Yawata, Hiratsuka-shi, Kanagawa Prefecture Mitsubishi Engineering-Plastics Corporation (72) Inventor Hidehiko Kamano 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Mitsubishi Engineering-Plastics Co., Ltd. Technical Center (56) References JP-A-52-114639 (JP, A) (58) ) Surveyed field (Int.Cl. ⁷ , DB name) C08L 69/00

Claims (11)

(57) [Claims] When blending talc and glass fiber with a polycarbonate resin, the thermoplastic resin (1) and talc, and the thermoplastic resin (2) and glass fiber are melt-mixed individually or simultaneously, and then the resulting mixture is obtained. And a polycarbonate resin or a polycarbonate resin and thermoplastic resins (1) and (2) are melt-mixed. 2. The polycarbonate resin composition according to claim 1, wherein the mixing ratio of the thermoplastic resin (1) and talc is 5 to 40% by weight of talc based on 95 to 60% by weight of the thermoplastic resin (1). 3. The polycarbonate resin according to claim 1, wherein the mixing ratio of the thermoplastic resin (2) and the glass fiber is 5 to 40% by weight of the glass fiber with respect to 95 to 60% by weight of the thermoplastic resin (2). Composition. 4. A mixture of the thermoplastic resin (1) and talc in an amount of 5 to 3 parts per 100 parts by weight of the polycarbonate resin or the polycarbonate resin and the thermoplastic resins (1) and (2).
2. The polycarbonate resin composition according to claim 1, wherein the composition is added in an amount of 00 parts by weight. 5. A polycarbonate resin or a mixture of a thermoplastic resin (2) and glass fiber with respect to 100 parts by weight of the polycarbonate resin and the thermoplastic resins (1) and (2).
The polycarbonate resin composition according to claim 1, wherein the composition is blended in an amount of from 300 to 300 parts by weight. 6. The polycarbonate resin composition according to claim 1, wherein the thermoplastic resin (1) is a thermoplastic polyester resin. 7. The polycarbonate resin composition according to claim 6, wherein the thermoplastic resin (1) is polyethylene terephthalate or polybutylene terephthalate. 8. The polycarbonate resin composition according to claim 1, wherein the thermoplastic resin (2) is at least one selected from a polycarbonate resin and a thermoplastic polyester resin. 9. The polycarbonate resin composition according to claim 8, wherein the thermoplastic resin (2) is a polycarbonate resin. 10. The polycarbonate resin composition according to claim 9, wherein the thermoplastic resin (2) is a thermoplastic polyester resin. 11. The polycarbonate resin composition according to claim 10, wherein the thermoplastic resin (2) is polyethylene terephthalate or polybutylene terephthalate.