JP3344444B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polycarbonate resin composition, and more particularly to a good appearance in which a thermoplastic resin other than a polycarbonate resin and talc are melt-mixed in advance and then melt-mixed with a polycarbonate resin or a thermoplastic resin. The present invention relates to a polycarbonate resin composition having a high strength, 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 when various properties are improved. Further, when high rigidity and high strength are required, it is known to use various inorganic fillers such as talc.

[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.

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 of the methods 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 as described above is increased in order to suppress the adverse effects, the adverse effects due to talc can be suppressed. There is a problem that the phyto-based antioxidant has an adverse effect and causes a decrease in strength and the like.

[0005]

Means for Solving the Problems The present inventors have conducted intensive studies on a polycarbonate resin composition capable of obtaining a molded article having improved appearance, strength, heat resistance and the like which has improved the above-mentioned drawbacks. By melting and mixing the thermoplastic resin other than the polycarbonate resin and talc and then melting and mixing the polycarbonate resin or the polycarbonate resin and the thermoplastic resin, the decomposition of the polycarbonate resin is suppressed, and a molded article having high strength and good appearance is obtained. I found what I could get.

That is, according to the present invention, when blending talc with a polycarbonate resin, a thermoplastic resin other than polycarbonate and talc are melt-mixed in advance, and then the resulting mixture is mixed with the polycarbonate resin or the polycarbonate resin and the thermoplastic resin. The present invention relates to a polycarbonate resin composition characterized by being melt-mixed. The resin composition of the present invention retains the mechanical strength and heat resistance of a polycarbonate resin or an alloy resin of a polycarbonate resin and another thermoplastic resin, and can provide a molded article having particularly 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 a carbonic acid diester. It is a union or a copolymer.

An example of the aromatic dihydroxy compound is 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
Polyhydroxy compounds exemplified by -hydroxy-5-methylbenzyl) -4-methylphenol, α, α ', α "-tri (4-hydroxyphenyl) -1,3,5-triisopropylbenzene, and 3 , 3-bis (4-
Hydroxyaryl) oxindole (= isatin bisphenol), 5-chlorisatin bisphenol,
Examples thereof include 5,7-dichloroisatin bisphenol and 5-bromoisatin bisphenol.

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.

The thermoplastic resin used in the present invention may be any resin that can be generally blended with a polycarbonate resin. Examples of these thermoplastic resins include thermoplastic polyester resins, polystyrene resins, polyarylene ester resins, polyolefin resins, diene resins, polyamide resins, polyether resins, polysulfone resins, polyphenylene resins, and the like. Or a mixture of two or more selected from the group consisting of:

The above-mentioned thermoplastic polyester resin is a polymer obtained by reacting an aromatic dicarboxylic acid or its diester with glycol or alkylene oxide by a known method, and specifically, terephthalic acid or terephthalic acid. Polyethylene terephthalate, polytetramethylene terephthalate (polyethylene methylene terephthalate (poly) Butylene 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 above thermoplastic polyester resin is
In a mixed solvent in which phenol and tetrachloroethylene are mixed at a weight ratio of 6: 4, an intrinsic viscosity (intrinsic viscosity) measured at 30 ° C. of 0.4 or more, usually 0.5 to 1.5 is preferable. If it is less than 4, the impact resistance and chemical resistance are not sufficiently improved, which is not preferable.

As the polystyrene resin, polystyrene (PS resin), ABS resin, AES resin, MBS resin, MAS resin, AAS resin, styrene-butadiene block copolymer, styrene-maleic anhydride copolymer and the like are desirable.

The polyarylene ester-based resin is a polymer or copolymer obtained by subjecting an aromatic dihydroxy compound or a derivative thereof and an aromatic dicarboxylic acid or a derivative thereof to a condensation reaction 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 monomers having a diene structure such as 1,2-polybutadiene resin and trans-1,4-polybutadiene resin alone or copolymers thereof with monomers copolymerizable therewith; Is a mixture of

The polyamide resin is preferably an aminocarboxylic acid compound alone, 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, a polyphenylene ether resin is desirable.

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

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 minor 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 and talc is 5 to 40% by weight of talc to 95 to 60% by weight of the thermoplastic resin. If it exceeds 40% by weight, the moldability (extrudability) deteriorates, which is not preferable.

In the present invention, the blending amount of the thermoplastic resin and talc is 20 parts by weight based on 100 parts by weight of the polycarbonate resin or the polycarbonate resin and the thermoplastic resin.
If it is less than 20 parts by weight, a sufficient reinforcing effect cannot be obtained, and if it is more than 300 parts by weight, fluidity tends to be insufficient and moldability tends to deteriorate, which is not preferable.

The composition of the present invention may further comprise,
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,
One or two or more reinforcing agents such as glass fibers, carbon fibers, and ceramic whiskers, fillers, dyes and pigments may be appropriately used.

In the present invention, a known method can be used as a method of melt-mixing the thermoplastic resin and talc and then melt-mixing the polycarbonate resin or the polycarbonate resin and the thermoplastic resin. For example, in an extruder having two or more material supply ports, a thermoplastic resin and talc are melt-kneaded in advance from the first material supply port, and then the polycarbonate resin or the talc is supplied from the second material supply port. A method in which a polycarbonate resin and a thermoplastic resin are added, and further melt-kneaded and pelletized. A method in which a thermoplastic resin and talc are previously melt-kneaded to obtain an extruded pellet, and the pellet and the polycarbonate resin are blended, melt-kneaded, extruded, and pelletized. And the like. As the extruder, a single-screw or twin-screw extruder can be suitably used.

[0026]

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., diamondite MA-523V)

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

D-1: Talc (Fuji Talc Kogyo Co., Ltd.)
LM-S # 100)

D-2: Talc (Enstal, manufactured by Hayashi Kasei Co., Ltd.)

D-3: Talc treated with surface silane (CHC-13S10, manufactured by Hayashi Kasei Co., Ltd.)

Reference Example 1 70% by weight of polybutylene terephthalate resin (C) and 30% by weight of talc (D-1) were mixed in a tumbler, and the barrel temperature was 250 ° C. using a biaxial vent type extruder having a diameter of 30 mm. To obtain pellets (hereinafter referred to as E
Abbreviated as -1).

Reference Example 2 Pellets were obtained in the same manner as in Reference Example 1 except that talc (D-2) was replaced by 30 parts by weight instead of talc (D-1) (hereinafter referred to as E-2). Abbreviated).

Reference Example 3 Pellets were obtained in the same manner as in Reference Example 1 except that talc (D-3) was replaced with 30 parts by weight of talc (D-1) (hereinafter, abbreviated as E-3). Do).

Reference Example 4 70% by weight of polybutylene terephthalate resin (C) was added to 8
0% by weight, 20% by weight of talc (D-1) 30% by weight
Other than the above, pellets were obtained in the same manner as in Reference Example 1 (hereinafter abbreviated as E-4).

Reference Example 5 70% by weight of polybutylene terephthalate resin (C) was added to 6
Pellets were obtained in the same manner as in Reference Example 1 except that 0% by weight and talc (D-1) 30% by weight and talc (D-2) 40% by weight were obtained (hereinafter abbreviated as E-5). ).

Reference Example 6 Polybutylene terephthalate resin (C) (15% by weight), polyethylene terephthalate resin (B) 55% by weight, and talc (D-2) 30% by weight were mixed, and the barrel temperature was 270.
Extruded pellets were obtained at ℃ (hereinafter, this is abbreviated as E-6).

Examples 1 to 7 Pellets obtained by previously melting and mixing a thermoplastic resin and talc described in each Reference Example were mixed at the ratios shown in Table 1 below.
The mixture was mixed with a polycarbonate resin and a thermoplastic resin using a tumbler, and extruded at a barrel temperature of 270 ° C. using a single-screw vented extruder having a diameter of 40 mm to obtain pellets. The pellet was dried in a hot air drier at 120 ° C. for 5 hours or more, and then injection molded at a resin temperature of 270 ° C. and a mold temperature of 80 ° C. to obtain a test piece for measuring physical properties. Table 1 shows the physical properties and the appearance of the molded product.

Comparative Examples 1-3 Polycarbonate resin, thermoplastic resin, and talc were mixed together at a ratio shown in Table 2 by a tumbler, and a barrel temperature of 2 was obtained using a uniaxial vent type extruder having a diameter of 40 mm.
Extruded at 70 ° C. to obtain each pellet. The pellet was dried in a hot air drier at 120 ° C. for 5 hours or more, and then injection molded at a resin temperature of 270 ° C. and a mold temperature of 80 ° C. to obtain a test piece for measuring physical properties. Table 2 shows each physical property value and appearance of the molded product.

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. Appearance: A disk with a diameter of 100 mm is visually observed. A indicates no silver on the surface of the molded product, B indicates a small amount of small silver generated, C indicates a small amount of medium silver generated, and C indicates a large silver. D was generated when the amount was moderate, and E was generated when a large amount of large silver was generated.

[Table 1] (In the table, "actual" means an example)

[Table 2] (`` Ratio '' in the table means a comparative example)

[0042]

The resin composition of the present invention retains the mechanical strength of an alloy resin of a polycarbonate resin and another thermoplastic resin, and provides a molded article having high strength and good appearance. It is useful as various molding materials having a good appearance, high strength, high heat resistance and the like.

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kazuo Okazaki 5-6-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Inside the Engineering Center of Mitsubishi Engineering-Plastics Corporation (72) Inventor Hidehiko Kamano 5-6-Higashi-Hachiman, Hiratsuka-shi, Kanagawa No. 2 Mitsubishi Engineering Plastics Co., Ltd. Technical Center (56) References JP-A-3-21664 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 69/00

Claims (5)

(57) [Claims] When blending talc with a polycarbonate resin, the thermoplastic resin and talc are melt-mixed in advance, and then the obtained mixture is melt-mixed with the polycarbonate resin or the polycarbonate resin and the thermoplastic resin. Polycarbonate resin composition. 2. The polycarbonate resin composition according to claim 1, wherein the mixing ratio of the thermoplastic resin and talc is 5 to 40% by weight of talc based on 95 to 60% by weight of the thermoplastic resin. 3. The polycarbonate resin composition according to claim 1, wherein 20 to 300 parts by weight of a mixture of the thermoplastic resin and talc is mixed with 100 parts by weight of the polycarbonate resin or the polycarbonate resin and the thermoplastic resin. 4. The polycarbonate resin composition according to claim 1, wherein the thermoplastic resin is a thermoplastic polyester resin. 5. The polycarbonate resin composition according to claim 4, wherein the thermoplastic polyester resin is polyethylene terephthalate or polybutylene terephthalate.