JP3341791B2 - 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 method of preliminarily melting and mixing a thermoplastic resin other than a polycarbonate resin and aluminum borate whiskers, and then melting the polycarbonate resin or the polycarbonate resin and the thermoplastic resin. The present invention relates to a polycarbonate resin composition which is capable of obtaining a molded article having good mixed properties and excellent 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 various thermoplastic resins to improve various properties. Further, when high rigidity and high strength are required, it is known to use various inorganic fillers such as aluminum borate whiskers.

[0003] However, when an inorganic filler having a fine shape such as aluminum borate whisker is added to a polycarbonate resin, whiskers agglomerate with each other, resulting in poor appearance of a molded product. As a method of solving such a defect, a method of generally performing a surface treatment of an inorganic filler with a silane coupling agent is known, but in the case of aluminum borate whiskers, even if such treatment is performed, it is still insufficient. In fact, no significant effect has been obtained, and further improvement is required.

[0004]

Means for Solving the Problems The present inventors have conducted intensive studies on a polycarbonate resin composition which can improve the above-mentioned drawbacks and can obtain a molded article excellent in appearance, strength, heat resistance and the like. By melt-mixing a thermoplastic resin other than the polycarbonate resin and aluminum borate whisker and then melt-mixing with the polycarbonate resin or the polycarbonate resin and the thermoplastic resin, whisker agglomeration is suppressed, and high strength and good appearance are formed. Product was obtained.

That is, according to the present invention, when blending an aluminum borate whisker with a polycarbonate resin, the thermoplastic resin and the aluminum borate whisker 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 with a resin. The resin composition of the present invention retains the mechanical strength, heat resistance, and the like 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 an aromatic dihydroxy compound or an optionally branched thermoplastic aromatic polycarbonate polymer obtained by reacting an aromatic dihydroxy compound or a small amount thereof with a phosgene or carbonic acid diester. Or it is a copolymer.

The aromatic dihydroxy compounds include 2,2-bis (4-hydroxyphenyl) propane (= bisphenol A) and 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, 1,1-bis (4-hydroxyphenyl-1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane Bis (hydroxyaryl) alkanes exemplified by 1, etc .; 1,1
-Bis (4-hydroxyphenyl) cyclopentane,
Bis (hydroxyaryl) cycloalkanes exemplified by 1,1-bis (4-hydroxyphenyl) cyclohexane and the like; 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxy-3,3′-dimethyldiphenyl ether and the like Dihydroxydiarylethers exemplified; 4,4'-dihydroxydiphenylsulfide, dihydroxydiarylsulfides exemplified by 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfide and the like; 4,4'-dihydroxydiphenylsulfoxide , 4,4'-dihydroxy-3,3'-dimethyldiphenylsulfoxide;dihydroxydiarylsulfoxides;4,4'-dihydroxydiphenylsulfone,4,4'-dihydroxy-3,
Dihydroxydiarylsulfones exemplified by 3′-dimethyldiphenylsulfone; hydroquinone, resorcinol, 4,4′-dihydroxydiphenyl and the like; 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 resins used in the present invention may be used alone or as a mixture of two or more.

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. One or a mixture of two or more selected from the following is used.

The thermoplastic polyester resin 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 dimethyl terephthalate. Polyethylene terephthalate, polytetramethylene terephthalate (polybutylene) obtained by reacting ethylene, glycol, butanediol, cyclohexane dimethanol or ethylene oxide with ethylene, naphthalenedicarboxylic acid or dimethyl naphthalenedicarboxylate as a main component of an aromatic dicarboxylic acid. 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. .

Further, the above-mentioned thermoplastic polyester resin comprises:
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 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, Ethylene-glycidyl (meth) acrylate copolymer, polypropylene, propylene-vinyl acetate copolymer, propylene-vinyl chloride copolymer and the like are desirable.

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 with monomers copolymerizable therewith; 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, 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 particularly preferred. Among these thermoplastic polyester resins, polyethylene terephthalate and polybutylene terephthalate are particularly preferably used.

The aluminum borate whisker used in the present invention are generally acicular crystal represented by the chemical composition of _{9Al 2 O 3 · 2B 2 O} 3, average fiber length 10 to 30
μm, and the average fiber diameter is 0.5 to 1.0 μm. As the aluminum borate whisker, one that has been previously treated with a surface treatment agent such as a silane coupling agent can be used.

In the present invention, the mixing ratio of the thermoplastic resin and the aluminum borate whisker is from 95 to 95% of the thermoplastic resin.
Aluminum borate whiskers 5 to 60% by weight
40% by weight, and aluminum borate whiskers are 5%.
If the amount is less than 10% by weight, a sufficient effect cannot be obtained.
On the other hand, if it exceeds 40% by weight, the fluidity becomes insufficient and the moldability (extrudability) deteriorates, which is not preferred.

In the present invention, the blending amount of the mixture of the thermoplastic resin and the aluminum borate whisker is a polycarbonate resin or a mixture of the polycarbonate resin and the thermoplastic resin.
It is 20 to 300 parts by weight with respect to 00 parts by weight, and if it is less than 20 parts by weight, a sufficient reinforcing effect cannot be obtained. .

The composition of the present invention may further include,
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 for melt-mixing the thermoplastic resin and the aluminum borate whisker 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 an aluminum borate whisker are melt-kneaded in advance from the first material supply port, and then the polycarbonate resin or the polycarbonate resin is supplied from the second material supply port. A method in which a resin and a thermoplastic resin are added, and further melt-kneaded and pelletized. A method in which a thermoplastic resin and aluminum borate whiskers are melt-kneaded in advance to obtain extruded pellets, and the pellets are blended with a polycarbonate resin or a polycarbonate resin and a thermoplastic resin, melt-kneaded, extruded, and pelletized. And the like. As the extruder, a single-screw or twin-screw extruder can be suitably used.

[0025]

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 (Dianight MA-523V, manufactured by Mitsubishi Rayon Co., Ltd.)

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

D-1: Untreated aluminum borate whisker (Alvolex Y, manufactured by Shikoku Chemicals Co., Ltd.)

D-2: Aluminum borate whisker treated with aminosilane coupling agent (Shikoku Chemicals Co., Ltd.)
Made by Albolex YS1)

Reference Example 1 70% by weight of polybutylene terephthalate resin (C) and 30% by weight of aluminum borate whisker (D-1) were mixed in a tumbler, and the mixture was barreled using a twin-screw extruder having a diameter of 30 mm. The pellets were extruded at a temperature of 250 ° C. (hereinafter, abbreviated as E-1).

Reference Example 2 The aluminum borate whisker (D) used in Reference Example 1
-1) instead of aluminum borate whiskers (D-
2) A pellet was obtained in the same manner as in Reference Example 1 except that the content was 30% by weight (hereinafter, this is abbreviated as E-2).

Reference Example 3 Reference Example 1 except that the polybutylene terephthalate resin was 60% by weight and the aluminum borate whisker was 40% by weight.
And pellets were obtained in the same manner as described above (hereinafter, abbreviated as E-3).

Reference Example 4 Pellets were obtained in the same manner as in Reference Example 1 except that the polyethylene terephthalate resin (C) was replaced by 70% by weight of the polyethylene terephthalate resin (B) and the barrel temperature was changed to 270 ° C. , Which is abbreviated as E-4).

Reference Example 5 70% by weight of polyethylene terephthalate resin (B) was added to 8
0% by weight of aluminum borate whisker (D-1)
Pellets were obtained in the same manner as in Reference Example 4 except that 30% by weight was changed to 20% by weight (hereinafter abbreviated as E-5).

Examples 1 to 6 Pellets obtained by melting and mixing the thermoplastic resin and aluminum borate whisker previously shown in the above reference examples were mixed with the polycarbonate resin and the thermoplastic resin at the ratios shown in Table 1. Mix with resin and tumbler, each 40mm in diameter
The pellets were extruded at a barrel temperature of 270 ° C. using a single-screw vented extruder. The pellets were dried in a hot air drier at 120 ° C. for 5 hours or more.
Injection molding was performed at 0 ° 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 aluminum borate whiskers were mixed at once in a tumbler at the ratios shown in Table 2, and then barreled using a 40 mm diameter uniaxial vented extruder. Each pellet was obtained by extruding at a temperature of 270 ° C. The pellets are placed in a hot air drier at 120 ° C.
After drying for 5 hours or more, injection molding was performed 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.

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 was visually observed, and the molded product surface was marked with A without any occurrence of bumps due to aggregation, B with a small amount generated, C with a moderate amount generated, and D with a large amount generated. did.

[Table 1] (In the table, `` actual '' means an example.)

[Table 2] (In the table, `` ratio '' means Comparative Example)

[0039]

According to the resin composition of the present invention, a molded article having high strength and good appearance can be obtained while maintaining the mechanical strength of an alloy resin of a polycarbonate resin and another thermoplastic resin. It has an appearance and is useful as various molding materials requiring high strength, high heat resistance and the like.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Kazuo Okazaki 5-6-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Prefecture Inside the Engineering Center, Mitsubishi Engineering-Plastics Corporation (72) Hidehiko Kamano 5-6-Higashi-Hachiman, Hiratsuka-shi, Kanagawa No. 2 Mitsubishi Engineering Plastics Co., Ltd. Technical Center (56) References JP-A-4-146957 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 69/00

Claims (5)

(57) [Claims] Claims: 1. When blending an aluminum borate whisker with a polycarbonate resin, a thermoplastic resin and an aluminum borate whisker are melt-mixed in advance,
A polycarbonate resin composition characterized by melting and mixing the obtained mixture with a polycarbonate resin or a polycarbonate resin and a thermoplastic resin. 2. The polycarbonate resin composition according to claim 1, wherein the mixing ratio of the thermoplastic resin and the aluminum borate whisker is 5 to 40% by weight of the aluminum borate whisker with respect to 95 to 60% by weight of the thermoplastic resin. 3. A polycarbonate resin or a mixture of a thermoplastic resin and aluminum borate whiskers is added to 100 parts by weight of the polycarbonate resin and the thermoplastic resin.
The polycarbonate resin composition according to claim 1, wherein the composition is contained in an amount of 0 to 300 parts by weight. 4. The polycarbonate resin composition according to claim 3, 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.