JP3451167B2 - Polycarbonate resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polycarbonate resin composition, and more particularly to a polycarbonate resin composition containing calcium silicate.

[0002]

2. Description of the Related Art Polycarbonate resins are widely used as resins having excellent mechanical strength, impact resistance and heat resistance. To improve various properties, they are blended with other thermoplastic resins, It is used as a polycarbonate resin that is a polymer alloy. In addition, high rigidity,
It is known to incorporate various inorganic fillers such as calcium silicate when high strength is required. But,
When calcium silicate is added to the polycarbonate resin, there arises a problem of poor appearance similar to the floating of glass fibers. As a method of solving such a drawback, a method of treating an inorganic filler with a silane coupling agent is generally known, but it cannot be said that a sufficient effect is obtained yet.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a polycarbonate resin composition which is excellent in strength and heat resistance and has a good molding appearance.

[0004]

The present invention has been made to solve the above-mentioned problems, and the gist thereof is a mixture obtained by previously melting and mixing a thermoplastic resin and calcium silicate and a polycarbonate. A polycarbonate-based resin composition obtained by melt-mixing a resin or a polycarbonate resin and a thermoplastic resin.

The present invention will be described in detail below. As the polycarbonate resin in the present invention, an aromatic dihydroxy compound or an optionally branched thermoplastic aromatic polycarbonate polymer or copolymer obtained by reacting a small amount of this polyhydroxy compound with phosgene or a diester of carbonic acid. Is.

As the aromatic dihydroxy compound, 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 , 1-bis (4-hydroxyphenyl) cyclohexane and the like, bis (hydroxyaryl) cycloalkanes; 4,4'-dihydroxydiphenyl ether 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, etc. Dihydroxy diaryl ethers; 4,4'-dihydroxy diphenyl sulfide, dihydroxy diaryl sulfides exemplified by 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide; 4,4'-dihydroxy diphenyl sulfoxide, 4,4 ' Dihydroxy -3,
Dihydroxydiaryl sulfoxides exemplified by 3′-dimethyldiphenyl sulfoxide and the like; Dihydroxydiaryl sulfones exemplified by 4,4′-dihydroxydiphenylsulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenylsulfone and the like; Hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, etc. are mentioned. You may use these aromatic dihydroxy compounds individually or in mixture of 2 or more types. The aromatic dihydroxy compound is preferably 2,2-bis (4-hydroxyphenyl) propane.

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)
Polyhydroxy compounds exemplified by -1,3,5-triisopropylbenzene and the like, 3,3-bis (4-hydroxyaryl) oxindole (= isatin bisphenol), 5-chloroisatin bisphenol, 5,
7-dichloroisatin bisphenol, 5-bromoisatin bisphenol and the like can be used.

In the case of the phosgene-processed polycarbonate, a terminal stopper or a molecular weight modifier may be used. Examples of the terminal terminator or the molecular weight modifier include compounds having a monovalent phenolic hydroxyl group, such as ordinary phenol and pt
-Butylphenol, tribromophenol, etc.,
Examples include long-chain alkylphenols, aliphatic carboxylic acid chlorides, aliphatic carboxylic acids, hydroxybenzoic acid alkyl esters, alkyl ether phenols and the like.
The polycarbonate resin in the present invention may be used alone or in combination of two or more kinds.

The molecular weight of the polycarbonate resin in the present invention is 2 at a temperature of methylene chloride as a solvent.
The viscosity average molecular weight converted from the solution viscosity measured at 5 ° C. is 10,000 to 100,000, preferably 15,000 to 50,000.

The thermoplastic resin in the present invention may be a thermoplastic resin other than a polycarbonate resin and is generally a resin that can be blended with a polycarbonate resin, preferably a thermoplastic polyester, a polystyrene resin, or a polyarylene ester resin. Resins, polyolefin-based resins, diene-based resins, polyamide-based resins, polyether-based resins, polysulfone-based resins and polyphenylene-based resins, and the like, since it is possible to significantly improve the chemical resistance of the polycarbonate resin, more preferably thermoplastic polyester Can be mentioned.

The thermoplastic polyester in the present invention is a polymer obtained by reacting an aromatic dicarboxylic acid or its diester with a glycol or an alkylene oxide by a known method, specifically, terephthalic acid or terephthalic acid. Polyethylene terephthalate, polytetramethylene terephthalate (polytetramethylene terephthalate obtained by reacting dimethyl acid, naphthalene dicarboxylic acid, dimethyl naphthalene dicarboxylic acid as a main component of aromatic dicarboxylic acid with ethylene glycol, butanediol, cyclohexanedimethanol or ethylene oxide, etc. Examples thereof include polybutylene terephthalate), polyethylene naphthalate, and polytetramethylene naphthalate (polybutylene naphthalate). Further, the polyester resin may be a copolymer, and examples thereof include a copolymer of cyclohexanedimethanol and terephthalic acid and isophthalic acid, and a copolymer of cyclohexanedimethanol and ethylene glycol and terephthalic acid. .

Preferred examples of the thermoplastic polyester include polyethylene terephthalate and polybutylene terephthalate. The intrinsic viscosity (intrinsic viscosity) of the thermoplastic polyester resin in the present invention is preferably 0.4 to 2 under measurement conditions at 30 ° C. in a mixed solvent in which phenol and tetrachloroethylene are mixed in a weight ratio of 6: 4.
Is. If it is less than 0.4, the impact resistance and chemical resistance tend to be insufficient, and if it exceeds 2, workability tends to deteriorate.
The intrinsic viscosity of the thermoplastic polyester resin is more preferably 0.5 to 1.5.

As the polystyrene resin in the present invention, PS resin, ABS resin, AES resin, MBS resin,
MAS resin, AAS resin, styrene-butadiene block copolymer, styrene-maleic anhydride copolymer, etc. may be mentioned.

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

Examples of the polyolefin resin in the present invention include polyethylene resin and polypropylene resin. Examples of the polyethylene resin include high-density polyethylene resin, low-density polyethylene resin, linear low-density polyethylene resin, ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, ethylene-acrylic ester copolymer, ethylene-glycidyl. (Meth) acrylate copolymer etc. are mentioned. Examples of the polypropylene resin include polypropylene resin, propylene-vinyl acetate copolymer, propylene-vinyl chloride copolymer and the like.

The diene-based resin in the present invention is a monomer having a diene structure alone, a copolymer with a monomer copolymerizable therewith, or a mixture thereof.
-Polybutadiene resin, trans-1,4-polybutadiene resin and the like can be mentioned.

The polyamide resin in the present invention may be an aminocarboxylic acid compound alone, a copolymer of a dicarboxylic acid compound and a diamine compound, or α, ω.
-A polymer obtained by ring-opening polymerization of caprolactam, and examples thereof include nylon 6, nylon 66, nylon 610, and nylon 11.

Examples of the polyether resin in the present invention include polyphenylene ether resin and polyacetal resin, and examples of the polysulfone resin include a polymer having a —SO 2 — bond in the molecule, such as polysulfone resin. Examples of the phenylene resin include polyphenylene sulfide.

As the calcium silicate in the present invention,
It may contain silicic acid and calcium oxide as the main components, and may contain aluminum oxide and iron oxide as the trace components, and commercially available products may be used. As the calcium silicate, it is possible to use one which has been treated with a surface treatment agent such as a silane coupling agent in advance.

The polycarbonate resin composition of the present invention is obtained by pre-melt mixing a thermoplastic resin other than the polycarbonate resin and calcium silicate to obtain a mixture, and blending the mixture with the polycarbonate resin or the polycarbonate resin and the thermoplastic resin. It is a resin composition obtained by melting and mixing. The mixing ratio of the thermoplastic resin to be melt-mixed in advance and the calcium silicate is 9
5 to 50% by weight to calcium silicate 5 to 50% by weight. If the calcium silicate content is less than 5% by weight, it is difficult to obtain a sufficient effect of addition, and if it exceeds 50% by weight, the extrudability tends to deteriorate. The mixing ratio of the thermoplastic resin and calcium silicate to be melt-mixed in advance is preferably 90 to 55% by weight of the thermoplastic resin and 10 to 45% by weight of calcium silicate.

In the present invention, the mixing ratio of the polycarbonate resin or the polycarbonate resin and the thermoplastic resin, and the mixture obtained by previously melting and mixing the thermoplastic resin and the calcium silicate is 100 parts by weight to 20 to 300 parts by weight. Is. If the amount of the mixture obtained by previously melting and mixing the thermoplastic resin and calcium silicate is less than 20 parts by weight, it is difficult to obtain a sufficient reinforcing effect, and if it exceeds 500 parts by weight, the fluidity tends to decrease. The mixing ratio of the polycarbonate resin or the polycarbonate resin and the thermoplastic resin, and the mixture obtained by previously melting and mixing the thermoplastic resin and the calcium silicate is preferably 100 parts by weight to 25 parts by weight.
It is 200 parts by weight.

When a polycarbonate resin or a polycarbonate resin and a thermoplastic resin are mixed and melt-mixed with a mixture obtained by previously melting and mixing a thermoplastic resin other than the polycarbonate resin and calcium silicate, the polycarbonate resin and the heat From the viewpoint of strength and heat resistance, the ratio with the plastic resin is preferably 100 to 50% by weight to 0 to 50% by weight, and more preferably 100 to 60% by weight to 0 to 40% by weight.

The composition of the present invention further has the following objects.
Other additives that give desired properties may be added. For example, impact modifier, flame retardant, antioxidant, heat stabilizer, antistatic agent, plasticizer, release agent, lubricant, compatibilizer, foaming agent,
Glass fiber, carbon fiber, ceramic whiskers, reinforcing agents such as talc, fillers, dyes and pigments, etc., alone or in combination of two or more,
You may use together suitably.

In the present invention, a known method may be used as a method of melt-mixing the thermoplastic resin and calcium silicate in advance and then melt-mixing the obtained mixture with the polycarbonate resin or the polycarbonate resin and the thermoplastic resin. For example, (1) In an extruder having two or more material supply ports, the thermoplastic resin and calcium silicate are melt-kneaded in advance from the first material supply port, and then the second material supply port is used. A method in which a polycarbonate resin or a polycarbonate resin and a thermoplastic resin are added, and further melt-kneaded to form pellets, (2) a thermoplastic resin and calcium silicate are melt-kneaded in advance with an extruder or the like to obtain pellets of a mixture. Blended pellets with polycarbonate resin or polycarbonate resin and thermoplastic resin Furthermore, the method of pelletizing and melt-kneaded by an extruder or the like, and the like. A single-screw or twin-screw extruder can be used as the extruder.

[0025]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples as long as the gist thereof is not exceeded. The raw materials used in each example are as follows. (1) Polycarbonate resin (manufactured by Mitsubishi Gas Chemical Co., Inc.
Iupilon S-2000, molecular weight 25,000) (2) Polyethylene terephthalate resin (Mitsubishi Rayon Co., Ltd., Diamondite PA-200V) (3) Polybutylene terephthalate resin (Polyplastics Co., Ltd., Duranex 600FP) (4) Untreated calcium silicate (Hayashi Kasei Co., Ltd., VM-
8N) (5) Aminosilane-treated calcium silicate (Tsuchiya Kaolin Industry Co., Ltd., S4-1100-1)

The evaluation of physical properties was performed as follows. (6) Tensile strength; measured based on ASTM D-638. (7) Flexural strength: Measured based on ASTM D-790. (8) Deflection temperature under load; measured based on ASTM D-648. (9) Appearance: By visually observing a φ100 mm disc, the case where no silver is generated is A, the case where a small amount of fine silver is generated is B, the case where small silver is generated is C, the large silver is medium. The generated one was designated as D, and the large amount of large silver was designated as E.

Reference Example 1 70% by weight of polybutylene terephthalate resin and 30% by weight of untreated calcium silicate were mixed in a tumbler and extruded at a barrel temperature of 250 ° C. using a φ30 mm twin-screw vent type extruder to form pellets. Was obtained (hereinafter abbreviated as mixture-1). [Reference Example 2] Pellets were obtained in the same manner as in Reference Example 1 except that the untreated calcium silicate was changed to the aminosilane-treated calcium silicate (hereinafter abbreviated as mixture-2).

Reference Example 3 The same as Reference Example 1 except that 70% by weight of polybutylene terephthalate resin was changed to 80% by weight and 30% by weight of untreated calcium silicate was changed to 20% by weight. Pellets were obtained (hereinafter abbreviated as mixture-3). [Reference Example 4] Reference Example-except that in Reference Example 1 70% by weight of polybutylene terephthalate resin was changed to 60% by weight and 30% by weight of untreated calcium silicate was changed to 40% by weight.
Pellets were obtained in the same manner as in 1 (hereinafter abbreviated as mixture-4). Reference Example 5 In Reference Example 1, 70% by weight of polybutylene terephthalate resin, 15% by weight of polybutylene terephthalate resin and 55% by weight of polyethylene terephthalate resin are used.
Pellets were obtained in the same manner as in Reference Example 1 except that the untreated calcium silicate was changed to the aminosilane-treated calcium silicate in weight%, and the barrel temperature of 250 ° C. was changed to 270 ° C. (hereinafter abbreviated as mixture 5).

[Examples 1 to 6] Pellets described in Reference Example obtained by melt-mixing a thermoplastic resin and calcium silicate in advance were mixed with a polycarbonate resin, a polyethylene terephthalate resin and / Or polybutylene terephthalate resin was mixed with a tumbler, and each was extruded at a barrel temperature of 270 ° C using a ø40 mm uniaxial vent type extruder to obtain pellets. The pellets were dried in a hot air dryer at 120 ° C. for 5 hours or more, and then a test piece for measuring physical properties was injection-molded at a resin temperature of 270 ° C. and a mold temperature of 80 ° C. The results are shown in Table-1.

[0030]

[Table 1]

[Comparative Examples 1 to 3] Polycarbonate resin,
Polybutylene terephthalate resin and calcium silicate were mixed together in a tumbler in the proportions shown in Table-1 and extruded at a barrel temperature of 270 ° C using a φ40 mm uniaxial vented extruder to obtain each pellet. It was The pellets were dried in a hot air dryer at 120 ° C. for 5 hours or more, and then a test piece for measuring physical properties was injection-molded at a resin temperature of 270 ° C. and a mold temperature of 80 ° C. The results are shown in Table-1.

[0032]

INDUSTRIAL APPLICABILITY The polycarbonate resin composition of the present invention has high strength and high heat resistance, and is remarkably excellent in the appearance of molded articles, and is suitable for automobile parts, electric and electronic parts, etc. which are required to have good appearance. It is useful in various molded products.

─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hidehiko Kamano 5-6-2 Higashi-Hachiman, Hiratsuka-shi, Kanagawa Mitsubishi Engineering Plastics Co., Ltd. Technical Center (56) Reference JP-A-4-80249 (JP, A) ) (58) Fields surveyed (Int.Cl. ⁷ , DB name) C08J 3/22 C08L 67/00-67/02 C08L 69/00

Claims (4)

(57) [Claims] 1. A mixture obtained by previously melting and mixing a thermoplastic polyester and calcium silicate with a polycarbonate resin or a polycarbonate resin and a thermoplastic polyester.
A polycarbonate-based resin composition obtained by melting and mixing stell . 2. The mixing ratio of the thermoplastic polyester to be melt-mixed in advance and the calcium silicate is 95 to 50% by weight to 5%.
It is -50 weight%, The polycarbonate type resin composition of Claim 1 characterized by the above-mentioned. 3. A pre thermoplastic port with a polycarbonate resin or a polycarbonate resin and a thermoplastic polyester
The polycarbonate resin composition according to claim 1 or 2, wherein the mixing ratio of the mixture obtained by melt-mixing the ester and calcium silicate is 100 parts by weight to 20 to 300 parts by weight. 4. The thermoplastic polyester is polyethylene terephthalate and / or polybutylene terephthalate, according to any one of claims 1 to 3.
The polycarbonate resin composition according to the item.