JP3519117B2 - Polyphenylene oxide resin composition - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to heat distortion resistance, workability,
The present invention relates to a polyphenylene oxide resin composition having excellent impact resistance and chemical resistance.

[0002]

2. Description of the Related Art Polyphenylene oxide resin is a resin having excellent heat resistance, hot water resistance, dimensional stability, chemical resistance, mechanical properties, electrical properties, etc. Also, it has a drawback that the impact resistance is not sufficiently large. Therefore, a method of blending a heterogeneous polymer material such as polystyrene resin is known, but the impact resistance is not sufficiently improved even by blending the polystyrene resin, and the heat resistance and chemical resistance of the polyphenylene oxide resin are further improved. Excellent properties such as properties are likely to be impaired.
As a polystyrene resin, a method in which butadiene rubber or EPDM modified is used or a styrene-based thermoplastic elastomer is compounded is known, but this compounding formulation is effective in improving impact resistance and chemical resistance Although the deterioration of the moldability is small, the melt viscosity is remarkably increased, and as a result, the moldability and the appearance of the molded product are largely impaired, so it cannot be said that the method can be widely adopted.

A method of further blending an ethylene / unsaturated carboxylic acid ester copolymer has been proposed in JP-A-58-17142 for the purpose of ameliorating the drawbacks caused by blending the above-mentioned styrenic resin. It has been shown to exert an excellent effect in improving impact resistance, chemical resistance and the like. However, this method has a drawback that a peeling phenomenon occurs in a molded article when the above ethylene copolymer is excessively added, and thus it is necessary to strictly control the addition amount.

[0004]

Therefore, the present inventors have the effect of addition equal to or more than that of the above-mentioned copolymer, and can add a large amount, and therefore, further processability, impact resistance, surface appearance. In order to find an additive capable of improving the above, etc., an intensive study was conducted. As a result, it has been found that the desired improvements can be achieved by using the ethylene copolymers described below. Therefore, an object of the present invention is to provide a polyphenylene oxide resin composition having excellent properties such as heat resistance, processability, impact resistance, chemical resistance, and surface appearance.

[0005]

According to the present invention, a polyphenylene oxide resin or a modified polyphenylene oxy resin is used.
Sid resin, or polyphenylene oxide resin and poly
(Meth) to 100 parts by weight of the mixture with styrene resin
1-10% by weight of acrylic acid polymer units and 5-40% by weight of (meth) acrylic acid ester polymer units of ethylene.
Provided is a polyphenylene oxide resin composition containing 0.1 to 20 parts by weight of a (meth) acrylic acid / (meth) acrylic acid ester copolymer.

The polyphenylene oxide resin used in the present invention has the general formula

[Chemical 1] (In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ are selected from hydrogen, a halogen atom, a hydrocarbon group or a substituted hydrocarbon group, and at least one of them is a hydrogen atom. .) One or two of the phenol compounds represented by
A polymer obtained by oxidative polymerization with oxygen or an oxygen-containing gas using at least one species and an oxidative coupling catalyst.

R ¹ , R ² , R ³ , R in the above general formula
Specific examples of ⁴ and R ⁵ are hydrogen, chlorine, bromine, fluorine, iodine, methyl, ethyl, n- or iso-propyl, pri-, sec- or t-butyl, chloroethyl, hydroxyethyl, phenylethyl, benzyl. , Hydroxymethyl, carboxyethyl, methoxycarbonylethyl, cyanoethyl, phenyl, chlorophenyl, methylphenyl, dimethylphenyl, ethylphenyl, allyl and the like.

Specific examples of the above general formula include phenol, o-, m-, or p-cresol, 2,6-,
2,5-, 2,4-, or 3,5-dimethylphenol, 2-methyl-6-phenylphenol, 2,6-diphenylphenol, 2,6-diethylphenol, 2
-Methyl-6-ethylphenol, 2,3,5-, 2
3,6- or 2,4,6-trimethylphenol, 3
-Methyl-6-t-butylphenol, thymol, 2-
Methyl-6-allylphenol and the like can be mentioned. Furthermore, phenol compounds other than the above general formula, for example, bisphenol-A, tetrabromobisphenol-A,
Copolymerization of a polyvalent hydroxyaromatic compound such as resorcin, hydroquinone, and novolac resin with a phenol compound of the above general formula may be used.

Preferred among these compounds are homopolymers of 2,6-dimethylphenol or 2,6-diphenylphenol and a large amount of 2,6-xylenol and a small amount of 3-methyl-6-. A copolymer of t-butylphenol or 2,3,6-trimethylphenol may be mentioned.

The polyphenylene oxide resin may also be the above homopolymer or copolymer graft-modified with another polymer. For example, oxidative polymerization of the phenols in the presence of EPDM, oxidative polymerization of the phenols in the presence of polystyrene resin, in the presence of the homopolymer or copolymer of the phenols,
Graft-polymerized styrene and / or other vinyl monomer using a radical initiator, and homopolymer or copolymer of the above-mentioned phenols and polystyrene resin are melt-kneaded and reacted in the presence of a radical generator. And the like. Among these, those modified with polystyrene resin are preferable. The polyphenylene oxide resin may also be a homopolymer or copolymer of the above phenols modified with a modifier such as a polyfunctional compound.

The polyphenylene oxide resin can also be used with other polymer components. Examples of such other polymer component include polystyrene resin, polyolefin, polyester, polycarbonate, polyamide, polyacetal, polyvinyl chloride, and synthetic rubber. Of these, use of polystyrene resin is particularly preferable.

Here, the polystyrene resin means a homopolymer or copolymer of a vinyl aromatic compound. More specifically, it has at least 25% by weight of styrene or its derivative such as styrene, α-methylstyrene, vinyltoluene and the like. Examples of the polystyrene resin include homopolymers of styrene or its derivatives as described above and polybutadiene, polyisoprene, butyl rubber, EPDM rubber, ethylene-propylene copolymer, natural rubber, polysulfide rubber, polyurethane rubber, epichlorohydrid. Styrene polymers modified by the mixing or interaction of natural or synthetic elastomeric substances, such as rubber, and further styrene-containing copolymers such as styrene-acrylonitrile copolymer (SAN), styrene-butadiene copolymer, Styrene-maleic anhydride copolymer, styrene-acrylonitrile-butadiene terpolymer (ABS), poly-α
Examples thereof include styrene-based thermoplastic elastomers such as -methyl-styrene, styrene-butadiene-styrene block copolymers and styrene-isobutylene-styrene block copolymers, or styrene-based thermoplastic elastomers obtained by hydrogenating the diene rubber central block. Further preferred resins for the present invention are polystyrene homopolymers or rubber modified polystyrenes obtained by polymerizing styrene in the presence of 3 to 30% by weight, preferably 4 to 12% by weight of polybutadiene rubber or EPDM rubber. .

The EPDM rubber is a rubber-like interpolymer composed of a mixture of monoolefins and polyene, and includes a rubber-like interpolymer produced from ethylene, α-olefin and polyene. A preferred type of rubbery interpolymer is 10 to 90 mol% ethylene, 10 to 90 mol% α-olefin containing 3 to 16 carbon atoms and 5 to 20 carbon atoms.
The polyene is a non-conjugated cyclic or chain diene having 0.1 to 12 mol%. A particularly preferred type of rubbery interpolymer is ethylene and an α-olefin having 3 to 10 carbon atoms, especially propylene, and 5 to 10 carbon atoms.
Non-conjugated cyclic or chain dienes such as 5-ethylidene-2-norbornene, dicyclopentadiene, 1,4
A hexadiene intercopolymer.

When the modified product is used as the polyphenylene oxide resin, or when it is used together with other polymer components, the unit of the polymer or copolymer of phenol is 15
The amount of the modifying component or other polymer component is not more than 85 parts by weight, preferably not more than 85 to 10 parts by weight, based on at least 15 parts by weight, preferably 15 to 90 parts by weight, and more preferably 30 to 70 parts by weight.
It is more preferable to use a composition having a composition of 70 to 30 parts by weight.

In the present invention, when 100 parts by weight of such a polyphenylene oxide resin is used, or when polyphenylene oxide is used as a modified product or together with other polymer components, the polyphenylene oxide and the other polymer are mixed. 0.1 to 2 per 100 parts by weight in total
0 parts by weight, preferably 0.5 to 10 parts by weight, more preferably 0.5 to 7 parts by weight of an ethylene / (meth) acrylic acid / (meth) acrylic acid ester copolymer is blended. Here, (meth) acrylic acid means acrylic acid or methacrylic acid, and (meth) acrylic acid ester means acrylic acid ester or methacrylic acid ester.
If the blending amount of the ethylene copolymer is small, the effect of addition is not sufficient, and if the blending amount is too large, the mechanical properties of the molded article, particularly the decrease in rigidity, increases,
Bamboo peel-like peeling easily occurs on the surface of the molded product, which is not preferable.

The polymer unit of (meth) acrylic acid in the copolymer is 1 to 10% by weight, preferably 1 to 5% by weight,
The (meth) acrylic acid ester is contained in an amount of 5 to 40% by weight, preferably 5 to 30% by weight. When the copolymer containing no (meth) acrylic acid is used, the physical properties are remarkably deteriorated when it is blended in a large amount.

Examples of the (meth) acrylic acid ester include an alkyl ester of acrylic acid or methacrylic acid having about 1 to 10 carbon atoms. More specifically, methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, isobutyl methacrylate, n methacrylate.
-Butyl and the like can be mentioned. Among these, it is particularly preferable to use an alkyl ester of acrylic acid or methacrylic acid having 1 to 4 carbon atoms.

The copolymer also includes 190 ° C., 21
Melt flow rate under load of 60g is 0.1-40
It is preferable to use one of 0 g / 10 minutes, particularly 1 to 100 g / 10 minutes. Melt flow rate is 0.1g / 1
When a resin having a particle size of less than 0 minutes is used, the dispersion with the polyphenylene oxide resin becomes insufficient, and it is difficult to sufficiently exert its compounding effect. On the other hand, if the melt flow rate becomes too high, the mechanical strength of the resin composition may be impaired, which is not desirable.

Further, a flame retarded thermoplastic resin composition can be obtained by adding a flame retardant for imparting nonflammability or self-extinguishing property to the composition of the present invention. As such a flame retardant, a halogenated organic compound, a mixture of a halogenated organic compound and an antimony compound, elemental phosphorus, a phosphorus compound, a compound containing a phosphorus-nitrogen bond, or a mixture of two or more thereof can be used.

The polyphenylene oxide resin composition of the present invention may contain a resin additive which is usually used depending on the application. For example, plasticizer, stabilizer,
Antioxidants, pigments, dyes, drip retarders, processing aids and the like or inorganic mineral fillers, fibrous, particulate, flake or crushed glass and the like can be contained.

The resin composition of the present invention can be easily manufactured by a known method of melting or solution mixing a thermoplastic resin. For example, a method in which pellets are mixed or pellets and powder are mixed, or powders are mixed in an extruder and kneaded and extruded, a method in which they are kneaded and kneaded using a kneader or a roll and extruded into a sheet, and mixed as a solution The method and the like are appropriately adopted.

[0022]

EXAMPLES The present invention will be described in more detail with reference to examples. The raw material resins used in Examples and Comparative Examples are as follows.

(1) Modified polyphenylene oxide resin: Asahi Kasei Zylon 500Z

(2) Ethylene / (meth) acrylic acid /
(Meth) acrylic acid ester copolymer: Methacrylic acid content 2% by weight Isobutyl acrylate content 24% by weight Melt flow rate (190 ° C., 2160 g) 5 g / 10 minutes

(3) Ethylene / ethyl acrylate copolymer: ethyl acrylate content 25% by weight, melt flow rate (190 ° C., 2160 g) 20 g / 10 minutes

[Examples 1 to 6] Modified polyphenylene oxide resin and ethylene / isobutyl acrylate / methacrylic acid copolymer were blended in the composition ratio shown in Table 1 to give a composition of 30 mmφ.
Using a twin-screw extruder (L / D = 25, rotating in the same direction), 30
Melt kneading was carried out at 0 ° C.

Various physical properties were measured using the obtained composition pellets or test pieces obtained by injection molding from the composition pellets. The results are shown in Table 1. Molding of test pieces for physical property evaluation,
The measurement and the like were performed under the following conditions and methods.

(1) Molding of test pieces for evaluation of physical properties The composition pellets obtained by melt-kneading are injection-molded by an injection molding machine at a cylinder temperature of 290 ° C. and a mold temperature of 70 to 75 ° C. Test pieces for measuring Izod impact strength and tensile strength were prepared.

(2) The heat distortion temperature was measured according to JIS K7207 using an injection molded test piece having a thickness of 6.4 mm and a load of 18.6 kg.

(3) Izod impact strength 3.2 mm thick injection-molded test pieces were provided with V notches and AS
It was measured according to TM D256.

(4) Tensile strength JIS K7113 No. 1 test piece shape, 3 mm thick test piece was measured in accordance with JIS K7113.

(5) Melt viscosity The composition pellets obtained by kneading with an extruder were used and measured with a Capillograph manufactured by Toyo Seiki Seisakusho. (Apparent melt viscosity is measured at a measurement temperature of 280 ° C. and a shear rate of 1385 / sec.)

(6) A 2 mm thick rectangular plate was obtained by bamboo peeling injection molding of a molded product, the rectangular plate was bent several times, and the following judgment was made based on the occurrence of peeling at the bent portion. ◯: No peeling Δ: Slight peeling X: Significant peeling

Comparative Example 1 The physical properties of the modified polyphenylene oxide resin alone were evaluated in the same manner as in Examples 1-6. The results are shown in Table 1.

[Comparative Examples 2 to 3] An ethylene / ethyl acrylate copolymer was used in place of the ethylene / isobutyl acrylate / methacrylic acid copolymer in the examples, and the composition thereof and the modified polyphenylene oxide resin were as shown in Table 1. The mixture was blended in a ratio and melt-kneaded using an extruder in the same manner as in the examples, and the physical properties of the composition were measured. The results are shown in Table 1.

[0036]

[Table 1]

As is clear from Table 1, according to the present invention, the melt viscosity of the modified polyphenylene oxide resin can be lowered without lowering the heat distortion temperature of the resin to improve the molding processability and also the impact resistance. It is possible to obtain a composition having improved

Further, as is clear from comparison with Comparative Examples 2 to 3, the composition of the present invention has ethylene as a modifier as compared with the composition containing the ethylene / unsaturated carboxylic acid ester copolymer. Even if a large amount of the copolymer is blended, the Izod impact strength does not tend to decrease and the exfoliation phenomenon of the molded product is excellent.

[0039]

According to the present invention, the characteristics of the polyphenylene oxide resin such as heat resistance and chemical resistance are not impaired,
Molding processability and impact resistance are simultaneously improved, and a polyphenylene oxide resin having excellent physical properties is obtained, and it can be used as a high-performance engineering plastic in a wide range of applications.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-52-886 (JP, A) JP-A-62-149769 (JP, A) JP-A-62-138552 (JP, A) JP-A-2- 187458 (JP, A) JP 58-17142 (JP, A) Special table 63-501509 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08L 71/12

Claims (2)

(57) [Claims] 1. A vinyl monomer polymer or EPDM modified
1 to 10% by weight of (meth) acrylic acid polymerized units per 100 parts by weight of the modified polyphenylene oxide resin ,
5 to 40% by weight of (meth) acrylic acid ester polymerized units
A polyphenylene oxide resin composition obtained by blending 0.1 to 20 parts by weight of the ethylene / (meth) acrylic acid / (meth) acrylic acid ester copolymer. 2. A polyphenylene oxide resin or a polyphenylene oxide resin.
Modified polyphenylene oxide modified with styrene resin
Resin, or polyphenylene oxide resin and polystyrene
For 100 parts by weight of the mixture with ren resin,
1-10% by weight of polymerized units of phosphoric acid, (meth) acrylic acid
Ester polymerized units of 5-40% by weight ethylene
A) Acrylic acid / (meth) acrylic acid ester copolymer
0.1 to 20 parts by weight of polyphenylene
Xide resin composition.