KR100573443B1 - Polyphenylene ether resin composition - Google Patents

Abstract

The polyphenylene ether thermoplastic resin composition according to the present invention comprises 100 parts by weight of a base resin (A) + (B) comprising 5 to 95 parts by weight of (A) polyphenylene ether resin and 5 to 95 parts by weight of (B) polyamide resin. 1 to 30 parts by weight of (C) styrenic copolymer resin, 1 to 30 parts by weight of (D) acrylate copolymer resin and 0.1 to 10% by weight of reactive monomer including (E) unsaturated carboxylic acid or anhydride group It is characterized by consisting of wealth.

Polyphenylene ether, polyamide, styrene copolymer, acrylic copolymer, reactive monomer, impact resistance

Description

Polyphenylene Ether Resin Composition

Field of invention

The present invention relates to a polyphenylene ether-based thermoplastic resin composition and a molded article using the same. More specifically, the present invention provides a polyphenyl containing a styrene copolymer, an acrylate copolymer and a reactive monomer in order to reinforce the impact resistance of a composition based on a mixture of a polyphenylene ether resin and a polyamide resin. It relates to a lene ether resin composition.

Background of the Invention

Polyphenylene ether resins or mixtures of polyphenylene ether resins and polystyrene resins have excellent mechanical and electrical properties at high temperatures and are widely used in various fields such as automobile parts, electrical parts, and electronic parts. However, polyphenylene ether-based resins have a disadvantage of poor solvent resistance and very poor workability.

In addition, the polyamide resin is excellent in chemical resistance and workability, but has a disadvantage in that heat resistance and impact resistance are not good, thereby limiting its use as an engineering plastic resin. Therefore, a lot of research has been conducted to compensate for the shortcomings of these two resins.

U.S. Patent No. 3,379,792 discloses a resin composition in which 0.1 to 25% of a polyamide resin is added to a polyphenylene ether resin. However, when the content of the polyamide resin is 20% or more, there is a disadvantage in that the physical separation of the molded article is remarkably lowered because a phase separation phenomenon occurs because there is no compatibility between the two resin components.

U.S. Patent No. 4,315,086 discloses (a) a liquid diene-based polymer and (b) an epoxy-based polymer based on 100 parts by weight of a resin composition composed of 5 to 95% by weight of polyphenylene ether resin and 95 to 5% by weight of polyamide resin. And (c) at least one compound selected from the group consisting of polymers having carbon-carbon double bonds or triple bonds and having carboxylic acids, anhydrides, acid amides, imides, carboxylic esters, amino or hydroxyl groups; A resin composition containing 30 parts by weight is disclosed.

U.S. Patent No. 4,943,399 discloses a monomer having a double bond capable of simultaneously polymerizing a polyphenylene ether (a1), a vinyl aromatic polymer (a2), an α, β-unsaturated dicarboxylic acid or a derivative thereof, and an amide group in the first region of the extruder. And a monomer (a3) selected from the group consisting of monomers having a lactam group and a polymerizable double bond simultaneously, another polymerizable monomer (a4), and a free radical initiator (a5) to react with the modified polyphenylene ether resin ( A), and in the second zone of the extruder, polyamide (B), unmodified polyphenylene ether resin (C), vinyl aromatic copolymer (D), impact modifier (E), and other additives (F Disclosed is a method for producing a polyphenylene ether resin composition by the addition of).

EP 046,040 discloses (a) a polyphenylene ether resin, (b) a copolymer comprising a vinyl aromatic polymer and an α, β-unsaturated dicarboxylic anhydride or an imide polymer thereof, and (c) a polyamide, And optionally (d) a resin composition having improved heat resistance, oil resistance, and impact resistance made of the impact modifier.

International patent application PCT / US86 / 01511 has at least one carbon-carbon double bond or triple bond in the molecule under the absence of a free group initiator, and has a carboxylic acid, acid anhydride, acid amide, imide, ester, amino And a method for modifying polyphenylene ether by mixing a functional compound having at least one functional group selected from the group consisting of hydroxyl groups with the polyphenylene ether in a molten state.

In the above-mentioned method, there was a limit in imparting excellent impact resistance due to the low compatibility of the polyphenylene ether resin and the polyamide resin. Accordingly, the present inventors use a reactive monomer having an unsaturated carboxylic acid together to induce chemical bonding at the interface between the polyphenylene ether resin and the polyamide resin, thereby improving compatibility and improving the styrene polymer and the acrylate polymer. The invention has led to the invention of a polyphenylene ether-based thermoplastic resin composition having excellent impact resistance.

 An object of the present invention is to provide a polyphenylene ether-based thermoplastic resin composition having excellent impact resistance.

Another object of the present invention is to provide a polyphenylene ether-based thermoplastic resin composition having excellent compatibility.

The above and other objects of the present invention can be achieved by the present invention described in detail.

Summary of the Invention

The present invention relates to (C) a styrene copolymer based on 100 parts by weight of the base resin (A) + (B) consisting of 5 to 95 parts by weight of (A) polyphenylene ether resin and 5 to 95 parts by weight of (B) polyamide resin. Polyphenylene ether-based thermoplastic resin composition comprising 1 to 30 parts by weight of the resin, 1 to 30 parts by weight of the (D) acrylate copolymer resin and 0.1 to 10 parts by weight of the reactive monomer containing the (E) unsaturated carboxylic acid or anhydride group thereof. It is about.

Hereinafter, the content of the present invention will be described in detail.

Detailed Description of the Invention

(A) polyphenylene ether resin

As the polyphenylene ether resin, which is the component (A) used in the preparation of the resin composition of the present invention, a polyphenylene ether resin may be used alone or a mixture of a polyphenylene ether resin and a vinyl aromatic polymer may be used. .

Examples of the polyphenylene ether resin include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether and poly (2,6-dipropyl -1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly ( 2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) Copolymer of ether with poly (2,3,6-trimethyl-1,4-phenylene) ether, poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-tri Copolymers of ethyl-1,4-phenylene) ether and the like can be used, among which poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1, It is preferable to use a copolymer of 4-phenylene) ether or poly (2,6-dimethyl-1,4-phenylene) ether, and to use poly (2,6-dimethyl-1,4-phenylene) ether It is more preferable to use.

The degree of polymerization of the polyphenylene ether resin used in the preparation of the resin composition of the present invention is not particularly limited, but considering the thermal stability and workability of the resin composition, the intrinsic viscosity when measured in a chloroform solvent at 25 ° C is measured. It is preferable that it is 0.2-0.8. It is also possible to use the above polyphenylene ether resins alone or to use two or more thereof in an appropriate ratio.

The composition of the polyphenylene ether resin (A) according to the present invention is preferably about 5 to 95 parts by weight based on the base resin. When the polyphenylene ether resin is used in less than 5 parts by weight, there is a disadvantage in that the properties of the polyphenylene ether resin are not expressed, and when used in excess of 95 parts by weight, a problem of significantly lower impact resistance occurs.

(B) polyamide resin

The polyamide resin (B) which is a component of the present invention is polycaprolactam (nylon 6), poly (11-aminoundecanoic acid) (nylon 11), polylauryllactam (nylon 12), polyhexamethylene adip Copolymerization thereof with amide (nylon 6,6), polyhexaethylene azelamide (nylon 6,9), polyhexaethylene sebacamide (nylon 6,10), polyhexaethylene dodecanodiamide (nylon 6,12) and the like Nylons such as chain nylon 6 / 6,10, nylon 6 / 6,6 and nylon 6/12 may be used alone, or two or more thereof may be mixed and used in an appropriate ratio.

The polyamide resin used in the present invention has a melting point of 250 ° C. or higher and a relative viscosity (measured at 25 ° C. by adding 1% by weight of polyamide resin to m-cresol) in consideration of mechanical properties and heat resistance of the resin composition. It is preferable that the composition is about 5 to 95 parts by weight with respect to the base resin. When using less than 5 weight part or more than 95 weight part of polyamide resins, the problem that compatibility with polyphenylene ether resin falls is produced.

(C) Styrene Copolymer

The styrenic copolymer (C) used in the preparation of the polyphenylene ether thermoplastic resin composition of the present invention is derived from a vinyl aromatic monomer, and may be a block or a radial tere block copolymer in the form of AB or ABA.

The composition of the styrenic copolymer according to the present invention is preferably 1 to 30 parts by weight based on 100 parts by weight of the base resin consisting of (A) + (B). If the styrene-based copolymer is used in less than 1 part by weight, there is a disadvantage that the effect of improving the impact resistance is not expressed, when using more than 30 parts by weight, the problem of lowering the compatibility of polyphenylene ether resin and polyamide resin This happens.

Blocks or radial block copolymers in the form of AB or ABA are copolymers of vinyl aromatic monomers and blocks of hydrogenated, partially hydrogenated or unhydrogenated unsaturated dienes. Examples of block copolymers of the AB diblock type include polystyrene. Polybutadiene, polystyrene-polyisoprene, polyalphamethylstyrene-polybutadiene copolymers, and hydrogenated forms thereof. Such AB diblock type copolymers are well known commercially and are typically represented by Phillips' Solprene and K-resin and Shell's Creton D. And Kraton G.

Examples of ABA triblock type block copolymers include polystyrene-polybutadiene-polystyrene (SBS), polystyrene-polyisoprene-polystyrene (SIS), polyalphamethylstyrene-polybutadiene-polyalphamethylstyrene, polyalphamethylstyrene-poly Copolymers such as isoprene-polyalphamethylstyrene and copolymers in hydrogenated form thereof. Such ABA triblock type copolymers are also widely known commercially, and are representative of Shell's Cariflex, Creton D, Kraton G, and Kuraray. Septon et al.

(D) acrylate copolymer

The acrylate copolymer as the component (D) of the present invention is an ethylene / alkyl acrylate copolymer composed of ethylene, vinyl acetate, and carbon monooxide, and specific examples thereof include alkyl (meth) acrylate. Alkyl may have up to 24 carbon atoms. Examples of alkyl acrylates or methacrylates include methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, 2-ethylhexyl acrylate, glycidyl methacrylate And n-octyl acrylate.

The composition of the styrenic copolymer according to the present invention is preferably 1 to 30 parts by weight based on 100 parts by weight of the base resin consisting of (A) + (B). If the styrene-based copolymer is used in less than 1 part by weight, there is a disadvantage that the effect of improving the impact resistance is not expressed, when using more than 30 parts by weight, the problem of lowering the compatibility of polyphenylene ether resin and polyamide resin This happens.

The acrylate copolymer according to the present invention is an ethylene / methyl acrylate (EMA), ethylene / ethyl acrylate (EEA), ethylene / butyl acrylate (EBA) copolymer, etc., depending on the type of alkyl added at the time of manufacture The density ranges from 1.0 to 1.3 g / cm 3 and the weight average molecular weight ranges from 100,000 to 400,000, and Duvalon, Inc., Elvaloy.

(E) reactive monomer

Reactive monomers having unsaturated carboxylic acids or anhydride groups thereof that may be used in the present invention include citric anhydride, maleic anhydride, maleic acid, itaconic anhydride, fumaric acid, acrylic acid, and methacrylic acid ester maleic anhydride. There is an advantage in that a modified polyphenylene ether resin can be made without a silver initiator. In the present invention, citric acid anhydride is used as the reactive monomer, and the method for producing the modified polyphenylene ether resin grafted to the polyphenylene ether resin (A) is not particularly limited, but phosphite is considered in view of the relatively high working temperature. It is preferable to perform graft reaction in melt-kneading state using a series stabilizer.

It is preferable to use 0.01-10 weight part with respect to 100 weight part of said component (A) + (B) base resin, and, as for the reactive monomer, it is more preferable to use 1-5 weight part. In the case of using less than 0.01 parts by weight, there is almost no effect of improving the compatibility of the final resin composition, when using in excess of 10 parts by weight there is a disadvantage that the impact resistance is lowered.

In the thermoplastic resin manufacturing method of the present invention, a plasticizer, an inorganic additive, a heat stabilizer, an antioxidant, a light stabilizer, a pigment, and / or a dye may be added according to each use. The inorganic additives to be added include asbestos, glass fibers, talc, ceramics and sulfates, and these may be used in an amount of 0 to 10 parts by weight based on 100 parts by weight of the base resin of the present invention.

The present invention may be better understood by the following examples, which are only specific examples of the present invention and are not intended to limit or limit the protection scope of the present invention.

Example

Specifications of each component used in the Examples and Comparative Examples according to the present invention are as follows.

(A) polyphenylene ether (PPE) resin

Poly (2,6-dimethyl-phenylether) (trade name GE Plastics HPP-820) manufactured by GE Plastics Corporation was used.

(B) polyamide resin

Solutia nylon 66 (trade name: VYDYNE 50BW) was used.

(C) Styrene Copolymer

A poly (styrene-ethylene-butadiene) triblock copolymer (trade name G1651) from Shell was used.

(D) acrylate copolymer

(D1) Dupont acrylate crab copolymer (trade name Elvaloy 1126AC) was used.

(D2) Dupont's acrylate crab copolymer (trade name Elvaloy 2116AC) was used.

(E) reactive monomer

Citric acid anhydrous from Samjeon Pure Chemical Co., Ltd. was used.

Example 1-2

Example 1-2 is to prepare a resin composition while changing the type and content of the (C) styrene copolymer and (D) acrylic copolymer in the resin composition components of the present invention as shown in Table 1.

Extruded in a twin screw extruder at a temperature range of 280 ~ 300 ℃ to produce a pellet. The prepared pellets were dried at 80 ° C. for 3 hours and then injected into a 10 Oz injection machine under molding conditions of 280 to 300 ° C. and mold temperatures of 80 to 100 ° C. to prepare physical specimens.

Izod impact strength (1/8, notched) was measured according to the ASTM D256 standard, and tensile strength and tensile elongation were measured according to ASTM D638. Each measurement result is shown in Table 1 below.

Comparative Example 1-7

Comparative Example 1-7 was prepared by the same method as in Example 1 with the composition shown in Table 1 below, optionally using the component (C) or (D), or without using both (C) and (D) After the pellets were prepared, physical properties were measured in the same manner, and the results are shown in Table 1 together.

Comparative Example Example One 2 3 4 5 6 7 One 2 (A) 40 40 40 40 40 40 40 40 40 (B) 50 50 50 50 50 50 50 50 50 (C) 5 10 5 5 (D1) 5 10 5 (D2) 5 10 5 (E) One One One One One One One One One Impact Strength (Kgf-cm / cm) 15 9 11 26 15 20 3 35 40 Tensile Strength (Kgf / ㎠) 470 420 450 580 520 540 280 570 580 % Elongation 53 48 49 73 65 68 2.7 72 75

As shown in Table 1, in Examples 1 and 2 in which both the styrene copolymer (C) and the acrylic copolymer (D) were added, (C) or (D) was selectively added or not added. Compared with the comparative examples, it can be seen that the impact strength, tensile strength and elongation are all excellent.

 The present invention has the effect of increasing the compatibility between polyphenylene-based resins and polyamide-based resins, and providing a polyphenylene ether-based resin composition excellent in impact resistance.

Simple modifications and variations of the present invention can be readily used by those skilled in the art, and all such variations or modifications can be considered to be included within the scope of the present invention.

Claims (5)

(A) 5 to 95 parts by weight of polyphenylene ether resin; (B) 5-95 parts by weight of polyamide resin; Based on 100 parts by weight of basic resin (A) + (B) (C) 1 to 30 parts by weight of styrene copolymer resin; (D) 1 to 30 parts by weight of acrylate copolymer resin; And (E) 0.1-10 weight part of reactive monomers containing an unsaturated carboxylic acid or its anhydride group; Polyphenylene ether-based thermoplastic resin composition comprising a. The polyphenylene ether resin (A) according to claim 1, wherein the polyphenylene ether resin (A) is poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether , Poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly (2-methyl-6-propyl-1, 4-phenylene) ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6- Copolymer of dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl-1,4-phenylene) ether, and poly (2,6-dimethyl-1,4-phenylene) ether And a copolymer of poly (2,3,6-triethyl-1,4-phenylene) ether, wherein the polyamide resin (B) is polycaprolactam (nylon 6), poly ( 11-aminoundecanoic acid) (nylon 11), polylauryllactam (nylon 12), polyhexamethylene adipamide (nylon 6,6), polyhexaethylene azelamide (nylon 6,9), polyhexae One or more selected from the group consisting of styrene sebacamide (nylon 6,10), polyhexaethylene dodecanoodiamide (nylon 6,12), and copolymers thereof, wherein the styrene-based copolymer (C) is AB, ABA Or an ABC block or a radial block copolymer, the polyphenylene ether-based resin composition comprising a vinyl aromatic monomer and a block of hydrogenated, partially hydrogenated or unsaturated hydrogen diene. According to claim 1, The acrylate copolymer (D) is an ethylene / alkyl acrylate copolymer selected from the group consisting of ethylene, vinyl acetate, carbon monooxide, ethylene / methyl acrylic according to the type of alkyl group A polyphenylene ether resin composition comprising a rate (EMA), an ethylene / ethyl acrylate (EEA) or an ethylene / butyl acrylate (EBA) copolymer. The reactive monomer (E) having an unsaturated carboxylic acid or anhydride group thereof is one from the group consisting of citric anhydride, maleic anhydride, maleic acid, itaconic anhydride, fumaric acid, acrylic acid, and methacrylic acid esters. The polyphenylene ether-based resin composition is selected above. Molded article processed with the resin composition of any one of Claims 1-3.