KR0149250B1 - Polyphenylene ether thermoplastic composition & its preparation method - Google Patents

Abstract

The polyphenylene ether-based thermoplastic resin composition of the present invention is (A) 5 to 95 parts by weight of a polyphenylene ether resin or a mixture of a vinyl aromatic polymer and a polyphenylene ether resin: (B) 1 to 80 parts by weight of a rubbery polymer 1 to 50 parts by weight of a graft copolymer obtained by graft polymerization of 20 to 99 parts by weight of an aromatic vinyl monomer; (C) 0.01 to 2 parts by weight of organic peroxide based on the component (B); (D) 0.01 to 10 parts by weight of a reactive monomer having an unsaturated carboxylic acid or an anhydride group thereof relative to component (B); (E) 5 to 95 parts by weight of polyamide resin; And (F) 0 to 40 parts by weight of a styrene impact modifier, wherein the components (A) and (F) are introduced into the first region using an extruder divided into three or more regions, and the component ( And B), (C) and (D), and the component (E) in the third region.

Description

[Name of invention]

Polyphenylene ether-based thermoplastic resin composition and its manufacturing method

Detailed description of the invention

[Field of Invention]

The present invention relates to a polyphenylene ether-based thermoplastic resin composition.

More specifically, the present invention relates to a polyphenylene ether thermoplastic resin composition based on polyphenylene ether and polyamide and comprising a rubber graft copolymer, an organic peroxide, a reactive monomer, and a styrene impact modifier, and a method of manufacturing the same. will be.

[Background of invention]

Polyphenylene ether resins or mixtures of polyphenylene ether resins and polystyrene resins are widely used in various fields, such as automotive parts, electrical and electronic parts, because of their excellent mechanical and electrical properties in a high temperature range. However, polyphenylene ether resin has a disadvantage in that solvent resistance and impact resistance are not good and workability is quite bad.

In addition, polyamide resins are also widely used as general purpose engineering plastics, but their use is limited as engineering plastics because of their excellent chemical resistance and excellent workability while their poor heat resistance and impact resistance. Therefore, a lot of researches have been conducted to complement the drawbacks of these two resins.

U.S. Patent No. 3,379,792 discloses resin compositions in which 0.1-25% by weight of polyamide resin is contained in polyphenylene ether resin. However, in this case, when the content of the polyamide resin is 20% by weight or more, phase compatibility occurs because of poor compatibility between the polyphenylene ether and the polyamide, and as a result, the physical properties of the molded article are significantly reduced.

U.S. Patent 4,315,086 discloses 100 parts by weight of a resin composition consisting of 5-95% by weight of polyphenylene ether and 95-5% by weight of polyamide (A) liquid diene polymer, (B) epoxy compound and (C) ( a resin composition containing 0.01-30 parts by weight of a compound selected from the group consisting of a) an ethylene carbon-carbon double bond or a triple bond and (b) a compound having a carboxylic acid, an acid anhydride, an acid amide, or a hydroxyl group It is starting.

European Patent No. 046,040 discloses an air structure comprising (a) a polyphenylene ether resin, (b) an imide compound unit of a vinyl aromatic compound and an α, β-unsaturated dicarboxylic acid to improve heat resistance, oil resistance, and impact resistance. A resin composition consisting of coalesce, and (c) polyamide, and optionally (d) impact reinforcing material, is disclosed.

In the PCT patent application PCD / US86 / 01511, in the absence of a free group initiator, at least one carbon-carbon double or triple bond and at least one carboxylic acid, acid anhydride, acidimide, imide, ester in the macromolecule A method for modifying polyphenylene ether is disclosed by mixing at least one functional compound having an amino or hydroxyl group with a liquid polyphenylene ether.

U.S. Patent No. 4,943,399 discloses (a ₁ ) polyphenylene ether, (a ₂ ) vinylaromatic polymer, (a ₃ ) (a ₃₁ ) α, β-unsaturated carboxylic acid or derivatives thereof in the first region of the extruder ( a ₃₂ ) at least one monomer selected from a monomer having an amide group and a polymerizable double bond and (a ₃₃ ) a monomer having a lactam group and a polymerizable double bond, (a ₄ ) a graft monomer and (a ₅ ) a free radical initiator Into the modified polyphenylene ether (A) obtained by the reaction, polyamide (B), unmodified polyphenylene ether (C), and vinyl aromatic polymer (D) are added to the second region, and third Disclosed is a method of continuously producing a polyphenylene ether and a polyamide-based thermoplastic resin composition by adding an impact modifier (E) and other additives (F) to a region.

However, resin compositions containing polyphenylene ether modified with unsaturated carboxylic acids or anhydrides thereof, such as maleic anhydride, used in the above-listed patents contain the drawback that the natural color of the resin is severely discolored during the extrusion process.

Polyphenylene ether resins, modified vinyl aromatic graft copolymers, polyamide resins and styrene-based impacts having improved compatibility with polyphenylene ether resins and polyamide resins and excellent natural colors to alleviate the above drawbacks. An invention related to a thermoplastic resin composition made of a reinforcing material has been filed in Korean Patent Application No. 95-9731.

The present invention relates to a method for producing a novel polyphenylene ether-based thermoplastic resin composition that can eliminate the drawbacks of the above patent and to manufacture the resin composition of the Republic of Korea Patent Application No. 95-9731.

[Purpose of invention]

An object of the present invention is a resin composition comprising a polyphenylene ether resin and a polyamide, and comprising a rubber graft copolymer, an organic peroxide, a reactive monomer, and a styrene impact modifier, wherein the polyphenylene ether resin and a polyamide resin are used. It is to provide a method for producing a polyphenylene ether-based thermoplastic resin composition with improved compatibility with.

Another object of the present invention is to provide a method for producing a polyphenylene ether-based thermoplastic resin composition excellent in natural color, that is, the natural color of the resin does not significantly change during the extrusion process.

Another object of the present invention is to provide a method for producing a polyphenylene ether thermoplastic resin composition having good impact resistance, heat resistance, chemical resistance and workability.

[Summary of invention]

The polyphenylene ether-based thermoplastic resin composition of the present invention comprises (A) 5 to 95 parts by weight of a polyphenylene ether resin or a mixture of a vinyl aromatic polymer and a polyphenylene ether resin; (B) 1 to 50 parts by weight of a graft copolymer obtained by graft polymerization of 20 to 99 parts by weight of an aromatic vinyl monomer to 1 to 80 parts by weight of a rubbery polymer; (C) 0.01 to 2 parts by weight of organic peroxide based on the component (B); (D) 0.01 to 10 parts by weight of a reactive monomer having an unsaturated carboxylic acid or an anhydride group thereof relative to component (B); (E) 5 to 95 parts by weight of polyamide resin; And (F) 0 to 40 parts by weight of a styrene impact modifier, wherein the components (A) and (F) are introduced into the first region using an extruder divided into three or more regions, and the component ( And B), (C) and (D), and the component (E) in the third region.

Detailed Description of the Invention

(A) polyphenylene ether resin which is a component of the thermoplastic resin composition of this invention, (B) vinyl aromatic graft copolymer, (C) organic peroxide, (D) reactive monomer which has unsaturated carboxylic acid or its anhydride group, The polyamide (E) and the styrene-based impact modifier (F) will be described in detail below.

(A) polyphenylene ether resin

In the present invention, polyphenylene ether resin may be used alone or a mixture of polyphenylene ether resin and a vinyl aromatic polymer may be used.

Examples of polyphenylene ether resins include poly (2, 6-dimethyl-1, 4-phenylene) ether, poly (2, 6-diethyl-1, 4-phenylene) ether, poly (2, 6-di Propyl-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 ) Ether and copolymer of poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) ether and poly (2,3, Copolymers with 6-triethyl-1,4-phenylene) ether. Among them, a copolymer of poly (2, 6-dimethyl-1, 4-phenylene) ether and poly (2, 3, 6-trimethyl-1, 4-phenylene) ether, and poly (2, 6-dimethyl -1,4-phenylene) ether is preferred, and poly (2, 6-dimethyl-1, 4-phenylene) ether is more preferred.

The degree of polymerization of the polyphenylene ether is not particularly limited, but considering the thermal stability and workability of the resin composition, the intrinsic viscosity is preferably 0.2 to 0.8 dl / g when measured in a 25 ° C. chloroform solvent. The polyphenylene ethers may be used alone or in combination of two or more compounds in an appropriate ratio.

Polyphenylene ether resins have good compatibility with vinyl aromatic polymers. Therefore, also in this invention, the mixture of a polyphenylene ether resin and a vinyl aromatic polymer can be used. Vinyl aromatic polymers include polystyrene, high impact polystyrene, polychlorostyrene, poly alpha-methylstyrene, and poly t-butylstyrene, which may be used alone or in a mixture of two or more. Of these, polystyrene or high impact polystyrene is preferred. Although the molecular weight of a vinyl aromatic polymer is not specifically limited, either, In consideration of thermal stability and workability of a resin composition, it is preferable that weight average molecular weights are 20,000-500,000.

The polyphenylene ether resin or the mixture of the vinyl aromatic polymer and the polyphenylene ether resin is used in an amount of 5 to 95 parts by weight based on the total resin composition.

(B) vinyl aromatic graft copolymer

The vinyl aromatic graft copolymer used in the present invention is a copolymer obtained by grafting an aromatic vinyl monomer to a rubbery polymer. In the present invention, it is preferable that the aromatic vinyl monomer is 20 to 99% graft reaction with respect to the rubbery polymer. In the preparation of the rubbery polymer of the present invention, one or more rubbers selected from the group consisting of diene rubber, ethylene rubber and ternary copolymer rubber of ethylene / propylene / diene monomer may be used, and the average particle diameter of the rubber particles of the rubbery polymer 0.02-1.0 μ can be used, preferably 0.05-0.5 μ. If the average particle diameter of the rubber particles is 0.05 μ or less, it is difficult to prepare a vinyl aromatic graft copolymer, and if it is 0.5 μ or more, there is little effect of improving compatibility through proper morphological control.

Aromatic vinyl monomers include styrene, para t-butylstyrene, alpha-methylstyrene, beta-methyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, chlorostyrene, ethyl styrene, vinyl naphthalene, and divinyl. Benzene and the like, of which styrene and alpha-methylstyrene are preferred.

The method for preparing the vinyl aromatic graft copolymer is well known to those skilled in the art, and may be any of emulsion polymerization, suspension polymerization, solution polymerization, or bulk polymerization. In the presence of a rubbery polymer, it is preferable to add the aromatic vinyl monomer in the emulsion polymerization or bulk polymerization as a polymerization initiator.

The vinyl aromatic graft copolymer of the present invention is used 1 to 50 parts by weight based on the total resin composition, preferably 3 to 30 parts by weight. If the amount of the vinyl aromatic graft copolymer is 3 parts by weight or less, there is little effect of improving the compatibility of the resin composition of the present invention, and if it is 30 parts by weight or more, the heat resistance of the resin composition is lowered.

(C) organic peroxide

Organic peroxides used in the present invention include diisopropylbenzenehydroperoxide, di-t-butylperoxide, p-ethane hydroperoxide, t-butyl cumyl peroxide, dicumyl peroxide, 2,5- Dimethyl 2, 5-di (t-butylperoxy) hexane, di-t-butyldiperoxyphthalate, succinic acid hydroxide, t-butyldiperoxybenzoate, t-butylperoxy maleic acid, t -Butyl peroxyisopropyl carbonate, methyl ethyl ketone peroxide, cyclohexanone peroxide, etc. may be used, and these may be used alone or in combination of two or more, and dicumyl in consideration of double reactivity and processability Peroxides are preferred.

The organic peroxide may be used in an amount of up to 2 parts by weight based on 100 parts by weight of the vinyl aromatic graft copolymer of the component (B), and when mixed therein, thermal stability and physical properties of the final resin composition may be due to decomposition of the resin. Significantly lowered.

(D) reactive monomer

Examples of the reactive monomer having an unsaturated carboxylic acid or anhydride group used in the present invention include maleic anhydride, maleic acid, itaconic anhydride, fumaric acid, acrylic acid, and teracrylic acid esters, of which maleic anhydride is preferably used. Do. The amount of the reactive monomer having an alpha or beta unsaturated carboxylic acid having a carboxylic acid or anhydrous acid is preferably 0.01 to 10 parts by weight based on 100 parts by weight of the vinyl aromatic graft copolymer of the component (B) of the present invention. Preferably 0.1 to 7 parts by weight is good. When the added amount is less than 0.1 part by weight based on 100 parts by weight of the vinyl aromatic graft copolymer (B), there is little effect of improving the compatibility of the final resin composition. There is a disadvantage that the physical properties of the composition is sharply lowered.

(E) polyamide resin

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

However, considering the mechanical properties and heat resistance of the resin composition, it is preferable to use a polyamide resin having a melting point of 200 ° C. or higher and a relative viscosity (measured at 25 ° C. by adding 1% by weight of polyamide resin to m-cresol). good.

(F) Styrenic impact modifiers

Styrene-based impact modifiers of the component (F) of the present invention are derived from vinyl aromatic monomers, and may be diblock or radial tereblock copolymers in the form of AB or ABA.

A diblock or radial tereblock copolymer in the form of AB or ABA is a copolymer consisting of a vinyl aromatic monomer and a block of hydrogenated, partially hydrogenated or non-hydrogenated unsaturated diene. Examples of block copolymers of AB diblock type Polystyrene-polybutadiene (SBR), polystyrene-polyisoprene, polyalphamethylstyrene-polybutadiene copolymers and hydrogenated forms thereof. Such AB diblock type copolymers are widely known commercially, and are representative of SOLPRENE and K-RESIN of PHILLIPS and KRATON D and KRATON G of SHELL. Examples of ABA terblock type block copolymers include polystyrene-polybutadiene-polystyrene (SBS), polystyrene-polyisoprene-polystyrene (SIS), polyalphamethylstyrene-polybutadiene-polyalphamethylstyrene, polyalphametalstyrene-poly Copolymers such as isoprene-polyalphamethylstyrene and copolymers in hydrogenated form thereof. Such ABA tereblock type copolymers are also widely known commercially, and examples thereof include CARIFLEX, KRATON D and KRATON G and KEPRAY SEPTON.

The method for producing the polyphenylene ether thermoplastic resin composition of the present invention is as follows.

In the production of the thermoplastic resin composition of the present invention, a single screw or twin screw extruder may be used, and in consideration of the self-pulsing characteristics and the distribution of residence time in the extruder, the co-rotating Preference is given to using twin screw extruders.

The extruder used in the present invention has a jacket (JACKET) to enable temperature control on each barrel (BARREL). There are no particular restrictions on the screw design of the extruder, and CONVEYOR ELEMENT, KNEADING ELEMENT and MIXING ELEMENT can be used and reverse direction to control the residence time and kneading degree in the extruder A BACKWARD-CONVEYING ELEMENT can be used. The extruder used in the present invention is divided into three zones or more.

In the manufacturing process of the polyphenylene ether resin composition of the present invention, first, the polyphenylene ether resin (A) and the styrene impact modifier (F) as constituents are added to the first region of the extruder, and the polyphenylene ether mixture To form. The length of the first region of the extruder is preferably 3-30 D, more preferably 5-20 D (D represents the diameter of the extruder screw).

In order to facilitate supply of the resin, it is preferable to attach a conveying element to the first region of the extruder, and then a kneading element and a mixing element may be attached thereto. One or more back-conveying elements may be attached to the end of the first region of the extruder to control the residence time. The marine temperature of the first zone of the extruder is preferably 240-330 ° C.

In the manufacturing process of this invention, a component vinyl aromatic graft copolymer (B), an organic peroxide (C), and a reactive monomer (D) are thrown into the 2nd area | region of an extruder. In order to be blended with the polyphenylene ether-based mixture prepared in the first zone of the extruder in the required composition, modified graphs reacted in the molten state by using an auxiliary extruder composed of a barrel (BARREL) which can be weighed at an appropriate ratio and temperature controlled It is fed to the inlet of the second zone of the extruder in the state of the copolymer. At this time, a single screw or twin screw extruder may be used as the auxiliary extruder, the diameter of the extruder screw is preferably smaller than the diameter of the main extruder screw, the length of the extruder is preferably 5-40 D, more preferably 10-35 D. Do. If the length is less than 10 D, the reaction between the graft copolymer and the reactive monomer does not proceed sufficiently, so that there is little effect of improving the compatibility of the resin composition of the present invention. Appearance color and physical properties may be reduced. The barrel temperature of the co-extruder is preferably 150-230 ° C.

In the manufacturing process of the present invention, the length of the second region of the extruder in which the polyphenylene ether-based mixture introduced in the first region of the extruder and the modified vinyl aromatic graft copolymer supplied from the auxiliary extruder is kneaded is 5-30 D. It is preferable and it is more preferable that it is 10-20D. KNEADING ELEMENT and MIXING ELEMENT can be attached to the second area of the extruder, and one or more back-conveying elements can be attached to the end to adjust the residence time. Good to do. The arrangement temperature of the second region of the main extruder is preferably used in the same range as the barrel temperature of the first region. The residence time in this region is preferably 0.1-10 minutes, more preferably in the range of 0.3-5 minutes.

In the production process of the present invention, the component polyamide resin (E) is introduced at the inlet of the third region of the extruder. In order to blend with the mixture extruded in the second zone of the extruder and the required composition, they are metered at an appropriate ratio and fed to the inlet of the third zone of the extruder using a SIDE-FEEDER. At this time, the polyamide resin (E) may be supplied in the form of pellets, or may be supplied in a molten state using a co-extruder.

In the manufacturing process of the present invention, the mixture of the polyphenylene ether resin and the modified graft copolymer extruded in the second zone of the extruder and the polyamide resin supplied from the auxiliary feeder are kneaded to have a length of the third zone of the extruder 5 It is preferable that it is -30D, and it is more preferable that it is 7-25D. KNEADING ELEMENT, MIXING ELEMENT, and BACKWARD-CONVEYING ELEMENT can also be used in the third zone of the extruder, and a vent zone can be installed to remove volatiles. In order to effectively remove volatiles, it is desirable to introduce a vacuum device. The barrel temperature of the third zone of the main extruder is also preferably used in the same range as the barrel temperature of the first and second zones.

The thermoplastic resin composition of the present invention may be used according to the use by adding other additives, and specifically, when an inorganic filler such as glass fiber, carbon fiber, talc, silica, mica or alumina is added, Properties such as strength and heat distortion temperature (HDT) can be improved, which can be supplied with the resins of components (A)-(F), but preferably after the third zone of the extruder. One or more extruder zones (fourth zones) may be additionally provided and fed through the auxiliary feeder, and the size and design of these zones should be based on the second or third zone of the extruder.

The thermoplastic resin composition of the present invention can be prepared using other ultraviolet absorbers, antioxidants, flame retardants, lubricants, dyes and pigments.

The following examples of the present invention will be more specific, and the following examples are only specific examples of the present invention and are not intended to limit or limit the protection scope of the present invention.

EXAMPLE

(A) polyphenylene ether (PPE) resin

In the embodiment of the present invention, the polyphenylene ether resin used is PPE (A-1) of Asahi Kasei Co., Ltd., Japan, and polystyrene is HR-2390 (A-2) which is a product of Cheil Industries Co., Ltd. of Korea.

(B) graft copolymer

In the embodiment of the present invention, a vinyl aromatic graft copolymer (B) was prepared and used as follows.

(B-1): 300 g of polybutadiene latex (based on solids) and 700 g of styrene having a rubber particle diameter of 0.1 μ was placed in a reactor, and 5 g of potassium persulfate and 5 g of sodium moleate were added to the mixture to emulsify and polymerize it. The graft copolymer (B-1) is obtained.

(B-2) As a product of Cheil Industries, Korea, HG-1760 (high impact high gloss polystyrene) having an average particle diameter of 0.38 μ was used.

(C) organic peroxide

The organic peroxide used in the examples of the present invention is dicumylperoxide from Aldrich, USA.

(D) reactive monomer

The reactive monomer used in the Example of this invention is maleic anhydride of a Japanese oil and fat company.

(E) polyamide resin

In the examples of the present invention, two kinds of polyamide resins (E-1) and (E-2) were used. (E-1) is nylon 6 (trade name; KN-171) of KOLON Co. Ltd. of Korea, and (E-2) is nylon 66 (trade name; 21SP) manufactured by Monsanto, USA.

(F) Styrenic impact modifiers

Styrene-based impact reinforcing material used in the present invention is KRATON G 1651 of Shell, USA.

Example 1-7

In Example 1-7 of the present invention, a resin composition was prepared using a twin screw extruder having φ = 40 mm divided into three zones.

The length of the first zone of the extruder was 12 D, and the screw under the feeder for feeding the weighed solid resin in the weighing scale was designed as a CONVEYING ELEMENT. The length of the feed screw element was 3D and the temperature was kept below 30 ° C. The screw portion 3 D was then heated to 240 ° C. and the remaining screw portion 6 D was kept at 280 ° C. A kneading screw element was designed in the middle of the first zone of the extruder and a reverse feed element was introduced at the end.

The length of the second region of the extruder was 9 D, the front part was equipped with a device for supplying the resin, and the rest part was sealed. Components (B), (C) and (D) were fed to the feeder via a coextruder and the temperature of the screw was maintained at 280 ° C. In the middle was a mixing screw element.

As a coextruder, a twin screw extruder with a screw diameter of 30 mm and a length of 17 D was used, and the extruder barrel temperature was heated to 200 ° C. At the front of the sub-extruder, the material to be extruded was metered in the weighing scale, and the end was connected to the resin feeder in front of the second zone of the main extruder.

The length of the third zone of the extruder was 15 D, the front part was equipped with a device for supplying the resin, the vacuum vent device for removing volatiles in the middle part, and all the rest were sealed. The polyamide resin, component (E), was fed in the form of pellets through the auxiliary feeder in front of the third zone of the extruder and the temperature of the screw was maintained at 280 ° C. A nissing screw element was installed in front of the intermediate venting device, followed by a mixing screw element.

In Example 1-7, the resin composition was prepared in the form of pellets by varying the type and content of each component by the composition and processing method as shown in Table 1, and the pellet was dried at 80 ° C. for 6 hours and then in a 6 Oz injection machine. Molded specimens were prepared by injection molding at a molding temperature of 230-320 ° C. and a mold temperature of 60-90 ° C. Specimens prepared according to Examples 1-7 were obtained with Izod impact strength (1/4, 1/8 notch) in accordance with ASTM D 256, tensile strength and tensile elongation in accordance with ASTM D 638, and heat deflection temperature in accordance with ASTM D 648. 1/4, 4.5 kg load), and whiteness was measured with a colorimeter. The measurement results are shown in Table 2.

As can be seen from the above results, when the content of maleic anhydride is 0.1 parts or less or 7 parts or more with respect to the graft copolymer, physical properties may be deteriorated.

Comparative Example 3A, 4A, 7A

Comparative Examples 3A, 4A and 7A are comparative examples for comparison with Examples 3, 4 and 7 of the present invention and include components (A), (B), (C), (D), (E) and (F) was weighed, mixed and extruded at the same time.

Comparative Example 3B, 4B, 7B

Comparative Examples 3B, 4B and 7B are also comparative examples for comparison with Examples 3, 4 and 7 of the present invention, wherein component (A) is introduced in the first zone of the extruder, and (B), (C) And (D) were added in the second region, and (E) and (F) were simultaneously added in the third region.

Comparative Example 3C, 4C, 7C

Comparative Examples 3C, 4C and 7C are also comparative examples for comparison with Examples 3, 4 and 7, after the components (B), (C) and (D) have been extruded in advance and prepared into pellets. The components (A) and (F) are mixed and introduced into the first zone of the extruder, and (E) is added again into the third zone of the extruder.

At this time, the extrusion, injection and physical property measurement methods were the same as in Example 1-7, and 0.2 parts by weight of antioxidant and thermal stabilizer were added. The measurement results are shown in Table 3.

As shown in the results of Table 3, when the components are simultaneously extruded, the overall physical properties are severely deteriorated (Comparative Examples 3A, 4A, and 7A), and when the impact modifier (F) is added in the third region as in the polyamide (E) However, the impact strength and the heat resistance are severely reduced (Comparative Examples 3B, 4B, and 7B). Also, when the pellets of vinyl aromatic graft copolymer modified with maleic anhydride are generally used, the overall physical properties are generally excellent. It can be seen that the natural color is reduced compared to using the modified vinyl aromatic graft copolymer in the molten state at the same time (Comparative Examples 3C, 4C, 7C).

Claims (14)

(A) 5 to 95 parts by weight of polyphenylene ether resin: (B) 1 to 50 parts by weight of a graft copolymer obtained by graft polymerization of 20 to 99 parts by weight of an aromatic vinyl monomer to 1 to 80 parts by weight of a rubbery polymer; C) 0.01 to 2 parts by weight of an organic peroxide relative to the component (B); (D) 0.01 to 10 parts by weight of a reactive monomer having an unsaturated carboxylic acid or an anhydride group relative to the component (B); (E) polyamide resin 5 to 95 parts by weight; And (F) 0 to 40 parts by weight of a styrene-based impact modifier; In the production of the polyphenylene ether-based thermoplastic resin composition comprising the components (A) and (F) to the first region of the extruder having a barrel temperature of 240-330 ° C and a length of 3-30 D step; Injecting the components (B), (C) and (D) into a second region of the extruder having a length of 5-30 D without cooling the components in the first region; And injecting the component (E) into the third region of the extruder having a length of 5-30 D while the components in the second region are not cooled; Method for producing a polyphenylene ether-based thermoplastic resin composition, characterized in that consisting of. The method for producing a polyphenylene ether-based thermoplastic resin composition according to claim 1, wherein the polyphenylene ether resin further comprises a vinyl aromatic polymer. The polyphenylene ether resin according to claim 1, wherein the polyphenylene ether resin is poly (2, 6-dimethyl-1, 4-phenylene) ether, poly (2, 6-diethyl-1, 4-phenylene) ether, (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- Copolymer with 1,4-phenylene) ether, poly (2, 3, 6-trimethyl-1, 4-phenylene) ether and poly (2, 6-dimethyl-1, 4-phenylene) ether with poly A method for producing a polyphenylene ether-based thermoplastic resin composition, characterized in that it is selected from the group consisting of copolymers with (2, 3, 6-triethyl-1, 4-phenylene) ether. The polyphenylene ether system according to claim 2, wherein the vinyl aromatic polymer is at least one selected from the group consisting of polystyrene, high impact polystyrene, polychlorostyrene, poly alpha-methylstyrene, and poly t-butylstyrene. Method for producing a thermoplastic resin composition. The polyphenylene ether-based thermoplastic resin according to claim 1, wherein the rubbery polymer is at least one selected from the group consisting of diene rubber, ethylene rubber, and ternary copolymer rubber of ethylene / propylene / diene monomer. Method of Preparation of the Composition. The method for producing a polyphenylene ether-based thermoplastic resin composition according to claim 5, wherein the rubbery polymer has an average particle diameter of 0.02-1 micron. The method of claim 1, wherein the aromatic vinyl monomer is styrene, para t-butylstyrene, alpha-methylstyrene, beta-methyl styrene, vinyl xylene, monochlorostyrene, dichlorostyrene, dibromostyrene, chlorostyrene, ethyl styrene At least one selected from the group consisting of vinyl naphthalene and divinylbenzene. 8. The reactive monomer having an unsaturated carboxylic acid or anhydride group thereof is at least one selected from the group consisting of maleic anhydride, maleic acid, itaconic anhydride, fumaric acid, acrylic acid, and methacrylic acid ester. A method for producing a polyphenylene ether-based thermoplastic resin composition. The method of claim 8, wherein the organic peroxide is diisopropylbenzenehydroperoxide, di-t-butyl peroxide, p-ethane hydroperoxide, t-butyl cumyl peroxide, dicumyl peroxide, 2, 5 -Dimethyl 2,5-di (t-butylperoxy) hexane, di-t-butyldiperoxyphthalate, succinic acid peroxide, t-butyldiperoxymentoate, t-butylperoxymaleate, t-butylper A method for producing a polyphenylene ether-based thermoplastic resin composition, characterized in that at least one selected from the group consisting of oxyisopropyl capcarbonate, methyl ethyl ketone peroxide, and cyclohexanone peroxide. The method for producing a polyphenylene ether-based thermoplastic resin composition according to claim 1, wherein the step of introducing into the second region is performed by a secondary extruder attached to the main extruder. The polyphenylene ether according to claim 10, wherein the components (B), (C) and (D) introduced into the second region are introduced into the main extruder after reacting in a molten state in the auxiliary extruder. Method for producing a thermoplastic resin composition. The method of claim 1, wherein the method further comprises the step of introducing other additives, such as glass fibers, carbon fibers, talc, silica, mica, alumina, etc., through a fourth continuous region behind the third region of the extruder. The manufacturing method of the polyphenylene ether-type thermoplastic resin composition made into. The method for producing a polyphenylene ether-based thermoplastic resin composition according to claim 1, wherein the residence time in the second region is 0.1 to 10 minutes. A polyphenylene ether-based thermoplastic resin composition prepared according to any one of claims 1 to 13.