JP5196630B2 - Process for producing polyphenylene ether resin composition - Google Patents

Description

  The present invention relates to a method for producing a polyphenylene ether-based resin composition excellent in heat aging resistance.

The polyphenylene ether composition has arbitrary heat resistance depending on the mixing ratio of polyphenylene ether and polystyrene. It has excellent properties such as insulation, dimensional stability, impact resistance, acid resistance, alkali resistance, low water absorption, and low specific gravity. In addition, it is flame retardant with phosphorus compounds and silicone compounds, and it is not necessary to use halogenated compounds and antimony trioxide, which are said to be harmful. . Because of these excellent characteristics, they are used in many applications. Examples include electrical / electronic parts, office equipment parts, automotive parts, various exterior materials, and industrial products.
However, very high heat resistance and heat aging characteristics (characteristics that maintain performance when exposed to high temperatures for long periods of time) Electrical and electronic internal parts applications that require flame retardancy, automotive parts applications In particular, sufficient performance has not been obtained as a material such as a deflection yoke for TV internal parts and a junction box for solar cells.

  In order to obtain a material having particularly high heat resistance among polyphenylene ether resin compositions, it is necessary to increase the amount of polyphenylene ether, but when polyphenylene ether powder is melt-kneaded using an extruder. A very high shear heat generation is generated and the temperature of the polyphenylene ether resin composition is increased. It has been desired to suppress this thermal degradation and improve the impact resistance and heat aging characteristics.

  Various techniques have been developed in the past to improve the impact resistance of polyphenylene ether compositions. Generally, high impact polystyrene, rubber component addition, etc., styrene-butadiene-styrene block copolymer and styrene-isoprene-styrene block copolymer are typical, but these are double in the molecule. It has bonds and has the disadvantages of low heat resistance, chemical resistance, and weather resistance.

  (Patent Document 1) discloses a technique for improving heat-resistant aging characteristics by using a hydrogenated styrene-butadiene-styrene block copolymer without using polystyrene. Polyphenylene ether having high heat resistance is disclosed. Since the detailed definition regarding the manufacturing method which is very important for obtaining the performance of the resin composition is not made, sufficient performance cannot be obtained.

  (Patent Document 2) discloses a composition and production technique using a hydrogenated styrene-butadiene-styrene block copolymer in order to improve impact resistance and flame retardancy, but a production method Therefore, it is not sufficient for improving the impact resistance and the heat aging characteristics by suppressing the shear heat generation during the melt kneading of the polyphenylene ether powder.

  Also, when powder raw material such as polyphenylene ether powder is continuously supplied to an extruder or the like for a long time and melt-kneaded, it is usually supplied to the extruder in large quantities due to the bulkiness of the powder. It is difficult. In addition, since the volatile components and moisture contained in these powder raw materials become a large amount of gas and water vapor by melt kneading in the extruder, the supply of the powder raw material to the extruder by back feed to the raw material supply port In addition, it becomes an incentive for strand take-off due to unstable discharge of the extruded resin, strand breakage, etc., and during the extrusion, the volatile components and moisture that have been back-fed back to the raw material supply port and moisture adhering to the raw material are fixed to the extruder. Mass production and production stability were not sufficient, such as forming a raw material lump near the raw material supply port and closing the raw material supply port, making it difficult to continue the extrusion operation.

(Patent Document 3) discloses a resin composition using a polyphenylene ether powder in a resin composition in which powder supply to an extruder is made smooth by a specific powder supply equipment arrangement and specific extrusion conditions. A method for improving product production stability is disclosed. However, this shows a method for improving productivity by dividing a resin composition mainly composed of polyphenylene ether powder, polystyrene resin and solid flame retardant into two steps.
Also, (Patent Document 4) discloses a method for producing a resin composition using polyphenylene ether powder. However, this is a method for improving the impact resistance of a resin composition mainly containing polyphenylene ether powder and inorganic filler powder. To improve high heat resistance, heat aging characteristics, flame retardancy, etc. It was not enough.
JP-A-9-227774 Japanese Patent No. 3735966 JP 2004-137450 A JP 2006-306061 A

  An object of this invention is to provide the polyphenylene ether resin composition excellent in heat-aging property, and its manufacturing method.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a resin composition containing polyphenylene ether powder, a styrene resin, and a hydrogenated block copolymer is melt-kneaded using an extruder. In addition, the present inventors have found that the object can be achieved by providing 45 to 75% as an unmelted mixing zone from the upstream side of the extruder and providing a 5 to 30% melt kneading zone after the unmelted mixing zone. It was.

That is, the present invention
[1] 60-98 parts by mass of (A) polyphenylene ether powder, (B) 1-25 parts by mass of styrene resin, (C) 1-20 parts by mass of hydrogenated block copolymer, and (A), (B ), (D) a resin composition containing 3 to 30 parts by mass of a phosphoric ester compound with respect to 100 parts by mass of the component, and the resin composition is melt-kneaded using an extruder when the barrel entire length of the extruder is 100% of 45 to 75% from the upstream side, as the non-melt mixing zone, 5-30% of the barrel full length and melt-kneading zone after the non-melt mixing zone ,
After (A) polyphenylene ether powder, (B) styrene resin, and (C) hydrogenated block copolymer are supplied from the first raw material supply port on the upstream side of the extruder, (D) phosphate ester compound is added. The manufacturing method of the polyphenylene ether-type resin composition supplied from the 2nd raw material supply port in the said unmelting mixing zone .
[ 2 ] The method for producing a polyphenylene ether-based resin composition as described in 1 above, wherein the barrel temperature of the unmelted mixing zone is set to 0 to 35% from the upstream side of the extruder to 200 ° C. or lower.
[ 3 ] The method for producing a polyphenylene ether-based resin composition as described in 1 or 2 above, wherein the screw speed of the extruder is 600 to 150 rpm.
[ 4 ] The method for producing a polyphenylene ether-based resin composition according to any one of the above items 1 to 3 , wherein the temperature of the resin composition extruded from the die outlet is 300 to 380 ° C.
[ 5 ] (B) The polyphenylene ether-based resin composition as described in any one of 1 to 4 above, wherein the styrene-based resin comprises polystyrene and rubber-reinforced polystyrene, and the rubber-reinforced polystyrene is 5 parts by weight or less. Manufacturing method.
[6] (D) phosphoric ester compound, described in any one of 1-5, which is a condensed phosphoric acid ester compounds represented by the following general formula (I) or formula (II) Of producing a polyphenylene ether-based resin composition.

（一般式（Ｉ）、（ＩＩ）中、Ｑ１、Ｑ２、Ｑ３、Ｑ４は、各々置換基であって各々独立に炭素数１から６のアルキル基を表し、Ｒ１、Ｒ２は各々置換基であってメチル基を表し、Ｒ３、Ｒ４は各々独立に水素原子またはメチル基を表す。ｎは１以上の平均値を有し、ｎ１、ｎ２は各々独立に０から２の整数を示し、ｍ１、ｍ２、ｍ３、ｍ４は各々独立に０から３の整数を示す。）
［７］（Ｃ）水添ブロック共重合体の数平均分子量が１５０，０００〜３５０，０００であることを特徴とする前記１〜６いずれか１項に記載のポリフェニレンエーテル系樹脂組成物の製造方法。
［８］（Ａ）ポリフェニレンエーテル粉体（Ｂ）スチレン系樹脂（Ｃ）水添ブロック共重合体の合計１００質量部に対して、（Ｅ）ポリオレフィンを０．５〜５質量部含有することを特徴とする前記１〜７のいずれか１項に記載のポリフェニレンエーテル系樹脂組成物の製造方法。
［９］ １５０℃、２００時間エージング後のＩＺＯＤ保持率が６５％以上であることを特徴とする前記１〜８のいずれか１項に記載の製造方法から得られるポリフェニレンエーテル系樹脂組成物。
［１０］前記１記載の製造方法より得られた樹脂組成物から成形されたテレビ内部部品の偏向ヨーク。

(In the general formulas (I) and (II), Q1, Q2, Q3 and Q4 are each a substituent and each independently represents an alkyl group having 1 to 6 carbon atoms, and R1 and R2 are each a substituent. R3 and R4 each independently represents a hydrogen atom or a methyl group, n has an average value of 1 or more, n1 and n2 each independently represents an integer of 0 to 2, m1, m2 , M3 and m4 each independently represents an integer of 0 to 3.)
[ 7 ] The production of the polyphenylene ether-based resin composition as described in any one of 1 to 6 above, wherein the number average molecular weight of the (C) hydrogenated block copolymer is from 150,000 to 350,000. Method.
[ 8 ] (A) Polyphenylene ether powder (B) Styrenic resin (C) 0.5 to 5 parts by mass of (E) polyolefin is contained relative to 100 parts by mass of the hydrogenated block copolymer. 8. The method for producing a polyphenylene ether-based resin composition according to any one of 1 to 7 above .
[ 9 ] The polyphenylene ether-based resin composition obtained from the production method according to any one of 1 to 8 , wherein the IZOD retention after aging at 150 ° C. for 200 hours is 65% or more.
[10] The 1 TV internal components of the deflection yoke which is molded from the resulting resin composition from production method according.

  The present invention makes it possible to provide a polyphenylene ether resin composition excellent in heat aging resistance and a method for producing the same.

  The present invention will be specifically described below.

  The (A) polyphenylene ether powder used in the present invention is a homopolymer or copolymer having a repeating unit represented by the following general formula (III) and / or general formula (IV).

（一般式（ＩＩＩ）、（ＩＶ）中、Ｒ１、Ｒ２、Ｒ３、Ｒ４、Ｒ５、Ｒ６は各々独立に水素原子、炭素数１〜４のアルキル基、炭素数６〜９のアリール基またはハロゲン原子を表す。但し、Ｒ５、Ｒ６は同時に水素ではない。）
ポリフェニレンエーテルの単独重合体の代表例としては、ポリ（２，６−ジメチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−エチル−１４−フェニレン）エーテル、ポリ（２，６−ジエチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−ｎ−プロピル−１，４−フェニレン）エーテルポリ（２，６−ジ−ｎ−プロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ｎ−ブチル−１，４−フェニレン）エーテル、ポリ（２−エチル−６−イソプロピル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−ヒドロキシエチル−１，４−フェニレン）エーテル、ポリ（２−メチル−６−クロロエチル−１，４−フェニレン）エーテル等が挙げられる。

(In the general formulas (III) and (IV), R1, R2, R3, R4, R5, and R6 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group having 6 to 9 carbon atoms, or a halogen atom. (However, R5 and R6 are not hydrogen at the same time.)
Representative examples of polyphenylene ether homopolymers include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl-14-phenylene) ether, poly (2,6- Diethyl-1,4-phenylene) ether, poly (2-ethyl-6-n-propyl-1,4-phenylene) ether poly (2,6-di-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4) -Phenylene) ether, poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether, poly (2-methyl-6-chloroethyl-1,4-phenylene) Ether and the like.

The polyphenylene ether copolymer is a copolymer having a repeating unit represented by general formula (III) and / or general formula (IV) as a main repeating unit. Examples thereof include a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol, a copolymer of 2,6-dimethylphenol and o-cresol, or 2,6-dimethylphenol and Examples thereof include copolymers with 2,3,6-trimethylphenol and o-cresol.
Of the polyphenylene ethers, poly (2,6-dimethyl-1,4-phenylene) ether is preferred. 2- (dialkylaminomethyl) -6-methylphenylene ether unit and 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene described in Japanese Patent Publication No. 63-301222 Polyphenylene ether containing an ether unit or the like as a partial structure is particularly preferable. The reduced viscosity (unit dl / g, chloroform solution, 30 ° C. measurement) of polyphenylene ether is preferably in the range of 0.25 to 0.6, more preferably in the range of 0.35 to 0.55.

  In the present invention, a modified polyphenylene ether in which a part or all of the polyphenylene ether is modified with an unsaturated carboxylic acid or a derivative thereof can be used. This modified polyphenylene ether is disclosed in Japanese Patent Publication No. 2-276823 (US Pat. Nos. 5,159,027 and 35695), Japanese Patent Publication Nos. 63-108059 (US Pat. Nos. 5,214,109 and 5216089), and Japanese Patent Publications. 59-59724 and the like. The modified polyphenylene ether is produced, for example, by melting and kneading an unsaturated carboxylic acid or a derivative thereof with polyphenylene ether in the presence or absence of a radical initiator. Alternatively, it is produced by dissolving polyphenylene ether, an unsaturated carboxylic acid or a derivative thereof in an organic solvent in the presence or absence of a radical initiator and reacting in a solution.

Examples of unsaturated carboxylic acids or derivatives thereof include maleic acid, fumaric acid, itaconic acid, halogenated maleic acid, cis-4-cyclohexene 1,2-dicarboxylic acid, and endo-cis-bicyclo (2,2,1)- 5-heptene-2,3-dicarboxylic acid, etc., acid anhydrides, esters, amides, imides, etc. of these dicarboxylic acids, acrylic acid, methacrylic acid, etc., esters of these monocarboxylic acids, amides, etc. . Moreover, although it is saturated carboxylic acid, the compound which can thermally decompose itself at the reaction temperature at the time of manufacturing modified polyphenylene ether, and can become the derivative | guide_body used by this invention can also be used. Specific examples include malic acid and citric acid. These may be used alone or in combination of two or more. (A) The preferred particle size of the polyphenylene ether powder is an average particle size of 1-1000 μm, more preferably 10-700 μm, particularly preferably 100-500 μm. is there. From the viewpoint of handleability during processing, it is preferably 1 μm or more, and preferably 1000 μm or less in order to suppress the occurrence of melt-kneaded and unmelted material.

  (A) The content of the polyphenylene ether powder in the polyferene ether resin composition of the present invention needs to be in the range of 60 to 98 parts by mass. Preferably it is 70-95 mass parts. When the content of the polyphenylene ether powder is less than 60 parts by mass, the heat-resistant temperature becomes too low, and the heat-resistant aging characteristics are deteriorated. On the other hand, when the content of the polyphenylene ether powder exceeds 95 parts by mass, the melt viscosity at the time of extrusion kneading becomes too high, so that the torque of the extruder becomes too high and stable production cannot be achieved.

  (B) Styrenic resin refers to a polymer obtained by polymerizing a styrene compound or a styrene compound and a compound copolymerizable with the styrene compound in the presence or absence of a rubbery polymer. Specific examples of the styrenic compound include styrene, α-methylstyrene, 2,4-dimethylstyrene, monochlorostyrene, p-methylstyrene, p-tert-butylstyrene, ethylstyrene, and the most preferable is styrene. It is. Examples of the compound copolymerizable with the styrene compound include methacrylic acid esters such as methyl methacrylate and ethyl methacrylate; unsaturated nitrile compounds such as acrylonitrile and methacrylonitrile; and acid anhydrides such as maleic anhydride. And used with styrenic compounds. The amount of the copolymerizable compound used is preferably 20% by mass or less, more preferably 15% by mass or less, based on the total amount with the styrene compound.

  Examples of the rubbery polymer include conjugated diene rubbers, copolymers of conjugated dienes and aromatic vinyl compounds, and ethylene-propylene copolymer rubbers. Specifically, polybutadiene and styrene-butadiene copolymer are preferable. Further, as the rubber polymer, it is particularly preferable to use polybutadiene having a degree of unsaturation of 80 to 20% partially hydrogenated or containing 90% or more of 1,4-cis bonds. Specific examples of the styrene resin include polystyrene and rubber-reinforced polystyrene, styrene-acrylonitrile copolymer (AS resin), rubber-reinforced styrene-acrylonitrile copolymer (ABS resin), other styrene copolymers, and the like. It is done. Particularly preferred is a combination of polystyrene and rubber reinforced polystyrene using partially hydrogenated polybutadiene having a degree of unsaturation of 80-20%.

  The content of the styrene resin in the polyphenylene ether resin composition of the present invention is 1 to 25 parts by mass.

  In particular, in an internal part of a home appliance OA device that requires heat resistance, polystyrene and rubber-reinforced polystyrene are preferably in the range of 1 to 25 parts by mass. More preferably, it is 1-15 mass. In order to obtain further excellent heat aging resistance, the styrenic resin is most preferably polystyrene. When rubber-reinforced polystyrene is used, the amount is preferably 5 parts by mass or less, more preferably 2 parts by mass or less. When rubber-reinforced polystyrene is used, if the amount exceeds 5 parts by mass, the impact resistance increases, but the impact resistance after heat aging decreases greatly, and the impact resistance retention decreases significantly. is there.

In the present invention, the (C) hydrogenated block copolymer is a hydrogenated block copolymer of styrene and a diene compound. The hydrogenation rate of the unsaturated bond derived from the diene compound is preferably 60% or more, more preferably 80% or more, and still more preferably 95% or more. When the styrene block chain is represented by S and the diene compound block chain is represented by B, the structures are S-B-S, S-B-S-B, (S-B-) ₄ -Si, S-B-S-. B-S etc. The microstructure of the diene compound polymer block can be arbitrarily selected. Usually, the 1,2-vinyl bond is in the range of 2 to 60%, preferably 8 to 40%, based on the total bond of the diene compound polymer.

  (C) The range that the styrene polymer block of the hydrogenated block copolymer occupies in the entire copolymer is preferably 25 to 80% by mass, more preferably 30 to 50% by mass.

The (C) hydrogenated block copolymer used in the present invention preferably has at least one styrene block chain having a number average molecular weight of 15,000 or more. More preferably, it is 20,000 or more and 50,000 or less. More preferably, the number average molecular weight of all styrene block chains is 15,000 or more.
(C) The number average molecular weight of the hydrogenated block copolymer is preferably 80,000 or more, more preferably 150,000 or more and 400,000 or less.

  (C) Two or more hydrogenated block copolymers may be used in combination.

  (C) The content of the hydrogenated block copolymer in the polyphenylene ether-based resin composition of the present invention needs to be in the range of 1 to 20 parts by mass. More preferably, it is 3-10 mass parts. If the content of the hydrogenated block copolymer is less than 1 part by mass, sufficient impact strength cannot be obtained. On the other hand, when the amount exceeds 20 parts by mass, the impact resistance increases, but there is a problem that the reduction in impact resistance retention after heat aging becomes large.

  The (D) phosphate ester used in the present invention is added to improve flame retardancy, and any organic phosphate ester generally used as a flame retardant for polyphenylene ether should be used. Can do. A condensed phosphate ester represented by the following formula (I) or the following formula (II) is preferable. The condensed phosphate ester may be one type or two or more types.

（一般式（Ｉ）、（ＩＩ）中、Ｑ１、Ｑ２、Ｑ３、Ｑ４は、各々置換基であって各々独立に炭素数１から６のアルキル基を表し、Ｒ１、Ｒ２は各々メチル基を表し、Ｒ３、Ｒ４は各々独立に水素原子またはメチル基を表す。ｎは１以上の整数であり、ｎ１、ｎ２は各々独立に０から２の整数を示し、ｍ１、ｍ２、ｍ３、ｍ４は各々独立に０から３の整数を示す。）
上記式（Ｉ）および（ＩＩ）で示される縮合リン酸エステルは、それぞれの分子が、ｎは１以上の整数、好ましくは１から３の整数である。
この中で、好ましい縮合リン酸エステルは、式（Ｉ）におけるｍ１、ｍ２、ｍ３、ｍ４、ｎ１、ｎ２がゼロであって、Ｒ３、Ｒ４がメチル基である縮合リン酸エステル、および式（Ｉ）におけるＱ１、Ｑ２、Ｑ３、Ｑ４、Ｒ３、Ｒ４がメチル基であり、ｎ１、ｎ２がゼロでありｍ１、ｍ２、ｍ３、ｍ４が１から３の整数の縮合リン酸エステルであって、ｎの範囲は１から３、特にｎが１であるリン酸エステルを５０質量％以上含有するものが好ましい。これらの難燃剤は、一般に市販されており、例えば大八化学（株）の商品名ＣＲ−７４１、ＣＲ７３３Ｓ、ＰＸ−２００等を挙げることができる。

(In the general formulas (I) and (II), Q1, Q2, Q3 and Q4 are each a substituent and each independently represents an alkyl group having 1 to 6 carbon atoms, and R1 and R2 each represents a methyl group. , R3 and R4 each independently represents a hydrogen atom or a methyl group, n is an integer of 1 or more, n1 and n2 each independently represents an integer of 0 to 2, and m1, m2, m3 and m4 are each independently Represents an integer from 0 to 3.)
In the condensed phosphate esters represented by the above formulas (I) and (II), each molecule is such that n is an integer of 1 or more, preferably an integer of 1 to 3.
Among these, preferred condensed phosphate esters are those in which m1, m2, m3, m4, n1, and n2 in formula (I) are zero and R3 and R4 are methyl groups, and in formula (I) Q1, Q2, Q3, Q4, R3, R4 are methyl groups, n1, n2 are zero, and m1, m2, m3, m4 are integer condensed phosphate esters of 1 to 3, The range is preferably 1 to 3, particularly preferably 50% by mass or more of a phosphoric acid ester in which n is 1. These flame retardants are generally commercially available, and examples thereof include trade names CR-741, CR733S, and PX-200 from Daihachi Chemical Co., Ltd.

Bisphenol A bisdiphenyl phosphate and resorcin bisdikyryl phosphate are particularly preferred as phosphate esters. The addition amount of the phosphate ester varies depending on the required flame retardant level, but 3 to 30 parts by mass of the phosphate ester with respect to 100 parts by mass of the total amount of polyphenylene ether, styrene resin and hydrogenated block copolymer. It is preferable that it is a range, More preferably, it is the range of 5-25 mass parts.
If it is less than 3 parts by mass of phosphate ester, sufficient combustibility cannot be obtained. On the other hand, if it exceeds 30 parts by mass, flame retardancy can be obtained, but there is a problem that heat resistance is lowered.

In this invention, it is preferable to contain (E) polyolefin further. Examples of the (E) polyolefin used in the present invention include low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer or ethylene. -An acrylic ester copolymer etc. are mentioned. Among these, low density polyethylene and ethylene-propylene copolymer are preferable. The ethylene-propylene copolymer, ethylene-butene copolymer, ethylene-octene copolymer or ethylene-acrylic acid ester copolymer is generally an amorphous or low-crystalline copolymer. These copolymers may be copolymerized with other monomers as long as the performance is not affected. The component ratio of ethylene and propylene, butene or octene is not particularly specified, but the component of propylene, butene or octene is generally in the range of 5 to 50 mol%. Two or more of these polyolefins can be used in combination.
(E) The MFR of polyolefin is preferably 0.1 to 50 g / 10 min, more preferably 0.2 to 20 g / 10 min as measured at a cylinder temperature of 230 ° C. according to ASTM D-1238.
(E) The addition amount of polyolefin is preferably 0.5 to 5 parts by mass, more preferably 0.1 to 3 parts by mass with respect to 100 parts by mass of the total amount of polyphenylene ether, styrene resin and hydrogenated block copolymer. Parts, more preferably 0.5 to 2 parts by mass.

  In the resin composition of the present invention, an inorganic filler such as glass fiber, glass flake, kaolin clay, talc, or other fibrous reinforcing agent is blended to obtain a high strength material excellent in fluidity and heat resistance. Can do. In addition, in order to impart further characteristics to the resin composition of the present invention, other additives such as a plasticizer, an antioxidant, various stabilizers, and an antistatic agent are provided as long as the effects of the present invention are not impaired. , Mold release agents, dyes and pigments, or other resins can be added. In addition, conventionally known various flame retardants and flame retardant assistants, for example, hydroxides such as magnesium hydroxide and aluminum hydroxide containing crystal water, zinc borate compounds, zinc stannate compounds, silica, kaolin It is possible to further improve flame retardancy by adding inorganic silicon compounds such as clay and talc.

  In the production method of the present invention, when the barrel total length of the twin-screw extruder is 100%, 45 to 75% from the upstream side needs to be an unmelted mixing zone. The unmelted mixing zone of the present invention refers to a zone that suppresses the melting of the polyphenylene ether powder and conveys it to the downstream side while mixing with other raw materials in a state where the polyphenylene ether powder is not completely melted. . The range of a preferable unmelted mixing zone is 50 to 70%, more preferably 60 to 70%.

  From the viewpoint of maintaining the physical properties of the composition and production stability, the unmelted mixing zone needs to be 45% or more. In addition, in order to ensure sufficient melt-kneading of the composition, a vacuum degassing zone and an addition zone from the second supply port need to be 75% or less.

  The extrusion screw in the unmelted mixing zone uses a feed screw element such as a single positive screw element or a double positive screw element, so that it is difficult to share and it is necessary to have a screw configuration with good powder component conveyance efficiency. is there. In particular, from the viewpoint of improving the conveying efficiency of the powder component, the ratio of the screw element length (L) to the screw diameter (D) (L / D) is 1.0 to 3.0 straight screw element, It is preferable to use a positive screw element.

  It is necessary to provide a melt kneading zone for sufficiently kneading the polyphenylene ether powder and other raw materials after the unmelted mixing zone. The range of the melt-kneading zone needs to be 5 to 30% of the total barrel length. Preferably it is 8 to 20% of range.

  The melt-kneading zone is a kneading disc R (3-7 discs combined at a twist angle of 15-75 degrees as a screw element for kneading resin, L / D = 0.5-2.0 positive screw Screw element), kneading disc N (3-7 discs combined with 90 ° twist angle L / D = 0.5-2.0 neutral screw element), kneading disc L (3-7 discs) Are combined with a twist angle of 15 to 75 degrees, L / D = 0.5 to 1.0 reverse screw element), reverse screw (L / D = 0.5 to 1.0, two reverse screw screws) Element), SME screw (L / D = 0.5 to 1.5 screw element with notched positive screw screw to improve kneadability), ZME screw -A zone in which screw elements such as (L / D = 0.5 to 1.5 screw elements with a notch in a reverse screw screw to improve kneadability) are appropriately incorporated in the screw structure and kneaded sufficiently Say. The melt-kneading zone can be divided into two or more places as necessary. Even when two or more melt-kneading zones are provided, the total melt-kneading zone needs to be 5 to 30% of the total barrel length. The remaining screw elements other than the unmelted mixing zone and the melt-kneading zone are preferably feed screw elements such as L / D = 0.5-3.0 double threaded screw elements.

  It is preferable to provide a vacuum degassing zone for removing volatile components and decomposition products from the melted resin after the melt-kneading zone. It is preferable that the screw in the vacuum degassing zone has a screw structure in which a shear is difficult to be applied by using a feed screw element such as a double-threaded screw. It is preferable to provide a decompression vent port in the vacuum deaeration zone and depressurize more strongly than −600 mmHg. Two or more decompression vents may be installed. Furthermore, if necessary, a second supply port can be provided to add a flame retardant, impact modifier, additive, inorganic filler, and the like. It is preferable to use a feed screw element such as a double thread screw for the screw of the second supply port. When the decompression vent port and the second supply port are provided in the kneading zone, the raw material overflows from the open portion, which causes a problem that stable extrusion cannot be performed.

  In the screw configuration of the present application, the barrel temperature of the unmelted mixing zone is preferably set to 280 ° C. or lower. The barrel of the first supply port of the raw material is preferably water-cooled, and the first 30% of the barrel length is preferably 200 ° C. or less. The barrel set temperature from the melt-kneading zone to the extruder outlet is preferably set to 240 to 330 ° C. More preferably, it is 250-300 degreeC, More preferably, it is 260-290 degreeC. If the set temperature exceeds 330 ° C., the resin temperature increases and the resin deteriorates. When the set temperature is less than 240 ° C., the polyphenylene ether powder does not melt, so that not only the mechanical properties are deteriorated, but also the torque at the time of extrusion becomes too high, causing problems such as stopping the extruder due to torque over.

  In the screw configuration of the present application, the screw rotation speed of the extruder is preferably 600 to 150 rpm, more preferably 500 to 200 rpm, still more preferably 450 to 300 rpm. When the screw rotation speed is 600 rpm or more, the resin temperature rises and the performance decreases. In addition, when the screw rotation speed is 150 rpm or less, the polyphenylene ether powder and other raw materials cannot be sufficiently kneaded.

  In the production method of the present invention, it is necessary to control the temperature of the resin composition extruded from the die outlet to less than 380 ° C. When the resin temperature is 380 ° C. or higher, problems such as deterioration in mechanical properties and impact resistance after exposure to heat occur due to deterioration and decomposition of the resin. Therefore, it is preferably 370 ° C. to 320 ° C., more preferably 360 to 360 ° C. It is necessary to keep the temperature at 330 ° C.

  In order to suppress the resin temperature to 380 ° C. or less, the length of the unmelted mixing zone and the melting zone, the screw configuration, the barrel set temperature, and the screw rotation speed are within the scope of the present invention according to the quantity ratio and type of the resin composition. It is necessary to adjust to.

  In order to keep the resin temperature below 380 ° C, the unmelted mixing zone is set to 75% or more and the melting zone is set to 5% or less, or the barrel set temperature of the melting zone is set to 240 ° C or less. When the number is reduced and the discharge rate is increased, the polyphenylene ether powder cannot be melted sufficiently, so that the extruder is overloaded and stable production cannot be achieved. There exists a problem which the fall and the surface external appearance of a molded article deteriorate.

  When the unmelted mixing zone is 45% or less and the melting zone is 30% or more, when the screw speed is 600 rpm or more, the unmelted mixing zone has a barrel set temperature of 280 ° C or higher, and the molten zone has a barrel set temperature of 330 ° C or higher. In such a case, the resin temperature rises due to heat generation during kneading, which causes deterioration and decomposition of the resin, which causes problems such as deterioration in mechanical properties and impact resistance after exposure to heat.

  In the production method of the present invention, (D) the method of supplying the phosphate ester compound is, in the case of a liquid phosphate ester compound, (A) polyphenylene ether powder, (B) styrene resin, (C) water. After feeding the block copolymer from the first raw material supply port on the upstream side of the extruder, it is preferable to side-feed from the second raw material supply port on the downstream side of the first raw material supply port, more preferably polyphenylene ether powder. In this method, a second raw material supply port is provided in an unmelted mixing zone that does not melt the body, and side feed is performed.

  When the phosphoric ester compound is supplied from the unmelted mixing zone, the kneading disc R (a combination of 3 to 7 discs with a twist angle of 15 to 75 degrees, L / D within a range in which the polyphenylene ether powder is not melted) = 1.0-1.5 positive screw element), it is preferable to mix the polyphenylene ether powder and the liquid phosphate ester compound.

  As a method of side-feeding a liquid phosphate ester compound, a gear pump, a plunger pump, or the like is used to feed from the injection nozzle to the side of the extruder.

The solid phosphate ester compound is supplied together with other components from the first supply port on the upstream side of the extruder, or is side-fed from the supply port provided on the downstream side of the first supply port.
(Example)
The present invention will be described based on examples, but the present invention is not limited to the following examples.

Each component used in the examples and comparative examples is as follows.
(A) Polyphenylene ether (PPE)
Poly-2,6-dimethyl-1,4-phenylene ether (B-1) polystyrene (GPPS) PS Japan Co., Ltd. polystyrene, product with reduced viscosity of 0.48 dl / g measured at 30 ° C. in chloroform solution Name “685”
(B-2) Rubber reinforced polystyrene (HIPS)
PS Japan Co., Ltd. high impact polystyrene, trade name “H9405”

(C) hydrogenated block copolymer;
(C-1)
Two styrene block chains with a number average molecular weight of about 41,000, SBSB structure with 1,2-vinyl structure 33%, styrene polymer block 33% by mass, butadiene unit hydrogenation rate 99%, number average molecular weight About 250,000 hydrogenated styrene block copolymers.
(C-2)
It has two styrene block chains with a number average molecular weight of about 34,000, SBSB structure with 36% 1,2-vinyl structure, 36% by mass of styrene polymer block, 99% hydrogenation rate of butadiene units, number average molecular weight About 180,000 hydrogenated styrene block copolymer.
(C-3)
It has two styrene block chains with a number average molecular weight of about 34,000, SBSB structure with 1,2-vinyl structure of 36%, styrene polymer block 60% by mass, hydrogenation rate of butadiene unit 99%, number average molecular weight About 110,000 hydrogenated styrene block copolymers.
(C-4)
It has two styrene block chains with a number average molecular weight of about 10,000, a 1,2-vinyl structure of 36% SBSB structure, styrene polymer block 40% by mass, butadiene unit hydrogenation rate 99%, number average molecular weight About 50,000 hydrogenated styrene block copolymers.

(G) a composite rubber-based graft copolymer;
Mitsubishi Rayon Co., Ltd. composite rubber-based graft copolymer, trade name “METABBRENE SRK200”
(D) phosphate ester;
(D-1): Daihachi Chemical Co., Ltd. condensed phosphate ester, trade name “CR-741”
(D-2): Condensed phosphate ester manufactured by Daihachi Chemical Co., Ltd., trade name “CR-733S”
(E) polyolefin;
Low density polyethylene: Asahi Kasei Chemicals Co., Ltd. product name "M2004" was used.
(F) heat stabilizer;
(F-1): Hindered phenol heat stabilizer manufactured by Ciba Specialty Chemicals Co., Ltd., trade name “IRGANOX565”
(F-2): ADEKA Co., Ltd. phosphite antioxidant trade name “PEP36”
(F-3): Phosphorus heat stabilizer trade name “IRGFOS168” manufactured by Ciba Specialty Chemicals Co., Ltd.

(1) Heat-resistant aging characteristics A 3.2 mm thick strip-notched IZOD test piece prepared based on ASTM D256 was aged for 100 hours, 200 hours, and 500 hours in an air circulation oven set at 150 ° C. IZOD measurement was performed after standing at room temperature of 23 ° C. and humidity of 50% for 24 hours, and the degree of change in impact resistance (retention rate with respect to IZOD impact strength before thermal aging) was measured.
(2) IZOD impact strength (notched)
Notched IZOD impact strength was measured according to ASTM D256 using 1/4 inch and 1/8 inch thick specimens.
(3) HDT (Flatwise)
Based on ASTM D648, load 18. Measurement was performed at 6 kg / cm 2.

(4) Flame Retardancy UL94 (Standard Specified by Under Writers Laboratories Inc., USA) The flame retardance class classified based on the vertical combustion test was shown. The test piece was measured using an injection-molded test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 1.0 mm.
All samples were tested 5 times and judged. The outline of the classification method is as follows. Other details conform to the UL94 standard. V-0: Average burning time 5 seconds or less Maximum burning time 10 seconds or less No flaming dripping V-1: Average burning time 25 seconds or less Maximum burning time 30 seconds or less No flaming dripping V-2: Average burning time 25 seconds or less Maximum burning time 30 seconds or less With flaming dripping HB: Those not corresponding to the above three items and those that burned up to the clamp holding the test piece The average burning time (seconds) is 2 for each sample, ie 10 times in total This is the average burning time of the extinguishing time after flame contact, and the maximum burning time (seconds) represents the burning time of the test piece that continued to burn for the longest time among the extinguishing times after 10 flames in total. .

(5) Black spot A compression molding machine in which the obtained resin composition pellets were set at 250 ° C .; a disk-shaped molded product having a diameter of 200 mm and a thickness of 1 mm was prepared using a YSR-10 model manufactured by Shindo Metal Industry Co., Ltd. Then, it was visually determined whether black carbide (black spots) remained. A sample having almost no black spots was indicated by ◯, a sample having slightly scattered dots was indicated by Δ, and a sample having many remaining black spots was indicated by ×.
(6) Unmelted material The obtained resin composition pellets were compressed using a compression molding machine: YSR-10 model manufactured by Shinto Metal Industry Co., Ltd. It is processed into a plate-like molded product of 220 mm × 220 mm thickness 1 mm. Next, the obtained plate-shaped molded product was made into a thin film with a bottom of 0.03-0.1 mm in a 200 mm × 200 mm × 150 mm box-shaped mold by a vacuum forming machine: manufactured by Nippon Electric Co., Ltd. Process by adjusting the processing temperature and molding speed. A thin film-like portion at the bottom of the molded product is cut out to form a thin film having a thickness of 200 mm × 200 mm and a thickness of 0.03 to 0.1 mm. The number of unmelted polyphenylene ethers in the film was visually judged. The number of unmelted polyphenylene ethers of 10 or less was indicated by ○, 10-30 by Δ, and 30 or more by ×.
(7) Bleed-out It was visually determined whether or not the strand was stably extruded during extrusion. The liquid material is not blown out from the die part of the extruder and the extrusion stability is good is ◯, the one that is not good is △, the liquid material is blown out from the die part of the extruder, and the strand breakage is caused by ×. expressed.
(8) Vent up The state in which the resin was accumulated in the opening of the vacuum deaeration zone during extrusion was visually determined. Extruders that have no resin pool at the opening in the vacuum degassing zone and that have good extrusion stability are indicated by ○, those that retain resin slightly are indicated by △, and those that gradually close and eventually close the opening are indicated by ×. did.

[ Reference Example 1]
(A) Polyphenylene ether (PPE): 87 parts by mass (B-1) Polystyrene (GPPS): 7 parts by mass (C-1) Hydrogenated block copolymer; 6 parts by mass (D-1) Phosphate ester; 14 1 part by weight (E) polyolefin; 1 part by weight (F-1) IRGANOX 565: 0.6 parts by weight (F-2) PEP36: a biaxial shaft with a 13-barrel vacuum vent with a screw diameter of 58 mm (A) Polyphenylene ether powder, (B-1) polystyrene, (C-1) hydrogenated block copolymer, (E) when melt-kneading using an extruder (ZSK58MC: manufactured by Werner & Pfleiderer, Germany) ) Polyolefin, (F-1) IRGANOX 565, (F-2) PEP 36 in the first feed in barrel 1 upstream with respect to the flow direction of the extruder. After further supplied, the (D-1) phosphoric acid ester, extruded and fed from the injection nozzle to the side of the extruder using a gear pump from the second feed port located from the first feed port to the downstream side. The extruded strand was cut by cooling to obtain a resin composition pellet. Next, the obtained resin composition pellets were evaluated by the above evaluation method, and the results shown in Table 1 were obtained.

  The screw configuration of the extruder was 65% of the total barrel length as an unmelted mixing zone and 12% of the remaining 35% barrel length as a melt-kneading zone. A vacuum degassing zone is provided in the barrel 11, vacuum degassing is performed at −670 mmhg, a second supply port for supplying phosphate ester is provided in the barrel 12, a barrel set temperature is barrel 1: water cooling, barrel 2: 100 ° C., barrel 3 : 150 ° C, barrel 4: 200 ° C, barrel 5: 250 ° C, barrel 7-10: 280 ° C barrel 11-13: 270 ° C, die: 320 ° C, screw rotation speed 400 rpm, discharge rate 300 kg / hr Did.

  As the screw configuration, a single positive screw screw and two positive screw screws were used for the unmelted mixing zone, and a combination of kneading disc R, kneading disc N, and kneading disc L was used for the melt-kneading zone. A reverse screw screw was used between the vacuum degassing zone and the phosphate ester supply port, and after supplying the phosphate ester, the kneading disc R and SME screw were used.

As the screw configuration, a single screw (L / D = 1.0) and two screws are used in the unmelted mixing zone, and a kneading disk R (twist angle of five disks) is used in the melt-kneading zone. L / D = 1.0 positive screw element combined at 45 degrees), kneading disk N (L / D = 1.0 neutral screw element combining 5 disks at a twist angle of 90 °), A combination of kneading discs L (reverse screw element of L / D = 0.52, in which 5 discs were combined at a twist angle of 45 degrees) was used. Between the vacuum degassing zone and the phosphate ester supply port, a reverse screw (L / D = 0.52, two reverse screw elements) is used, and after supplying the phosphate ester, the kneading disc R (L / D = 1.0), SME screw (L / D = 0.69) was used.
The length% of the unmelted zone and the molten zone means the screw configuration, and the length of the unmelted zone and the molten zone can be changed by changing the screw configuration as described in (Tables 1, 2, and 3). % Can be adjusted.

[ Reference Example 2]
In Reference Example 1, a test was performed in the same manner except that the screw was configured as shown in Table 1 and the length of the unmelted mixing zone was changed to 72%, and the results shown in Table 1 were obtained.
[ Reference Example 3]
In Reference Example 1, the test was performed in the same manner except that the screw was configured as shown in Table 1, and the length of the unmelted mixing zone was changed to 50%, and the results shown in Table 1 were obtained.
[Example 4]
In Reference Example 1, a second supply port for supplying a phosphate ester is provided between the barrels 5 and 6 (38% position from the upstream side of the entire barrel length), and the kneading disc R is incorporated after the phosphate ester is supplied. The test was conducted in the same manner except that phosphate ester was supplied as the screw configuration, and the results shown in Table 1 were obtained.
[Example 5]
In Reference Example 2, the second supply port for supplying the phosphate ester is provided between the barrels 5 and 6 (38% position from the upstream side of the total barrel length), and the kneading dish R is incorporated after the phosphate ester is supplied. The test was conducted in the same manner except that the screw configuration was changed, and the results shown in Table 1 were obtained.

[Example 6]
In Reference Example 3, the second supply port for supplying the phosphate ester is provided between the barrels 5 and 6 (38% position from the upstream side of the total barrel length), and the kneading disc R is incorporated after the phosphate ester is supplied. The test was conducted in the same manner except that the screw configuration was changed, and the results shown in Table 1 were obtained.
[Example 7]
In Reference Example 1, a second supply port for supplying a phosphate ester was provided between the barrels 5 and 6 (38% position from the upstream side of the entire barrel length), and the phosphate ester was supplied in the same manner. Tests were performed and the results in Table 1 were obtained.
[ Reference Example 8]
The test was performed in the same manner as in Reference Example 1 except that the screw rotation speed was 500 rpm, and the results shown in Table 2 were obtained.
[ Reference Example 9]
The test was performed in the same manner as in Reference Example 1 except that the screw rotation speed was 600 rpm, and the results shown in Table 2 were obtained.

[ Reference Example 10]
The test was performed in the same manner as in Reference Example 1 except that the screw rotation speed was 200 rpm, and the results shown in Table 2 were obtained.
[ Reference Example 11]
In Reference Example 1, the test was performed in the same manner except that the screw was configured as shown in Table 2 and the length of the melt-kneading zone was 25%, and the results shown in Table 2 were obtained.
[ Reference Example 12]
The test was performed in the same manner as in Reference Example 11 except that the barrel set temperature was changed to barrel 1: 250 ° C. and barrel 2-13: 300 ° C., and the results shown in Table 2 were obtained.
[ Reference Example 13]
In Reference Example 1, the test was conducted in the same manner except that the screw was configured as shown in Table 2 and the length of the melt-kneading zone was changed to 8%, and the results shown in Table 2 were obtained.

[Comparative Example 1]
In Reference Example 1, the test was performed in the same manner except that the screw was configured as shown in Table 3 and the length of the unmelted mixing zone was set to 80%, and the results shown in Table 3 were obtained.
[Comparative Example 2]
In Reference Example 1, the test was performed in the same manner except that the screw was configured as shown in Table 3, the length of the unmelted mixing zone was 50%, and the length of the melt kneading zone was 35%. Got.
[Comparative Example 3]
In Reference Example 1, the test was conducted in the same manner except that the screw was configured as shown in Table 3, the length of the unmelted mixing zone was 50%, and the length of the melt kneading zone was 4%. Got.

[Comparative Example 4]
In Reference Example 1, the test was performed in the same manner except that the screw was configured as shown in Table 3, the length of the unmelted mixing zone was 23%, and the length of the melt kneading zone was 25%. Got.
[Comparative Example 5]
In Comparative Example 4, the test was performed in the same manner except that the barrel set temperature was barrel 1: 250 ° C. and barrel 2-13: 300 ° C., and the results shown in Table 3 were obtained.
[Comparative Example 6]
In Comparative Example 5, a second supply port for supplying the phosphate ester was provided between the barrels 5 and 6 (position 38% from the upstream side of the entire barrel length), and the phosphate ester was supplied in the same manner. Tests were performed and the results in Table 3 were obtained.
[ Reference Examples 14-23, Comparative Examples 7-10]
A test was conducted in the same manner as in the production method of Reference Example 1 except that the composition was changed to the composition shown in Table 4, and the results in Table 4 were obtained.

  The resin composition of the present invention is remarkably excellent in heat aging resistance, is environmentally preferable, and can be suitably used in the fields of television and home appliance OA equipment parts. It is a material suitable for electrical / electronic internal parts applications that require particularly high heat resistance, heat aging characteristics, flame retardancy, etc., particularly for TV internal parts deflection yokes, solar cell junction boxes, and the like.

Claims (10)

(A) 60-98 parts by mass of polyphenylene ether powder, (B) 1-25 parts by mass of styrene resin, (C) 1-20 parts by mass of hydrogenated block copolymer, and (A), (B), ( C) A resin composition containing 3 to 30 parts by mass of a phosphate ester compound with respect to a total of 100 parts by mass of the component, and when the resin composition is melt-kneaded using an extruder When the barrel length of the extruder is 100%, 45 to 75% from the upstream side is used as an unmelted mixing zone, and 5-30% of the barrel length is set as a melt-kneading zone after the unmelted mixing zone .
After (A) polyphenylene ether powder, (B) styrene resin, and (C) hydrogenated block copolymer are supplied from the first raw material supply port on the upstream side of the extruder, (D) phosphate ester compound is added. The manufacturing method of the polyphenylene ether-type resin composition supplied from the 2nd raw material supply port in the said unmelting mixing zone . The method for producing a polyphenylene ether resin composition according to claim 1, wherein the barrel temperature of the unmelted mixing zone is set to 0 to 35% from the upstream side of the extruder to 200 ° C or lower. The method for producing a polyphenylene ether-based resin composition according to claim 1 or 2, wherein the screw speed of the extruder is 600 to 150 rpm. The method for producing a polyphenylene ether-based resin composition according to any one of claims 1 to 3 , wherein the temperature of the resin composition extruded from the die outlet is 300 to 380 ° C. (B) The styrene-based resin is made of polystyrene and rubber-reinforced polystyrene, and the rubber-reinforced polystyrene is 5 parts by weight or less, The polyphenylene ether-based resin composition according to any one of claims 1 to 4 , Production method. The polyphenylene according to any one of claims 1 to 5, wherein (D) the phosphate ester compound is a condensed phosphate ester compound represented by the following general formula (I) or formula (II): A method for producing an ether-based resin composition.

(In the general formulas (I) and (II), Q1, Q2, Q3 and Q4 are each a substituent and each independently represents an alkyl group having 1 to 6 carbon atoms, and R1 and R2 are each a substituent. R3 and R4 each independently represents a hydrogen atom or a methyl group, n has an average value of 1 or more, n1 and n2 each independently represents an integer of 0 to 2, m1, m2 , M3 and m4 each independently represents an integer of 0 to 3.) (C) The method according to claim 1 to 6 polyphenylene ether-based resin composition according to any one of a number average molecular weight of the hydrogenated block copolymer is characterized in that it is a 150,000～350,000. (A) Polyphenylene ether powder (B) Styrenic resin (C) 0.5 to 5 parts by mass of polyolefin is contained with respect to a total of 100 parts by mass of hydrogenated block copolymer. method for producing a polyphenylene ether-based resin composition according to any one of claims 1-7. The polyphenylene ether-based resin composition obtained from the production method according to any one of claims 1 to 8 , wherein the IZOD retention after aging at 150 ° C for 200 hours is 65% or more. A deflection yoke for TV internal parts molded from the resin composition obtained by the manufacturing method according to claim 1.