JPH06136202A - Polypropylene resin composition and its production - Google Patents
Polypropylene resin composition and its productionInfo
- Publication number
- JPH06136202A JPH06136202A JP29102192A JP29102192A JPH06136202A JP H06136202 A JPH06136202 A JP H06136202A JP 29102192 A JP29102192 A JP 29102192A JP 29102192 A JP29102192 A JP 29102192A JP H06136202 A JPH06136202 A JP H06136202A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- weight
- polypropylene resin
- polypropylene
- melt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、ポリプロピレン系樹脂
中にポリスチレン系樹脂が均一に微分散した、剛性が高
く、耐熱性、耐油性、耐薬品性、特に耐衝撃性に優れた
ポリプロピレン系樹脂組成物に関する。FIELD OF THE INVENTION The present invention relates to a polypropylene resin in which a polystyrene resin is uniformly finely dispersed in a polypropylene resin, has high rigidity, and is excellent in heat resistance, oil resistance, chemical resistance, and particularly impact resistance. It relates to a composition.
【０００２】[0002]
【従来の技術】ポリプロピレンは、耐薬品性、耐溶剤
性、耐熱性、成形性等に優れており、電気製品、自動車
部品等の様々な工業分野で広く利用されている。しか
し、ポリプロピレンは結晶性樹脂のため、成形収縮率が
大きく、成形片にヒケが生じたり、寸法安定性に欠け、
剛性が不足する場合がある。一方、ポリスチレンは高剛
性で、非晶性樹脂のため、寸法安定性が良いが、耐薬品
性、耐溶剤性に欠ける。したがって、これらの樹脂の欠
点を補完すべく、両樹脂を溶融混練して樹脂を得ること
は行われているが、これらの樹脂は相溶性が悪く、従っ
て物性の低下が著しいため実用に耐え得るものではな
い。この両樹脂の相溶性を改善するため、相溶化剤とし
て、スチレン−共役ジエンブロック共重合体やその水素
添加ブロック共重合体を配合して成る組成物が、特開昭
５８−２１３０３９、特開昭５９−１８９１４７、特公
昭６２−３４７８２、特開昭６３−２７７２５３、特開
昭６４−８７６４５、特開平１−１７４５５０、特開平
２−１６０８５５、特開平２−１７４５５０、特開平３
−１５７４３６等に開示されている。また、特開平４−
１２２７５１には、ポリスチレン系樹脂としてポリフェ
ニレンエーテル系樹脂との混合物でもよいことが記載さ
れているが、ポリフェニレンエーテル系樹脂の配合によ
る具体例は実施されておらず、その効果は示されていな
い。2. Description of the Related Art Polypropylene has excellent chemical resistance, solvent resistance, heat resistance, moldability and the like, and is widely used in various industrial fields such as electric products and automobile parts. However, since polypropylene is a crystalline resin, it has a large molding shrinkage rate, which causes sink marks on molded pieces and lacks dimensional stability.
The rigidity may be insufficient. On the other hand, polystyrene has high rigidity and is an amorphous resin, and therefore has good dimensional stability, but lacks chemical resistance and solvent resistance. Therefore, in order to complement the drawbacks of these resins, resins have been melt-kneaded to obtain resins, but these resins have poor compatibility, and therefore physical properties are significantly deteriorated, so that they can be put to practical use. Not a thing. In order to improve the compatibility of these two resins, a composition comprising a styrene-conjugated diene block copolymer or its hydrogenated block copolymer as a compatibilizer is disclosed in JP-A-58-213039 and JP-A-58-213039. 59-189147, JP-B-62-34782, JP-A-63-277253, JP-A-64-87645, JP-A-1-174550, JP-A-2-160855, JP-A-2-174550, JP-A-3-174550.
-157436 and the like. In addition, JP-A-4-
122751 describes that a mixture with a polyphenylene ether-based resin may be used as the polystyrene-based resin, but a specific example of blending the polyphenylene ether-based resin has not been carried out and its effect is not shown.
【０００３】[0003]
【発明が解決しようとする課題】しかし、スチレン−共
役ジエンブロック共重合体、および、スチレン−共役ジ
エンブロック共重合体の水素添加物では、相溶化能力が
不十分のため大量に配合する必要がある。そのため、耐
衝撃強度は向上するが、剛性の向上がほとんど見られ
ず、実用上好ましくない。However, in the styrene-conjugated diene block copolymer and the hydrogenated product of the styrene-conjugated diene block copolymer, the compatibilizing ability is insufficient, and thus it is necessary to blend a large amount thereof. is there. Therefore, the impact strength is improved, but the rigidity is hardly improved, which is not preferable in practical use.
【０００４】[0004]
【課題を解決するための手段】上記課題を解決するため
に、本発明者らは種々の方法を検討した結果、ポリプロ
ピレン系樹脂とポリスチレン系樹脂の相溶化剤として、
芳香族ビニル化合物部分の、ブロック共重合体の重量に
占める割合の高い、芳香族ビニル化合物−共役ジエン化
合物ブロック共重合体の共役ジエンの二重結合部分を水
素添加して得られるブロック共重合体を用い、さらに、
ポリフェニレンエーテル系樹脂を少量配合することによ
り、水素添加ブロック共重合体と、ポリスチレンの相溶
性を向上させて、水素添加ブロック共重合体を、ポリプ
ロピレン系樹脂と、ポリスチレン系樹脂の界面に効率よ
く存在させることに成功した。このことにより、相溶化
剤である水素添加ブロック共重合体の配合量を減少させ
ることができ、ひいては、ポリプロピレン系樹脂、ポリ
スチレン系樹脂の本来の特徴をほとんど損なうこと無
く、優れた機械的特性が発現することを見いだし、本発
明に至った。In order to solve the above-mentioned problems, the present inventors have studied various methods, and as a result, as a compatibilizer for polypropylene resin and polystyrene resin,
A block copolymer obtained by hydrogenating a double bond portion of a conjugated diene of an aromatic vinyl compound-conjugated diene compound block copolymer, which has a high ratio of the aromatic vinyl compound portion to the weight of the block copolymer. Using
By adding a small amount of polyphenylene ether resin, the compatibility of the hydrogenated block copolymer and polystyrene is improved, and the hydrogenated block copolymer is efficiently present at the interface between the polypropylene resin and the polystyrene resin. I succeeded in making it happen. By this, it is possible to reduce the amount of the hydrogenated block copolymer as a compatibilizer, and, as a result, the polypropylene resin, without impairing the original characteristics of the polystyrene resin, excellent mechanical properties It was found that they were expressed, and the present invention was achieved.
【０００５】すなわち、本発明は、（ａ）ポリプロピレ
ン系樹脂９５〜５１重量％、（ｂ）ポリスチレン系樹脂
４．５〜４８．９重量％、（ｃ）ポリフェニレンエーテ
ル系樹脂０．１〜４．９重量％からなり、（ｃ）／
（（ｂ）＋（ｃ））が０．１以下である、前記（ａ）ポ
リプロピレン系樹脂と、（ｂ）ポリスチレン系樹脂と、
（ｃ）ポリフェニレンエーテル系樹脂の合計１００重量
部に対して、（ｄ）芳香族ビニル化合物重合体ブロック
を少なくとも１個と、共役ジエン化合物重合体ブロック
を少なくとも１個有し、共役ジエン化合物重合体ブロッ
クの二重結合部分の７０％以上を水素添加して得られる
ブロック共重合体を、１〜４０重量部配合して成るポリ
プロピレン系樹脂組成物および、上記のポリプロピレン
系樹脂組成物の製造にあたり、（ｂ）ポリスチレン系樹
脂と、（ｃ）ポリフェニレンエーテル系樹脂を別途溶融
混練したのち、全成分を溶融混練することを特徴とす
る、ポリプロピレン系樹脂組成物の製造方法に関する。That is, the present invention comprises (a) polypropylene resin 95 to 51% by weight, (b) polystyrene resin 4.5 to 48.9% by weight, (c) polyphenylene ether resin 0.1 to 4% by weight. 9% by weight, (c) /
((B) + (c)) is 0.1 or less, (a) the polypropylene resin, (b) polystyrene resin,
(C) A conjugated diene compound polymer having at least one aromatic vinyl compound polymer block and at least one conjugated diene compound polymer block, based on 100 parts by weight of the polyphenylene ether resin. A block copolymer obtained by hydrogenating 70% or more of the double bond portion of the block is a polypropylene-based resin composition obtained by blending 1 to 40 parts by weight, and in the production of the above polypropylene-based resin composition, (B) Polystyrene resin and (c) Polyphenylene ether resin are separately melt-kneaded, and then all components are melt-kneaded, and the present invention relates to a method for producing a polypropylene resin composition.
【０００６】本発明の（ａ）成分として用いるポリプロ
ピレン系樹脂は、プロピレンモノマーを主成分として重
合したポリマーであれば特に制限はなく、エチレン、１
−ブテン、４−メチルペンテン−１等の他のα−オレフ
ィンとのランダムもしくはブロック共重合体、あるいは
これらの混合物である。また、これらは、エチレン，１
−ブテン、４−メチルペンテン−１等のα−オレフィン
の２種または３種以上の複数種から成るポリプロピレン
系共重合体であってもよい。また、これらのプロピレン
系樹脂の混合物であってもかまわない。The polypropylene resin used as the component (a) of the present invention is not particularly limited as long as it is a polymer obtained by polymerizing a propylene monomer as a main component.
A random or block copolymer with another α-olefin such as butene or 4-methylpentene-1, or a mixture thereof. Also, these are ethylene, 1
It may be a polypropylene-based copolymer composed of two or more of α-olefins such as butene and 4-methylpentene-1. Also, a mixture of these propylene-based resins may be used.
【０００７】これらの中でも、特にプロピレン単独重合
体が好ましい。また、その結晶化度は制限無く用いるこ
とができるが、結晶化度が高いものが好ましい。また、
メルトフローレート（ＭＦＲ，ＡＳＴＭ Ｄ１２３８，
２３０℃，２．１６Ｋｇ荷重）は０．０１〜１００．０
ｇ／１０分が好ましく、さらに好ましくは、ＭＦＲが
０．３〜３０．０／１０分である。ＭＦＲが０．０１ｇ
／１０分未満の場合は、溶融混練及び成形性が著しく困
難であり、１００．０ｇ／１０分より上では機械的強度
が充分でない。Of these, propylene homopolymer is particularly preferable. The crystallinity can be used without limitation, but one having a high crystallinity is preferable. Also,
Melt flow rate (MFR, ASTM D1238,
230 ° C, 2.16 kg load) is 0.01 to 100.0
g / 10 minutes is preferable, and MFR is more preferably 0.3 to 30.0 / 10 minutes. MFR is 0.01g
If it is less than / 10 minutes, melt-kneading and moldability are extremely difficult, and if it is more than 100.0 g / 10 minutes, the mechanical strength is insufficient.
【０００８】本発明の（ｂ）成分として用いるポリスチ
レン系樹脂は、スチレン単独重合体（ＧＰＰＳ）、ゴム
変性ハイインパクトポリスチレン（ＨＩＰＳ）、アクリ
ロニトリル−スチレン共重合体（ＡＳ）、アクリロニト
リル−ブタジエン−スチレン共重合体（ＡＢＳ）、メチ
ルメタクリレート−スチレン共重合体、及び、これらの
混合物から成る樹脂であるが、ＧＰＰＳやＨＩＰＳが好
ましく、特に、ＧＰＰＳが好ましい。ＭＦＲ（ＡＳＴＭ
Ｄ１２３８，２３０℃，２．１６Ｋｇ荷重）は０．０
１〜１００．０ｇ／１０分が好ましく、さらに好ましく
は、ＭＦＲが０．３〜３０．０／１０分である。ＭＦＲ
が０．０１ｇ／１０分未満の場合は、溶融混練及び成形
性が著しく困難であり、１００．０ｇ／１０分より上で
は機械的強度が充分でない。The polystyrene resin used as the component (b) of the present invention includes styrene homopolymer (GPPS), rubber-modified high-impact polystyrene (HIPS), acrylonitrile-styrene copolymer (AS), and acrylonitrile-butadiene-styrene copolymer. Although it is a resin composed of a polymer (ABS), a methylmethacrylate-styrene copolymer, and a mixture thereof, GPPS and HIPS are preferable, and GPPS is particularly preferable. MFR (ASTM
D1238, 230 ° C, 2.16Kg load) is 0.0
1 to 100.0 g / 10 minutes is preferable, and MFR is more preferably 0.3 to 30.0 / 10 minutes. MFR
Is less than 0.01 g / 10 minutes, melt-kneading and moldability are extremely difficult, and above 100.0 g / 10 minutes, mechanical strength is insufficient.
【０００９】さらに、上記（ａ）ポリプロピレン系樹脂
と、（ｂ）ポリスチレン系樹脂のＭＦＲの比（ポリプロ
ピレン系樹脂のＭＦＲ／ポリスチレン系樹脂のＭＦＲ）
は、０．２〜５となるのが好ましく、さらに好ましく
は、１〜５であり、特に、１〜１．５が好ましい。本発
明の（ｃ）成分として用いるポリフェニレンエーテル系
樹脂（以下単にＰＰＥと略記する）は、結合単位：Further, the ratio of MFR of the above-mentioned (a) polypropylene resin and (b) polystyrene resin (MFR of polypropylene resin / MFR of polystyrene resin).
Is preferably 0.2 to 5, more preferably 1 to 5, and particularly preferably 1 to 1.5. The polyphenylene ether resin (hereinafter simply abbreviated as PPE) used as the component (c) of the present invention has a bonding unit:
【００１０】[0010]
【化１】 [Chemical 1]
【００１１】（ここで、Ｒ１、Ｒ２、Ｒ３、およびＲ４
はそれぞれ、水素、ハロゲン、炭化水素、または置換炭
化水素からなる群から選択されるものであり、互いに同
一でも異なっていてもよい。）からなり、還元粘度
（０．５ｇ／ｄｌ、クロロホルム溶液、３０℃測定）
が、０．１５〜０．７０の範囲、より好ましくは、０．
０２〜０．６０の範囲にあるホモ重合体および／または
共重合体である。このＰＰＥの具体的な例としては、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−１，４−フェニ
レンエーテル）、ポリ（２−メチル−６−フェニル−
１，４−フェニレンエーテル）、ポリ（２，６−ジクロ
ロ−１，４−フェニレンエーテル）等が挙げられ、さら
に、２，６−ジメチルフェノールと他のフェノール（例
えば、２，３，６−トリメチルフェノールや２−メチル
−６−ブチルフェノール）との共重合体が好ましく、中
でも、ポリ（２，６−ジメチル−１，４−フェニレンエ
ーテル）、２，６−ジメチルフェノールと２，３，６−
トリメチルフェノールとの共重合体が好ましく、さら
に、ポリ（２，６−ジメチル−１，４−フェニレンエー
テル）が特に好ましい。(Where R1, R2, R3, and R4
Are each selected from the group consisting of hydrogen, halogen, hydrocarbon, or substituted hydrocarbon, and may be the same or different from each other. ), And reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.)
Is in the range of 0.15 to 0.70, more preferably 0.
It is a homopolymer and / or copolymer in the range of 02 to 0.60. Specific examples of the PPE include poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), poly (2-methyl-). 6-phenyl-
1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether), and the like, and further, 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethyl). A copolymer with phenol or 2-methyl-6-butylphenol) is preferable, and among them, poly (2,6-dimethyl-1,4-phenylene ether), 2,6-dimethylphenol and 2,3,6-
A copolymer with trimethylphenol is preferable, and poly (2,6-dimethyl-1,4-phenylene ether) is particularly preferable.
【００１２】上記の、（ａ）ポリプロピレン系樹脂と、
（ｂ）ポリスチレン系樹脂と、（ｃ）ＰＰＥの配合比
は、（ａ）＋（ｂ）＋（ｃ）を１００重量％として
（ａ）が９５〜５１重量％、好ましくは９０〜５５重量
％、（ｂ）が４．５〜４８．９重量％、好ましくは９〜
３９．９重量％、（ｃ）が０．１〜４．９重量％であ
る。（ａ）ポリプロピレン系樹脂が５１重量％未満で
は、ポリプロピレン系樹脂の特性である耐薬品性、耐溶
剤性、耐油性が低下し、（ａ）ポリプロピレン系樹脂が
９５重量％を越えると、ポリスチレン系樹脂の剛性改善
の効果が低下する。また、（ｃ）ＰＰＥは、（ｃ）／
（（ｂ）＋（ｃ））が０．１以下となるように配合し、
好ましくは、０．０３〜０．０６である。０．１より上
では、剛性が低下する。The above-mentioned (a) polypropylene resin,
The blending ratio of (b) polystyrene-based resin and (c) PPE is such that (a) + (b) + (c) is 100% by weight and (a) is 95 to 51% by weight, preferably 90 to 55% by weight. , (B) is 4.5 to 48.9% by weight, preferably 9 to
39.9% by weight, and (c) is 0.1 to 4.9% by weight. If (a) the polypropylene resin is less than 51% by weight, the chemical resistance, solvent resistance and oil resistance which are the characteristics of the polypropylene resin are deteriorated, and if (a) the polypropylene resin exceeds 95% by weight, the polystyrene resin is The effect of improving the rigidity of the resin decreases. Also, (c) PPE is (c) /
((B) + (c)) is blended so as to be 0.1 or less,
It is preferably 0.03 to 0.06. Above 0.1, the rigidity decreases.
【００１３】また、本発明の（ｄ）成分として用いる水
素添加ブロック共重合体は、芳香族ビニル化合物重合体
ブロック（Ａ）を少なくとも１個と、共役ジエン重合体
ブロック（Ｂ）を少なくとも１個有し、結合芳香族ビニ
ル化合物含有量が１５〜８５重量％であり、共役ジエン
部分の二重結合の少なくとも７０％水素添加されてい
る、下記の構造を有するブロック共重合体である。The hydrogenated block copolymer used as the component (d) of the present invention has at least one aromatic vinyl compound polymer block (A) and at least one conjugated diene polymer block (B). A block copolymer having the following structure, having a bound aromatic vinyl compound content of 15 to 85% by weight, and being hydrogenated with at least 70% of the double bonds of the conjugated diene moiety.
【００１４】（Ａ−Ｂ）n Ａ−（Ｂ−Ａ）n （ｎ
は１〜１０の整数） 芳香族ビニル化合物重合体ブロック（Ａ）は、スチレ
ン、α−メチルスチレン、ｐ−エチルスチレン、２，４
−ジメチルスチレン、ビニルナフタレン、ビニルアント
ラセンまたはこれらの混合物からなる重合体であり、好
ましくは、スチレン単独重合体、α−メチルスチレンで
あり、特にスチレン単独重合体が好ましい。 共役ジエ
ン重合体ブロック（Ｂ）は、１，３−ブタジエン、イソ
プレン、１，３−ペンタジエン、３−ブチル−１，３−
オクタジエン、４−エチル−１，３−ヘキサジエンまた
はこれらの混合物からなる重合体、あるいは上記共役ジ
エンと芳香族ビニル化合物との混合物からなる重合体で
ある。好ましくは、１，３−ブタジエン、イソプレンで
ある。(AB) n A- (BA) n (n
Is an integer of 1 to 10) The aromatic vinyl compound polymer block (A) is styrene, α-methylstyrene, p-ethylstyrene, 2,4.
A polymer composed of dimethylstyrene, vinylnaphthalene, vinylanthracene or a mixture thereof, preferably a styrene homopolymer and α-methylstyrene, and particularly preferably a styrene homopolymer. The conjugated diene polymer block (B) is 1,3-butadiene, isoprene, 1,3-pentadiene, 3-butyl-1,3-
It is a polymer composed of octadiene, 4-ethyl-1,3-hexadiene or a mixture thereof, or a polymer composed of a mixture of the conjugated diene and an aromatic vinyl compound. Of these, 1,3-butadiene and isoprene are preferable.
【００１５】なお、共役ジエン重合体ブロック（Ｂ）が
１，３−ブタジエンの場合は、水素添加すると、１，４
結合で重合した部分からはエチレンが、１，２結合で重
合した部分からはブチレンが生成し、エチレン・ブチレ
ン共重合体になる（ＳＥＢＳ）。エチレン・ブチレン共
重合部分のエチレン対ブチレン比や、重合形式に特に制
限はない。When the conjugated diene polymer block (B) is 1,3-butadiene, hydrogenation will give 1,4 butadiene.
Ethylene is produced from the portion polymerized by the bond and butylene is produced from the portion polymerized by the 1,2 bond to form an ethylene / butylene copolymer (SEBS). There are no particular restrictions on the ethylene to butylene ratio of the ethylene / butylene copolymerization portion or the polymerization mode.
【００１６】水素添加ブロック共重合体の数平均分子量
は３万〜３０万が好ましく、特に、６万〜１０万が好ま
しい。数平均分子量が３万未満の場合は、相溶化能力が
低下し、３０万より上では、溶融混練が困難である。水
素添加ブロック共重合体に占めるブロック（Ａ）の割合
は、１５〜８５重量％が好ましく、特に、５０〜７０重
量％が好ましい。この範囲未満では、相溶化能力が不足
し、この範囲より上の場合は、耐衝撃強度が低下する。The number average molecular weight of the hydrogenated block copolymer is preferably 30,000 to 300,000, and particularly preferably 60,000 to 100,000. If the number average molecular weight is less than 30,000, the compatibilizing ability is lowered, and if it exceeds 300,000, melt-kneading is difficult. The proportion of the block (A) in the hydrogenated block copolymer is preferably 15 to 85% by weight, particularly preferably 50 to 70% by weight. If it is less than this range, the compatibilizing ability is insufficient, and if it is above this range, the impact strength is lowered.
【００１７】なお、上記水素添加ブロック共重合体のブ
ロック（Ｂ）の二重結合部分の水素添加率は、７０％以
上が好ましく、より好ましくは、９０％以上である。７
０％未満では相溶化能力が不足する。本発明のポリプロ
ピレン系樹脂組成物は、必要に応じて、炭酸カルシウ
ム、タルク、ガラス繊維、ガラスビーズ、シリカ、ウィ
スカー、酸化チタン、水酸化アルミニウム、水酸化アン
モニウム、酸化アンチモン等の無機充填材、カーボンブ
ラック、カーボン繊維等の有機充填材、および酸化防止
剤、顔料、難燃材、帯電防止剤、滑剤、紫外線吸収剤等
の任意の添加剤を含むことができる。充填剤、添加剤の
種類はプラスチックの配合に一般的に用いられているも
のであれば特に制限はない。The hydrogenation rate of the double bond portion of the block (B) of the hydrogenated block copolymer is preferably 70% or more, more preferably 90% or more. 7
If it is less than 0%, the compatibilizing ability is insufficient. The polypropylene resin composition of the present invention, if necessary, calcium carbonate, talc, glass fiber, glass beads, silica, whiskers, titanium oxide, aluminum hydroxide, ammonium hydroxide, inorganic fillers such as antimony oxide, carbon It may contain organic fillers such as black and carbon fibers, and optional additives such as antioxidants, pigments, flame retardants, antistatic agents, lubricants, and ultraviolet absorbers. The types of fillers and additives are not particularly limited as long as they are generally used in plastic compounding.
【００１８】また、有機過酸化物等のラジカル発生剤を
用いて、流動特性をコントロールする溶融混練も差し支
えない。本発明のポリプロピレン系樹脂組成物は、上記
（ａ）ポリプロピレン系樹脂、（ｂ）ポリスチレン系樹
脂、（ｃ）ＰＰＥ、（ｄ）水素添加ブロック共重合体を
溶融混練することにより得られる。その場合、（ａ）〜
（ｄ）成分を一括溶融混練してもよいが、（ｃ）成分
が十分溶融する温度条件で溶融混練すると（ｃ）成分以
外の樹脂の熱劣化が起こりやすい。Further, a radical kneading agent such as an organic peroxide may be used for melt kneading for controlling the fluidity. The polypropylene-based resin composition of the present invention is obtained by melt-kneading the above-mentioned (a) polypropylene-based resin, (b) polystyrene-based resin, (c) PPE, and (d) hydrogenated block copolymer. In that case, (a) ~
Although the component (d) may be melt-kneaded at once, the component (c)
When melt-kneading is carried out under the temperature condition in which is sufficiently melted, heat deterioration of the resin other than the component (c) is likely to occur.
【００１９】ところで、（ｂ）成分と（ｃ）成分は完全
相溶性であり、（ｃ）成分の配合量が少ない場合は
（ｂ）成分と（ｃ）成分を一度溶融混練して得られる組
成物はポリプロピレンとほぼ同じ温度で溶融混練が可能
である。よって、本発明の組成物を得るには、（ｂ）成
分と（ｃ）成分を高温で混練し、（ａ）成分と（ｄ）成
分をそれに配合して低温で溶融混練する方法が好まし
い。たとえば、押出機等で連続的に製造する過程で、
（ｂ）成分と（ｃ）成分をバレル温度２６０〜３２０℃
で溶融混練し、途中からバレルの温度を１８０〜２５０
℃に下げ、その部分から（ａ）、（ｄ）成分を添加して
溶融混練する方法を用いることができる。また、高温部
分で（ｂ）成分６０〜９８重量％と（ｃ）成分４０〜２
重量％を溶融混練し、低温部分で本発明の組成となるよ
うに（ａ）、（ｂ）、（ｄ）成分を添加してもよい。By the way, the component (b) and the component (c) are completely compatible, and when the amount of the component (c) is small, the composition obtained by melt-kneading the component (b) and the component (c) once. The product can be melt-kneaded at about the same temperature as polypropylene. Therefore, in order to obtain the composition of the present invention, a method of kneading the component (b) and the component (c) at a high temperature, blending the component (a) and the component (d) therein, and melt-kneading at a low temperature is preferable. For example, in the process of continuously manufacturing with an extruder,
(B) component and (c) component barrel temperature 260-320 ℃
Melt and knead with the barrel temperature from 180 to 250
It is possible to use a method of lowering the temperature to 0 ° C., adding the components (a) and (d) from that portion, and melt-kneading. Further, in the high temperature portion, 60 to 98% by weight of the component (b) and 40 to 2 of the component (c) are used.
You may melt-knead weight% and may add (a), (b), (d) component so that it may become a composition of this invention in a low temperature part.
【００２０】さらに、（ｂ）成分と（ｃ）成分を高温で
予備混練した後に、（ａ）成分と（ｄ）成分と再度低温
で溶融混練する方法も良い。好ましくのは、（ｂ）ポリ
スチレン系樹脂（ＰＳ）６０〜９８％と（ｃ）ＰＰＥ４
０〜２％を２６０〜３２０℃で溶融混練し、ＰＳ／ＰＰ
Ｅのマスターバッチを作成し、これを本発明の組成比と
なるように（ａ）、（ｂ）、（ｄ）成分とともに再度１
８０〜２５０℃で溶融混練する方法である。Further, it is also possible to pre-knead the components (b) and (c) at a high temperature and then melt-knead the components (a) and (d) again at a low temperature. Preferably, (b) polystyrene resin (PS) 60 to 98% and (c) PPE4
Melt kneading 0-2% at 260-320 ℃, PS / PP
A masterbatch of E was prepared, and this was again added together with the components (a), (b) and (d) so that the composition ratio of the present invention was obtained.
This is a method of melt-kneading at 80 to 250 ° C.
【００２１】[0021]
【実施例】本発明を以下の実施例によりさらに詳細に説
明する。ただし、本発明は、これらの実施例により限定
されるものではない。各実施例および比較例の原料樹脂
として、以下のものを用いた。 ［１］ポリプロピレン系樹脂（ＰＰ） ＰＰ−：プロピレン単独重合体 メルトフローレート(MFR)(230 ℃,2.16Kg 荷重)＝
０．５ｇ／１０分 ＰＰ−：プロピレン単独重合体 ＭＦＲ(230℃,2.16Kg 荷重)＝ ２．０ｇ／１０分 ［２］ポリスチレン系樹脂（ＰＳ） ＰＳ−：スチレン単独重合体 ＭＦＲ(230℃,2.16Kg 荷重)＝ １．４ｇ／１０分 ＰＳ−：スチレン単独重合体 メルトフローレート(MFR)(230 ℃,2.16Kg 荷重)＝
１．６ｇ／１０分 ［３］ポリフェニレンエーテル系樹脂（ＰＰＥ） 酸素吹き込み部を反応器底部に有し、内部に冷却溶コイ
ル、撹拌羽根を有するステンレス製反応器内部を窒素で
充分置換した後、臭化第二銅５３．６ｇ、ジ−ｎ−ブチ
ルアミン１１１０ｇ、さらに、トルエン２０リットル、
ｎ−ブタノール１６リットル、メタノール４リットルの
混合溶媒に、２，６−キシレノール８．７５Ｋｇを溶解
して反応器に仕込んだ。撹拌しながら反応器内部に酸素
を吹き込み続け、１８０分間重合を行った。なお、内温
は３０℃に維持するため、重合中、冷却コイルに水を循
環させた。重合終了後、析出したポリマーを濾別し、メ
タノール／塩酸混合液を添加し、ポリマー中の残存触媒
を分解し、さらに、メタノールを用いて充分洗浄した後
乾燥し、白色粉末状のＰＰＥ（還元粘度０．５４）を得
た。 ［４］水素添加ブロック共重合体（ＳＥＢＳ） スチレン−ブタジエンテトラブロック共重合体の水素添
加物を用いた。The present invention will be described in more detail by the following examples. However, the present invention is not limited to these examples. The following materials were used as the raw material resins of the examples and comparative examples. [1] Polypropylene resin (PP) PP-: Propylene homopolymer Melt flow rate (MFR) (230 ° C, 2.16 kg load) =
0.5 g / 10 min PP-: Propylene homopolymer MFR (230 ° C, 2.16 Kg load) = 2.0 g / 10 min [2] Polystyrene resin (PS) PS-: Styrene homopolymer MFR (230 ° C, 2.16Kg load) = 1.4g / 10min PS-: Styrene homopolymer Melt flow rate (MFR) (230 ° C, 2.16Kg load) =
1.6 g / 10 min [3] Polyphenylene ether-based resin (PPE) After the oxygen blowing part is at the bottom of the reactor and the inside of the stainless steel reactor having the cooling melt coil and the stirring blade inside is sufficiently replaced with nitrogen, Cupric bromide 53.6 g, di-n-butylamine 1110 g, further 20 liters of toluene,
8.75 kg of 2,6-xylenol was dissolved in a mixed solvent of 16 liters of n-butanol and 4 liters of methanol and charged into a reactor. Oxygen was continuously blown into the reactor while stirring to carry out polymerization for 180 minutes. In addition, in order to maintain the internal temperature at 30 ° C., water was circulated through the cooling coil during the polymerization. After the polymerization was completed, the precipitated polymer was filtered off, a methanol / hydrochloric acid mixture was added to decompose the residual catalyst in the polymer, and the polymer was thoroughly washed with methanol and dried to give a white powder PPE (reduction A viscosity of 0.54) was obtained. [4] Hydrogenated block copolymer (SEBS) A hydrogenated product of a styrene-butadiene tetrablock copolymer was used.
【００２２】数平均分子量 ８５０００ 結合スチレン量 ６０重量％ ブチレン量 ３５％ 水素添加率 ９５％Number average molecular weight 85,000 Bound styrene amount 60% by weight Butylene amount 35% Hydrogenation rate 95%
【００２３】[0023]
【実施例１〜５および比較例１、５】上記ＰＰ、ＰＳ、
ＰＰＥ、ＳＥＢＳを表１に示した組成で配合し、バレル
温度を２７０℃に設定した２５ｍｍφ同方向回転二軸押
出機（ＺＳＫ−２５；Ｗ＆Ｐ製）で一括溶融混練した
後、水冷し、切断してペレット状樹脂組成物を得た。Examples 1 to 5 and Comparative Examples 1 and 5 PP, PS,
PPE and SEBS were blended in the composition shown in Table 1 and melt-kneaded together with a 25 mmφ co-rotating twin-screw extruder (ZSK-25; made by W & P) having a barrel temperature of 270 ° C., then water-cooled and cut. To obtain a pellet-shaped resin composition.
【００２４】[0024]
【比較例２〜４】上記ＰＰ、ＰＳ、ＳＥＢＳを表１に示
した組成で配合し、バレル温度を２３０℃に設定した２
５ｍｍφ同方向回転二軸押出機（ＺＳＫ−２５；Ｗ＆Ｐ
製）で一括溶融混練した後、水冷し、切断してペレット
状樹脂組成物を得た。[Comparative Examples 2 to 4] The above PP, PS and SEBS were blended in the composition shown in Table 1 and the barrel temperature was set to 230 ° C.
5mmφ co-rotating twin screw extruder (ZSK-25; W & P
Melt-kneading in batch, followed by cooling with water and cutting to obtain a pellet-shaped resin composition.
【００２５】[0025]
【実施例６〜８および比較例６】ＰＳ／ＰＰＥ＝６０／
４０の組成比で、バレル温度を２８０℃に設定した２軸
押出機で予備混練してマスターバッチを製造し、このマ
スターバッチとＰＰ、ＰＳ、ＳＥＢＳを配合し、バレル
温度を２３０℃に設定した２５ｍｍφ同方向回転二軸押
出機（ＺＳＫ−２５；Ｗ＆Ｐ製）で一括溶融混練した
後、水冷し、切断してペレット状樹脂組成物を得た。Examples 6 to 8 and Comparative Example 6 PS / PPE = 60 /
A masterbatch was prepared by pre-kneading with a twin screw extruder having a composition ratio of 40 and a barrel temperature of 280 ° C. The masterbatch, PP, PS and SEBS were blended, and the barrel temperature was set to 230 ° C. A 25 mmφ co-rotating twin-screw extruder (ZSK-25; made by W & P) was melt-kneaded together, then cooled with water and cut to obtain a pellet-shaped resin composition.
【００２６】これらのペレットを用い、シリンダー温度
２３０℃、金型温度５０℃に設定した射出成形機（ＦＡ
Ｓ−５０Ｄ；ファナック製）試験片を成形した。また、
実施例１、３、４および比較例１、２の上記ペレットを
ウルトラミクロトームを用いて超薄膜を作成し、四酸化
ルテニウム蒸気で染色した後、透過電子顕微鏡（ＪＥＭ
−１２００ＥＸＩＩ；日本電子製）を用い、下記［８］
の手法でモルフォロジーを観察し、写真撮影を行い、ネ
ガを得た。それらを引き延ばしてプリントした写真を、
図１〜５として示した。図中、連続相はポリプロピレ
ン、分散相はポリスチレンとＰＰＥの混合物である。Using these pellets, an injection molding machine (FA with a cylinder temperature of 230 ° C. and a mold temperature of 50 ° C.) was used.
S-50D; manufactured by FANUC) A test piece was molded. Also,
An ultrathin film was prepared from the pellets of Examples 1, 3, 4 and Comparative Examples 1 and 2 using an ultramicrotome and stained with ruthenium tetroxide vapor, followed by transmission electron microscopy (JEM).
-1200EXII; manufactured by JEOL Ltd.) and the following [8]
The morphology was observed by the method described in 1 above, and a photograph was taken to obtain a negative. Photos that stretched and printed them,
Shown as FIGS. In the figure, the continuous phase is polypropylene and the dispersed phase is a mixture of polystyrene and PPE.
【００２７】さらに、上記写真のうち、比較例１を除く
４点について、下記の［９］の方法で画像解析を行い、
分散相の円相当径を求め、その粒度分布を得た。この結
果を、図６〜９に示した。本発明に用いた各種物性の測
定方法は以下の通りである。 ［１］曲げ弾性率（ＦＭ） ＡＳＴＭ Ｄ７９０ オートグラフ ＡＧ−５０００Ｄ 島津
製作所製 ［２］曲げ強度（ＦＳ） ＡＳＴＭ Ｄ７９０ オートグラフ ＡＧ−５０００Ｄ 島津
製作所製 ［３］アイゾット衝撃強度 ＡＳＴＭ Ｄ２５６；２３℃ ユニバーサルインパクトテスター 東洋
精機製 ［４］熱変形温度（ＨＤＴ） ＡＳＴＭ Ｄ６４８；４．６Ｋｇ荷重 ヒートディストーションテスター No.148 HDA TYPE 安田精機製 ［５］メルトフローレート（ＭＦＲ） ＡＳＴＭ Ｄ１２３８；２３０℃，２．１６Ｋｇ荷重 メルトインデクサー TYPE C-5059D2 東洋
精機製 ［６］表面剥離性テスト １４８×１４８×２ｍｍの射出成形板の表面に剃刀を用
いて１×１ｍｍのます目を１００個付け、セロハンテー
プ（ニチバン製）を張り付けた後、はぎ取って成形片の
表面に残ったます目の数を数えた。 ［７］耐サラダ油テスト ダンベル型成形片（ＡＳＴＭ・Ｔｙｐｅ−１）を直径１
７ｃｍの円柱に沿って曲げ、試験片の中央部分に約１ｃ
ｃの日清サラダ油を染み込ませた長さ約５ｃｍのガーゼ
を載せ、７２時間後にクラックの発生状態を観察した。 ［８］透過電子顕微鏡写真の撮影 装置；ＪＥＭ−１２００ＥＸＩＩ 日本
電子製 加速電圧；１００ＫＶ ビーム電流；９３〜９８μＡ 集束レンズ絞り；最小 対物レンズ絞り；中間 拡大倍率；５０００倍 露出時間；１秒 試料傾斜；０° ［９］粒度分布の測定 画像解析装置；ＩＰ−１０００ 旭化
成工業製 画像入力装置；カラースキャナ ＪＸ−４５０ シャ
ープ製 ２００００倍に引き延ばした１１×１１Ｃｍの写真を、
画像入力装置を用い、解像度２００ドット／インチで読
み込ませたデータを二値化し、そして、マトリックスと
ドメインに分離し、ドメインの面積をそれが占めるドッ
ト数から求め、その面積の円相当径を求め、算術平均し
た値を平均粒径とした。Further, among the above photographs, four points except Comparative Example 1 were subjected to image analysis by the following method [9],
The equivalent circle diameter of the dispersed phase was determined and the particle size distribution was obtained. The results are shown in FIGS. The methods for measuring various physical properties used in the present invention are as follows. [1] Flexural Modulus (FM) ASTM D790 Autograph AG-5000D made by Shimadzu [2] Bending Strength (FS) ASTM D790 Autograph AG-5000D made by Shimadzu [3] Izod Impact Strength ASTM D256; 23 ° C Universal Impact Tester Toyo Seiki [4] Heat distortion temperature (HDT) ASTM D648; 4.6 Kg load Heat distortion tester No.148 HDA TYPE Yasuda Seiki [5] Melt flow rate (MFR) ASTM D1238; 230 ° C, 2.16 Kg load Melt Indexer TYPE C-5059D2 made by Toyo Seiki [6] Surface peeling test 100 pieces of 1 x 1 mm squares are attached to the surface of the injection molded plate of 148 x 148 x 2 mm using a razor, and cellophane tape (made by Nichiban) After attaching, peel off and attach to the surface of the molded piece. The number of remaining squares was counted. [7] Salad oil resistance test Dumbbell shaped molded pieces (ASTM Type 1) with a diameter of 1
Bend along a 7 cm cylinder, approximately 1c in the center of the test piece.
A gauze having a length of about 5 cm impregnated with Nissin salad oil of c was placed, and the state of crack generation was observed after 72 hours. [8] Photograph of transmission electron microscope photograph; JEM-1200EXII JEOL accelerating voltage; 100 KV beam current; 93 to 98 μA focusing lens diaphragm; minimum objective lens diaphragm; intermediate magnifying power; 5000 times exposure time; 1 second sample inclination; 0 ° [9] Measurement of particle size distribution Image analyzer: IP-1000 Image input device manufactured by Asahi Kasei; Color scanner JX-450 Sharp manufactured 11 × 11 Cm photograph stretched 20000 times,
Using an image input device, binarize the data read at a resolution of 200 dots / inch, separate it into a matrix and a domain, find the area of the domain from the number of dots it occupies, and find the equivalent circle diameter of that area. The value obtained by arithmetic averaging was used as the average particle size.
【００２８】これらの結果より、本発明のポリプロピレ
ン系樹脂組成物は、耐熱性、剛性、耐衝撃強度、耐油性
に優れ、分散状態も非常に優れていることが明らかにな
った。From these results, it was revealed that the polypropylene resin composition of the present invention is excellent in heat resistance, rigidity, impact resistance, oil resistance, and also in a dispersed state.
【００２９】[0029]
【表１】 [Table 1]
【００３０】[0030]
【表２】 [Table 2]
【００３１】[0031]
【発明の効果】本発明は、ポリプロピレン系樹脂とポリ
スチレン系樹脂を主体とし、これらに相溶化剤として特
定のブロック共重合体を配合し、さらに、少量のＰＰＥ
を配合したものであって、剛性が高く、耐溶剤性、耐油
性、耐薬品性、耐熱性、特に、耐衝撃性に優れたポリプ
ロピレン系樹脂組成物が得られる。EFFECT OF THE INVENTION The present invention is mainly composed of a polypropylene resin and a polystyrene resin, in which a specific block copolymer is blended as a compatibilizer, and a small amount of PPE is added.
A polypropylene resin composition having a high rigidity, excellent solvent resistance, oil resistance, chemical resistance, heat resistance, and particularly excellent impact resistance can be obtained.
【図１】実施例１で得られた本発明組成物の粒子の構造
を示す電子顕微鏡写真である。FIG. 1 is an electron micrograph showing the structure of particles of the composition of the present invention obtained in Example 1.
【図２】実施例３で得られた組成物の粒子の構造を示す
電子顕微鏡写真である。2 is an electron micrograph showing the structure of particles of the composition obtained in Example 3. FIG.
【図３】実施例４で得られた組成物の粒子の構造を示す
電子顕微鏡写真である。FIG. 3 is an electron micrograph showing the structure of particles of the composition obtained in Example 4.
【図４】比較例１で得られた組成物の粒子の構造を示す
電子顕微鏡写真である。FIG. 4 is an electron micrograph showing the structure of particles of the composition obtained in Comparative Example 1.
【図５】比較例２で得られた組成物の粒子の構造を示す
電子顕微鏡写真である。5 is an electron micrograph showing the structure of particles of the composition obtained in Comparative Example 2. FIG.
【図６】実施例１で得られた試料の組成物中の分散相の
粒度分布と平均粒径（”△”で示す）を示すグラフであ
る。FIG. 6 is a graph showing the particle size distribution and average particle size (indicated by “Δ”) of the dispersed phase in the composition of the sample obtained in Example 1.
【図７】実施例３で得られた試料の組成物中の分散相の
粒度分布と平均粒径（”△”で示す）を示すグラフであ
る。FIG. 7 is a graph showing the particle size distribution and average particle size (indicated by “Δ”) of the dispersed phase in the composition of the sample obtained in Example 3.
【図８】実施例４で得られた試料の組成物中の分散相の
粒度分布と平均粒径（”△”で示す）を示すグラフであ
る。FIG. 8 is a graph showing the particle size distribution and average particle size (indicated by “Δ”) of the dispersed phase in the composition of the sample obtained in Example 4.
【図９】比較例２で得られた試料の組成物中の分散相の
粒度分布と平均粒径（”△”で示す）を示すグラフであ
る。9 is a graph showing the particle size distribution and average particle size (indicated by “Δ”) of the dispersed phase in the composition of the sample obtained in Comparative Example 2. FIG.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成４年１１月４日[Submission date] November 4, 1992
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図１[Name of item to be corrected] Figure 1
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図１】 [Figure 1]
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図２[Name of item to be corrected] Figure 2
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図２】 [Fig. 2]
【手続補正３】[Procedure 3]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図３[Name of item to be corrected] Figure 3
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図３】 [Figure 3]
【手続補正４】[Procedure amendment 4]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図４[Name of item to be corrected] Fig. 4
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図４】 [Figure 4]
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】図面[Document name to be corrected] Drawing
【補正対象項目名】図５[Name of item to be corrected] Figure 5
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【図５】 [Figure 5]
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 71:12 53:02） ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display area C08L 71:12 53:02)
Claims (2)
重量％、（ｂ）ポリスチレン系樹脂４．５〜４８．９重
量％、（ｃ）ポリフェニレンエーテル系樹脂０．１〜
４．９重量％からなり、かつ、（ｃ）／（（ｂ）＋
（ｃ））が０．１以下である、前記（ａ）ポリプロピレ
ン系樹脂と、（ｂ）ポリスチレン系樹脂と、（ｃ）ポリ
フェニレンエーテル系樹脂の合計１００重量部に対し
て、（ｄ）芳香族ビニル化合物重合体ブロックを少なく
とも１個と、共役ジエン化合物重合体ブロックを少なく
とも１個有し、共役ジエン化合物重合体ブロックの二重
結合部分の７０％以上を水素添加して得られるブロック
共重合体を、１〜４０重量部配合して成るポリプロピレ
ン系樹脂組成物。1. (a) Polypropylene resin 95 to 51
% By weight, (b) polystyrene-based resin 4.5 to 48.9% by weight, (c) polyphenylene ether-based resin 0.1 to
4.9% by weight and (c) / ((b) +
(C)) is 0.1 or less, (d) aromatic based on 100 parts by weight of the total of the (a) polypropylene-based resin, (b) polystyrene-based resin, and (c) polyphenylene ether-based resin. A block copolymer having at least one vinyl compound polymer block and at least one conjugated diene compound polymer block, and obtained by hydrogenating 70% or more of the double bond portion of the conjugated diene compound polymer block. 1 to 40 parts by weight of a polypropylene resin composition.
成物の製造にあたり、（ｂ）ポリスチレン系樹脂と、
（ｃ）ポリフェニレンエーテル系樹脂を別途溶融混練し
たのち、全成分を溶融混練することを特徴とするポリプ
ロピレン系樹脂組成物の製造方法。2. In the production of the polypropylene resin composition according to claim 1, (b) a polystyrene resin,
(C) A method for producing a polypropylene resin composition, which comprises melt-kneading a polyphenylene ether-based resin separately and then melt-kneading all components.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29102192A JP3319789B2 (en) | 1992-10-29 | 1992-10-29 | Polypropylene resin composition and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29102192A JP3319789B2 (en) | 1992-10-29 | 1992-10-29 | Polypropylene resin composition and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06136202A true JPH06136202A (en) | 1994-05-17 |
| JP3319789B2 JP3319789B2 (en) | 2002-09-03 |
Family
ID=17763431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29102192A Expired - Lifetime JP3319789B2 (en) | 1992-10-29 | 1992-10-29 | Polypropylene resin composition and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3319789B2 (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002327120A (en) * | 2001-04-27 | 2002-11-15 | Jsr Corp | Compatibilizing agent composition, modifier composition, and thermoplastic polymer composition and method for producing the same |
| US6495630B2 (en) | 2000-12-28 | 2002-12-17 | General Electric Company | Poly(arylene ether)-polyolefin compositions and articles derived therefrom |
| US6545080B2 (en) | 2000-12-28 | 2003-04-08 | General Electric Company | Glass-filled poly(arylene ether)-polyolefin composition and articles derived therefrom |
| US6660794B2 (en) | 2000-12-28 | 2003-12-09 | General Electric Company | Glass-filled poly(arylene ether)-polyolefin composition and articles derived therefrom |
| US6855767B2 (en) | 2000-12-28 | 2005-02-15 | General Electric | Poly(arylene ether)-polyolefin composition and articles derived therefrom |
| US6861472B2 (en) | 2000-12-28 | 2005-03-01 | General Electric Company | Poly(arylene ether)-polyolefin compositions and articles derived therefrom |
| JP2006124580A (en) * | 2004-10-29 | 2006-05-18 | Nippon Zeon Co Ltd | Vinyl alicyclic hydrocarbon polymer composition and molded product |
| CN109825059A (en) * | 2019-01-11 | 2019-05-31 | 金发科技股份有限公司 | A kind of polypropylene polyphenyleneoxidepolystyrene ternary alloy three-partalloy and preparation method thereof and a kind of application |
-
1992
- 1992-10-29 JP JP29102192A patent/JP3319789B2/en not_active Expired - Lifetime
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6495630B2 (en) | 2000-12-28 | 2002-12-17 | General Electric Company | Poly(arylene ether)-polyolefin compositions and articles derived therefrom |
| US6545080B2 (en) | 2000-12-28 | 2003-04-08 | General Electric Company | Glass-filled poly(arylene ether)-polyolefin composition and articles derived therefrom |
| US6660794B2 (en) | 2000-12-28 | 2003-12-09 | General Electric Company | Glass-filled poly(arylene ether)-polyolefin composition and articles derived therefrom |
| US6855767B2 (en) | 2000-12-28 | 2005-02-15 | General Electric | Poly(arylene ether)-polyolefin composition and articles derived therefrom |
| US6861472B2 (en) | 2000-12-28 | 2005-03-01 | General Electric Company | Poly(arylene ether)-polyolefin compositions and articles derived therefrom |
| JP2002327120A (en) * | 2001-04-27 | 2002-11-15 | Jsr Corp | Compatibilizing agent composition, modifier composition, and thermoplastic polymer composition and method for producing the same |
| JP2006124580A (en) * | 2004-10-29 | 2006-05-18 | Nippon Zeon Co Ltd | Vinyl alicyclic hydrocarbon polymer composition and molded product |
| CN109825059A (en) * | 2019-01-11 | 2019-05-31 | 金发科技股份有限公司 | A kind of polypropylene polyphenyleneoxidepolystyrene ternary alloy three-partalloy and preparation method thereof and a kind of application |
| WO2020143447A1 (en) * | 2019-01-11 | 2020-07-16 | 金发科技股份有限公司 | Polypropylene-polyphenylene ether-polystyrene ternary alloy, preparation method therefor and use thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3319789B2 (en) | 2002-09-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5071911A (en) | Thermoplastic resin composition and process for producing the same | |
| CA1335127C (en) | Thermoplastic resin composition | |
| EP1404761B1 (en) | Poly(arylene ether)-polyolefin composition, method for the preparation thereof, and articles derived therefrom | |
| JP5797710B2 (en) | Resin composition and molded body thereof | |
| CA2039720A1 (en) | Thermoplastic resin composition | |
| JP2683829B2 (en) | Resin composition | |
| CA1267741A (en) | Polyphenylene ether resin compositions containing olefin polymer or copolymer | |
| JP3319789B2 (en) | Polypropylene resin composition and method for producing the same | |
| US20030148116A1 (en) | Articles and sheets containing glass-filled poly(arylene ether)-polyolefin composition | |
| KR101194205B1 (en) | Low-odor resin composition | |
| JP2016194030A (en) | Resin composition, molded article, film, and laminated film | |
| JP3181702B2 (en) | Method for producing resin composition having excellent thermal stability | |
| JPH07304908A (en) | Thermoplastic resin composition | |
| JPH0657128A (en) | Resin composition excellent in low-temperature impact resistance | |
| JP3264468B2 (en) | Impact resistant polystyrene resin composition | |
| JPH101603A (en) | Thermoplastic resin composition and ic tray | |
| JPH11116794A (en) | Ic tray-molding resin composition | |
| JP2837709B2 (en) | Polymer composition | |
| JP4291012B2 (en) | Conductive resin composition | |
| JP3622339B2 (en) | Thermoplastic resin composition | |
| JP3335477B2 (en) | Thermoplastic resin composition | |
| JP3812612B2 (en) | Polyphenylene ether resin composition that resists photo-discoloration | |
| JPH09241499A (en) | Production of resin composition | |
| JPH08199012A (en) | Thermoplastic resin composition | |
| JPH0959508A (en) | Polyphenylene ether resin composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20020604 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080621 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090621 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090621 Year of fee payment: 7 |
|
| S531 | Written request for registration of change of domicile |
Free format text: JAPANESE INTERMEDIATE CODE: R313531 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090621 Year of fee payment: 7 |
|
| R350 | Written notification of registration of transfer |
Free format text: JAPANESE INTERMEDIATE CODE: R350 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090621 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100621 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110621 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110621 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120621 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120621 Year of fee payment: 10 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130621 Year of fee payment: 11 |
|
| EXPY | Cancellation because of completion of term | ||
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130621 Year of fee payment: 11 |