JPH0649256A - Foamed polystyrene resin - Google Patents
Foamed polystyrene resinInfo
- Publication number
- JPH0649256A JPH0649256A JP20646792A JP20646792A JPH0649256A JP H0649256 A JPH0649256 A JP H0649256A JP 20646792 A JP20646792 A JP 20646792A JP 20646792 A JP20646792 A JP 20646792A JP H0649256 A JPH0649256 A JP H0649256A
- Authority
- JP
- Japan
- Prior art keywords
- resin
- weight
- styrene
- hydrogenated
- foaming
- 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
Landscapes
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、耐衝撃吸収性、剛性及
び耐油性に優れ、かつ発泡性及び二次加工性に特に優れ
たポリスチレン系樹脂発泡体に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polystyrene resin foam which is excellent in shock absorption resistance, rigidity and oil resistance, and particularly excellent in foamability and secondary processability.
【０００２】[0002]
【従来の技術】ポリスチレン樹脂は剛性があり寸法安定
性がよく、廉価であることから、成形用途に広く使用さ
れているが、耐衝撃性が不足しているため、用途の拡大
が妨げられている。特に発泡成形体においては、柔らか
さや衝撃吸収性に欠ける。一方、ポリエチレン系樹脂か
らなる発泡成形体は、柔軟性があるが剛性に欠け、また
発泡に適した溶融粘度領域が狭いため、架橋が必要とな
り、用途が限られている。更に、ポリプロピレン系樹脂
からなる発泡成形体は、柔軟性や衝撃吸収性に優れ、ポ
リエチレン系発泡体に比べて、剛性を有する。しかしポ
リプロピレン系樹脂の発泡工程には前処理などの工程が
必要であり、ポリスチレン系樹脂又はポリエチレン系樹
脂の発泡体に比べて、製造コストが高くなる。ポリエチ
レン系樹脂の欠点を補うために、ポリエチレン系樹脂と
ポリスチレン樹脂との複合化が試みられてきた。ビーズ
発泡成形においては、スチレンモノマーをポリエチレン
系樹脂に含浸させた後、グラフト重合させ、複合化した
樹脂組成物、予備発泡粒子及び発泡成形体が提案されて
いる。たとえば、特公昭５２−３３１５６号公報、特公
昭５８−５７４５３号公報には、ポリエチレン系樹脂の
スチレンモノマーのグラフト重合方法及びスチレン改質
ポリエチレン系樹脂の発泡体が開示されている。しか
し、この方法は、ポリエチレン系樹脂のグラフト重合工
程が煩雑であるのみならず、架橋も必要であり、製造コ
ストも高くなる。特公昭６３−３８０５８号公報及び特
公平２−１８６９２号公報には、ポリスチレン系樹脂と
ポリエチレン系樹脂の混合物の押出発泡成形についての
技術がに開示されている。しかし、ポリスチレン系樹脂
とポリオレフィン系樹脂とは相溶性が乏しいため、両者
を機械的に混合しても剛性、耐衝撃性の乏しい物しか得
られない。両者の相溶性を向上させるために、ポリスチ
レン系樹脂とポリオレフィン系樹脂に、特定のスチレン
−共役ジエンブロック共重合体、その水素添加ブロック
共重合体又はエチレン−酢酸ビニル共重合体を添加した
組成物が提案されている。たとえば、特公昭６２−１２
８１２号公報、特公昭６３−３４７８２号公報及び特開
平１−１７４５５０号公報には、スチレン−ブタジエン
−スチレンブロック共重合体水素添加物又は（スチレン
−ブタジエン）ｎブロック共重合体水素添加物をポリス
チレン系樹脂とポリオレフィン系樹脂の相溶化剤として
使用する技術が開示されている。しかしながら、ポリス
チレン系樹脂とポリオレフィン系樹脂の特性をバランス
よく併せ持つ発泡成形体は未だ得られていない。BACKGROUND OF THE INVENTION Polystyrene resins are widely used in molding applications because they are rigid, have good dimensional stability, and are inexpensive, but their impact resistance is insufficient, which hinders their expansion. There is. In particular, the foamed product lacks in softness and shock absorption. On the other hand, a foamed molded product made of a polyethylene-based resin has flexibility but lacks rigidity, and has a narrow melt viscosity region suitable for foaming, so that cross-linking is required and its use is limited. Further, the foamed molded product made of polypropylene resin is excellent in flexibility and impact absorption and has rigidity as compared with the polyethylene foamed product. However, the foaming process of the polypropylene resin requires a process such as pretreatment, and the manufacturing cost is higher than that of the foamed product of the polystyrene resin or the polyethylene resin. In order to make up for the drawbacks of polyethylene resins, attempts have been made to combine polyethylene resins and polystyrene resins. In the bead foam molding, a resin composition, pre-expanded particles, and a foam molded product, which are obtained by impregnating a polyethylene resin with a styrene monomer and then graft-polymerizing the resin, have been proposed. For example, JP-B-52-33156 and JP-B-58-57453 disclose a method for graft-polymerizing a styrene monomer of a polyethylene resin and a foam of a styrene-modified polyethylene resin. However, this method not only complicates the polyethylene-based resin graft polymerization step, but also requires cross-linking, resulting in high manufacturing cost. Japanese Patent Publication No. 63-38058 and Japanese Patent Publication No. 2-18692 disclose a technique for extrusion foam molding of a mixture of a polystyrene resin and a polyethylene resin. However, since the polystyrene-based resin and the polyolefin-based resin have poor compatibility, even if they are mechanically mixed, only a product having poor rigidity and impact resistance can be obtained. A composition obtained by adding a specific styrene-conjugated diene block copolymer, a hydrogenated block copolymer thereof, or an ethylene-vinyl acetate copolymer to a polystyrene resin and a polyolefin resin in order to improve the compatibility of both. Is proposed. For example, Japanese Patent Publication No. 62-12
No. 812, JP-B-63-34782 and JP-A-1-174550 disclose styrene-butadiene-styrene block copolymer hydrogenated products or (styrene-butadiene) n block copolymer hydrogenated products as polystyrene. A technique of using as a compatibilizing agent for a base resin and a polyolefin resin is disclosed. However, a foamed molded article having a well-balanced combination of properties of polystyrene resin and polyolefin resin has not yet been obtained.
【０００３】[0003]
【発明が解決しようとする課題】かかる状況に鑑み、本
発明が解決しようとする課題は、従来の技術の問題点を
解消し、耐衝撃吸収性、剛性及び耐油性に優れ、かつ発
泡性及び二次加工性に特に優れたポリスチレン系樹脂発
泡体を提供する点に存する。In view of the above situation, the problem to be solved by the present invention is to solve the problems of the prior art, and to provide excellent shock absorption resistance, rigidity and oil resistance, and foamability and This is to provide a polystyrene-based resin foam that is particularly excellent in secondary processability.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、上記に課
題を解決すべく鋭意検討の結果、本発明に到達したもの
である。すなわち、本発明は、下記（Ａ）〜（Ｃ）成分
からなる樹脂組成物を発泡させて得られるポリスチレン
系樹脂発泡体に係るものである。 （Ａ）ポリスチレン系樹脂 ３５〜７５重量％ （Ｂ）ポリエチレン系樹脂 １０〜５０重量％ （Ｃ）スチレンブロック−イソプレンブロック−スチレ
ンブロックからなるトリブロック共重合体のイソプレン
ブロック部分の二重結合の７０％以上が水素添加された
水素添加トリブロック共重合体であって、その数平均分
子量が１０，０００〜４００，０００であり、スチレン
ブロック部分の重量割合が４０〜７０重量％である水素
添加トリブロック共重合体 ３〜３５重量ｗｔ％The present inventors have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention relates to a polystyrene-based resin foam obtained by foaming a resin composition comprising the following components (A) to (C). (A) Polystyrene resin 35 to 75% by weight (B) Polyethylene resin 10 to 50% by weight (C) 70 of double bond of isoprene block portion of triblock copolymer consisting of styrene block-isoprene block-styrene block % Hydrogenated triblock copolymer having a hydrogen content of 10,000 to 400,000, and a styrene block portion weight ratio of 40 to 70% by weight. Block copolymer 3-35 wt%
【０００５】以下、詳細に説明する。本発明の（Ａ）ポ
リスチレン系樹脂とは、スチレンモノマーを塊状重合法
又は懸濁重合法により重合させて得られるポリスチレン
（ＧＰＰＳ）及びブタジエンゴムやスチレン−ブタジエ
ンブロック共重合体をスチレンモノマー中に溶解した
後、塊状重合法や塊状−懸濁二段重合法により重合させ
て得られるゴム変性ポリスチレン（ＨＩＰＳ）、更に、
ＧＰＰＳとスチレン−ブタジエンブロック共重合体を１
軸又は多軸の押出機やバンバリーミキサーなどの汎用混
練機を用いて加熱混練して得られるポリスチレン樹脂組
成物を含む概念である。ポリスチレン系樹脂には、流動
性調節のために、ミネラルオイル、流動パラフィンなど
パラフィン系、ナフテン系、芳香族系の炭化水素の１種
又は２種以上混合した可塑剤が用いられるが、この可塑
剤の含有量は、通常５重量％以下、好ましくは３重量％
以下である。該含有量が５重量％を超えると流動性が高
すぎ、ポリエチレン系樹脂との混練性が悪くなり、発泡
時に良好な発泡体を得ることが難しくなることがある。The details will be described below. The (A) polystyrene resin of the present invention means polystyrene (GPPS) obtained by polymerizing a styrene monomer by a bulk polymerization method or a suspension polymerization method and a butadiene rubber or a styrene-butadiene block copolymer dissolved in the styrene monomer. After that, rubber-modified polystyrene (HIPS) obtained by polymerizing by bulk polymerization method or bulk-suspension two-stage polymerization method,
1 of GPPS and styrene-butadiene block copolymer
This is a concept including a polystyrene resin composition obtained by heating and kneading using a general-purpose kneader such as a twin-screw or multi-screw extruder or a Banbury mixer. For the polystyrene-based resin, a plasticizer in which one or more of paraffin-based, naphthene-based, and aromatic hydrocarbons such as mineral oil and liquid paraffin are mixed is used for fluidity control. Content of 5% by weight or less, preferably 3% by weight
It is the following. When the content exceeds 5% by weight, the fluidity is too high, the kneading property with the polyethylene resin is deteriorated, and it may be difficult to obtain a good foam at the time of foaming.
【０００６】本発明の（Ｂ）ポリエチレン系樹脂とは、
エチレンホモ重合体、エチレン−α−オレフィン共重合
体、エチレン−酢酸ビニル共重合体、又はこれらの混合
物を含む概念であり、たとえば低密度ポリエチレン（Ｌ
ＤＰＥ）、高密度ポリエチレン（ＨＤＰＥ）、直鎖状低
密度ポリエチレン（ＬＬＤＰＥ）、エチレン−プロピレ
ン共重合体、エチレン−酢酸ビニル共重合体（ＥＶＡ）
などを例示することができる。ここで、ポリエチレン系
樹脂の５重量％以上が、密度０．９４ｇ／ｃｍ 3 以上の
高密度ポリエチレン樹脂であることが好ましい。このこ
とにより、通常の発泡成形温度（１００〜１３０℃）に
おける溶融収縮を防止し、高倍率発泡が可能となる。The (B) polyethylene resin of the present invention is
Ethylene homopolymer, ethylene-α-olefin copolymerization
Polymer, ethylene-vinyl acetate copolymer, or a mixture thereof
This is a concept that includes a product such as low density polyethylene (L
DPE), high density polyethylene (HDPE), linear low
Density polyethylene (LLDPE), ethylene-propylene
Copolymer, ethylene-vinyl acetate copolymer (EVA)
And the like. Where polyethylene type
5% by weight or more of the resin has a density of 0.94 g / cm 3More than
It is preferably a high density polyethylene resin. this child
By, the normal foam molding temperature (100 ~ 130 ℃)
Melt shrinkage is prevented and high-magnification foaming becomes possible.
【０００７】本発明の（Ｃ）水素添加トリブロック共重
合体とは、スチレンブロック−イソプレンブロック−ス
チレンブロックからなるトリブロック共重合体のイソプ
レンブロック部分の二重結合の７０％以上が水素添加さ
れた水素添加トリブロック共重合体であって、その数平
均分子量が１０，０００〜４００，０００であり、スチ
レンブロック部分の重量割合が４０〜７０重量％である
水素添加トリブロック共重合体である。本発明の（Ｃ）
成分は、相溶化剤として作用する。The hydrogenated triblock copolymer (C) of the present invention means that 70% or more of the double bonds in the isoprene block portion of the triblock copolymer comprising styrene block-isoprene block-styrene block are hydrogenated. A hydrogenated triblock copolymer having a number average molecular weight of 10,000 to 400,000 and a styrene block portion weight ratio of 40 to 70% by weight. . (C) of the present invention
The component acts as a compatibilizer.
【０００８】水素添加トリブロック共重合体のイソプレ
ンブロック部分の二重結合の水素添加割合は７０％以
上、好ましくは９０％以上である。該割合が過少な場
合、相溶性が悪く、発泡性に劣る。水素添加トリブロッ
ク共重合体の数平均分子量は１０，０００〜４００，０
００、好ましくは１２，０００〜３５０，０００であ
る。該分子量が過小な場合は、相溶性が悪く、発泡性に
劣り、一方該分子量が過大な場合も発泡性に劣る。水素
添加トリブロック共重合体のスチレンブロック部分の重
量割合は４０〜７０重量％、好ましくは４０〜６５重量
％である。該割合が過小な場合は発泡性及び二次加工性
に劣り、一方該割合が過大な場合は、発泡性及び二次加
工性に劣る。本発明の（Ｃ）成分は、スチレンブロック
−イソプレンブロック−スチレンブロックからなるトリ
ブロック共重合体であることが必要である。本発明によ
ることなく、スチレンブロック−イソプレンブロックか
らなるジブロック共重合体を用いた場合には、発泡性及
び二次加工性に劣る。The hydrogenation ratio of the double bond in the isoprene block portion of the hydrogenated triblock copolymer is 70% or more, preferably 90% or more. When the ratio is too small, the compatibility is poor and the foamability is poor. The number average molecular weight of the hydrogenated triblock copolymer is 10,000 to 400,0.
00, preferably 12,000 to 350,000. If the molecular weight is too small, the compatibility is poor and the foamability is poor, while if the molecular weight is too large, the foamability is poor. The weight ratio of the styrene block portion of the hydrogenated triblock copolymer is 40 to 70% by weight, preferably 40 to 65% by weight. When the ratio is too small, the foaming property and the secondary processability are poor, while when the ratio is too large, the foaming property and the secondary processability are poor. The component (C) of the present invention needs to be a triblock copolymer composed of styrene block-isoprene block-styrene block. When a diblock copolymer composed of a styrene block-isoprene block is used without depending on the present invention, the foamability and the secondary processability are poor.
【０００９】本発明の条件を満足しない水素添加ブロッ
ク共重合体を用いても、ポリスチレン樹脂とポリエチレ
ン系樹脂との相溶性が改善されないめ、樹脂組成物を発
泡成形したときに気泡の破れが多く発生し、連泡率が高
くなり、更に収縮が生じ易く、高発泡倍率を得ることが
できない。また、発泡体の剛性、衝撃吸収性が劣り、発
泡体を圧縮したときの気泡膜の破れも起こり易い。Even if a hydrogenated block copolymer which does not satisfy the conditions of the present invention is used, the compatibility between the polystyrene resin and the polyethylene resin is not improved, and the foaming of the resin composition often causes the bubbles to be broken. It occurs, the open cell ratio becomes high, and further shrinkage easily occurs, so that a high expansion ratio cannot be obtained. In addition, the rigidity and impact absorption of the foam are poor, and tearing of the cell membrane when the foam is compressed is likely to occur.
【００１０】本発明の（Ｃ）水素添加ブロック共重合体
を得るには、公知の未水素添加ブロック共重合体を、た
とえば特公昭４２−８７０４号公報、特公昭４３−６６
３６号公報などに記載された方法により、水素添加すれ
ばよい。なお、（Ｃ）水素添加ブロック共重合体とし
て、市販の該当品を用いてもよい。In order to obtain the (C) hydrogenated block copolymer of the present invention, known non-hydrogenated block copolymers can be prepared, for example, from Japanese Examined Patent Publication Nos. 42-8704 and 43-66.
Hydrogen may be added by the method described in Japanese Patent Publication No. 36-36. A commercially available product may be used as the (C) hydrogenated block copolymer.
【００１１】本発明における（Ａ）〜（Ｃ）成分の使用
量割合は、（Ａ）ポリスチレン系樹脂３５〜７５重量
％、好ましくは４０〜７０重量％であり、（Ｂ）ポリエ
チレン系樹脂１０〜５０重量％、好ましくは１５〜５０
重量％であり、（Ｃ）水素添加トリブロック共重合体３
〜２５重量％、好ましくは５〜２０重量％である。
（Ａ）ポリスチレン系樹脂が過少であると発泡性及び二
次加工性に劣り、一方過多であると発泡体の剛性が高く
なりすぎ、二次加工性に劣る。（Ｂ）ポリエチレン系樹
脂が過少又は過多であると発泡性及び二次加工性に劣
る。（Ｃ）水素添加トリブロック共重合体が過少である
と発泡性及び二次加工性に劣り、一方過多であると剛性
などの機械的特性に劣る。The proportions of the components (A) to (C) used in the present invention are 35 to 75% by weight, preferably 40 to 70% by weight of the (A) polystyrene resin, and (B) the polyethylene resin 10 to 10. 50% by weight, preferably 15-50
% By weight, and (C) hydrogenated triblock copolymer 3
-25% by weight, preferably 5-20% by weight.
If the amount of the polystyrene resin (A) is too small, the foaming property and the secondary processability are poor, while if it is too large, the rigidity of the foam becomes too high and the secondary processability is poor. If the polyethylene resin (B) is too little or too much, the foamability and the secondary processability will be poor. If the amount of the hydrogenated triblock copolymer (C) is too small, the foamability and the secondary processability will be poor, while if it is too large, the mechanical properties such as rigidity will be poor.
【００１２】本発明における樹脂組成物では、ポリスチ
レン樹脂のマトリックス中に、ポリエチレン系樹脂が微
細な共連続相又は島状になって存在するが、共連続相の
場合はポリエチレン系樹脂相の幅を、また島状の場合は
平均粒子径を、それぞれ１０μｍ以下、好ましくは５μ
ｍ以下に調節することが望ましい。ポリエチレン系樹脂
相の幅が１０μｍを超えたり、平均粒子径が１０μｍを
超えると、発泡成形した時に気泡の破れが多くなり、ま
た発泡体の剛性や衝撃吸収性も劣ったものとなることが
ある。該樹脂相の幅又は平均粒子径としては、樹脂組成
物の薄片の透過型電子顕微鏡写真及び画像解析装置によ
り得られる値を用いる。In the resin composition of the present invention, the polyethylene-based resin is present in the matrix of the polystyrene resin in the form of a fine co-continuous phase or island. In the case of the co-continuous phase, the width of the polyethylene-based resin phase is reduced. In the case of islands, the average particle size is 10 μm or less, preferably 5 μm.
It is desirable to adjust to m or less. If the width of the polyethylene-based resin phase exceeds 10 μm or the average particle size exceeds 10 μm, the cells are often broken during foam molding, and the rigidity and impact absorption of the foam may be poor. . As the width or average particle diameter of the resin phase, a value obtained by a transmission electron micrograph of a thin piece of the resin composition and an image analyzer is used.
【００１３】本発明の樹脂組成物を用いて発泡体を得る
には、（Ａ）ポリスチレン系樹脂、（Ｂ）ポリエチレン
系樹脂及び（Ｃ）水素添加トリブロック共重合体の所定
量を、たとえば単軸押出機、二軸押出機などの溶融混練
機で溶融混練してペレット化したもの（１９７３年初版
「プラスチック フォームハンドブック」牧 廣、小坂
田 篤編、日刊工業新聞社発行、第１５８頁〜１７４
頁、１９８２年；初版「プラスチック加工の基礎」高分
子学会編、工業調査会発行，第２９８頁〜第３１０頁に
記載されている。）を、型内発泡法や押出発泡法により
発泡体とすればよい。発泡剤としては、ブタン、ペンタ
ン、フレオンなどの揮発性溶剤型発泡剤を用いることが
できる。発泡体の平均発泡倍率は、好ましくは５〜６０
倍である。In order to obtain a foam using the resin composition of the present invention, a predetermined amount of (A) polystyrene resin, (B) polyethylene resin and (C) hydrogenated triblock copolymer is used, for example. Melt-kneaded and pelletized by a melt-kneader such as a twin-screw extruder or twin-screw extruder (1973 first edition "Plastic Form Handbook" Makihiro, Atsushi Kosakada, Nikkan Kogyo Shimbun, pp. 158-174
Pp. 1982; first edition "Basics of Plastic Processing" edited by The Polymer Society of Japan, published by Industrial Research Society, pp. 298 to 310. ) May be made into a foam by an in-mold foaming method or an extrusion foaming method. As the foaming agent, a volatile solvent type foaming agent such as butane, pentane or freon can be used. The average expansion ratio of the foam is preferably 5 to 60.
Double.
【００１４】なお、本発明の樹脂組成物を用いるに際し
ては、必要に応じて任意の充填剤、たとえばガラス繊
維、チタン白、カーボン、シリカ、タルク、マイカ、酸
化亜鉛などを併用することがき、更に必要に応じて、難
燃剤、酸化防止剤、熱安定剤、紫外線吸収剤、滑剤、帯
電防止剤などの添加剤を用いることもできる。When using the resin composition of the present invention, if desired, any filler such as glass fiber, titanium white, carbon, silica, talc, mica, zinc oxide, etc. may be used in combination. If necessary, additives such as flame retardants, antioxidants, heat stabilizers, ultraviolet absorbers, lubricants and antistatic agents can be used.
【００１５】かくして得られる本発明のポリスチレン系
樹脂発泡体は、耐衝撃吸収性、剛性及び耐油性に優れ、
かつ発泡性及び二次加工性に特に優れたものであり、家
電部品、自動車部品、食品包装等用、その他の広範囲な
用途に使用可能である。The polystyrene resin foam of the present invention thus obtained is excellent in impact resistance, rigidity and oil resistance,
In addition, it is particularly excellent in foamability and secondary processability, and can be used for a wide range of applications such as home electric appliance parts, automobile parts, food packaging, and the like.
【００１６】[0016]
【実施例】以下に実施例を示す。本発明はこれらの実施
例に限定されるものではない。実施例に示されたデータ
は、次の方法に基づいて測定されたものである。 （１）発泡性：ペッレト５ｇをオートクレーブに入れ、
ｎ−ブタン１５ｇ加えて、６０℃で５時間放置し、その
後１２０℃で発泡させ、予備発泡粒子を得た。評価結果
は下記のように表示した。 〇：５〜６０倍に発泡、割れ、ひびなどがない。 ×：発泡せず、割れ、ひびがある。 （２）二次成形性：予備発泡粒子を１００ｍｍ×１００
ｍｍ×１０ｍｍの型に入れ１１０℃で加熱成形し、得ら
れた成形品を割って１００ｍｍ×１０ｍｍの面にある予
備発泡粒子の中で界面で剥がれた割合を融着率とした。
評価結果は下記のように表示した。 〇：良好な成形品が得られ、融着率８０％以上。 △：良好な成形品が得られるが、融着率が８０％未満。 ×：未融着、収縮が起こり、成形品が得られない。EXAMPLES Examples will be shown below. The invention is not limited to these examples. The data shown in the examples are measured according to the following method. (1) Foamability: 5 g of pellets was put in an autoclave,
15 g of n-butane was added, the mixture was allowed to stand at 60 ° C. for 5 hours, and then foamed at 120 ° C. to obtain pre-expanded particles. The evaluation results are displayed as follows. ◯: No foaming, cracking, cracking, etc. 5 to 60 times. X: No foaming, cracking, and cracking. (2) Secondary moldability: 100 mm × 100 of pre-expanded particles
It was put in a mold of mm × 10 mm, heat-molded at 110 ° C., the obtained molded product was divided, and the rate of peeling at the interface in the pre-expanded particles on the surface of 100 mm × 10 mm was defined as the fusion rate.
The evaluation results are displayed as follows. ◯: A good molded product was obtained, and the fusion rate was 80% or more. Δ: A good molded product is obtained, but the fusion rate is less than 80%. X: Unbonding and shrinkage occur, and a molded product cannot be obtained.
【００１７】実施例１〜６、比較例１〜６ 表１〜２記載の成分を、二軸スクリュー押出器（東洋精
機製作所製 型式２Ｓ２５）を用い、２２０℃の温度で
溶融混練し、その後、造粒及び発泡を行った。結果を表
１〜２に示した。Examples 1 to 6 and Comparative Examples 1 to 6 Components shown in Tables 1 and 2 were melt-kneaded at a temperature of 220 ° C. using a twin-screw extruder (Model 2S25 manufactured by Toyo Seiki Seisakusho Co., Ltd.), and then, Granulation and foaming were performed. The results are shown in Tables 1-2.
【００１８】結果から、次のことがわかる。本発明によ
るすべての実施例は、すべての評価項目において満足す
べき結果を示している。一方、（Ｃ）成分を用いなかっ
た比較例１、（Ｃ）成分の代わりにスチレン含有量が過
少な水素添加トリブロック共重合体を用いた比較例２、
（Ａ）成分が過少で、（Ｂ）成分か過多な比較例３、
（Ｃ）成分の代わりにスチレン−ブタジエン共重合体ゴ
ムを用いた比較例５、及び（Ｂ）成分が過少な比較例６
は、発泡性及び二次加工性に劣り、また（Ａ）成分か過
多な比較例４は二次加工性に劣る。The results show the following. All examples according to the present invention show satisfactory results in all evaluation items. On the other hand, Comparative Example 1 in which the component (C) was not used, Comparative Example 2 in which a hydrogenated triblock copolymer having an excessively low styrene content was used in place of the component (C),
Comparative Example 3 in which the component (A) is too small and the component (B) is too large,
Comparative Example 5 in which a styrene-butadiene copolymer rubber was used instead of the component (C), and Comparative Example 6 in which the amount of the component (B) was too small.
Is inferior in foamability and secondary processability, and Comparative Example 4 containing too much component (A) is inferior in secondary processability.
【００１９】[0019]
【表１】 [Table 1]
【００２０】[0020]
【表２】 [Table 2]
【００２１】＊１ ＧＰＰＳ：ポリスチレン樹脂（住友
化学工業社製 スミブライトＥ１６３、ＭＩ＝７、密度
１．０５のＧＰＰＳ） ＊２ ＥＶＡ：酢酸ビニル含有量５重量％のエチレン−
酢酸ビニル共重合体（住友化学工業社製 エバテートＤ
１０４２、密度０．９２、ＭＩ＝１．６） ＊３ ＬＬＤＰＥ：直鎖状低密度ポリエチレン（住友化
学工業社製 スミカセン−Ｌ ＧＡ４０１、密度０．９
３５、ＭＩ＝３） ＊４ ＨＤＰＥ：高密度ポリエチレン（ユニオンポリマ
ー社製 ＵＰポリエチレンＨＤ １１５０−１、密度
０．９５６、ＭＩ＝１５）* 1 GPPS: polystyrene resin (Sumibrite E163 manufactured by Sumitomo Chemical Co., MI = 7, GPPS with a density of 1.05) * 2 EVA: ethylene with a vinyl acetate content of 5% by weight
Vinyl Acetate Copolymer (Evatate D manufactured by Sumitomo Chemical Co., Ltd.
1042, density 0.92, MI = 1.6) * 3 LLDPE: Linear low density polyethylene (Sumikasen-L GA401 manufactured by Sumitomo Chemical Co., Ltd., density 0.9
35, MI = 3) * 4 HDPE: High-density polyethylene (UP Polyethylene HD 1150-1, Union Polymer Co., density 0.956, MI = 15)
【００２２】＊５ ＳＥＰＳ１：水素添加スチレン−イ
ソプレン−スチレントリブロック共重合体（クラレ社製
セプトン ＫＬ２１０４、イソプレンブロック部分の
二重結合の水素添加された割合９７％以上、スチレンブ
ロック部分の重量割合６５重量％、数平均分子量６０，
０００） ＊６ ＳＥＰＳ２：水素添加スチレン−イソプレン−ス
チレントリブロック共重合体（クラレ社製 セプトン
ＫＬ２００３、イソプレンブロック部分の二重結合の水
素添加された割合９７％以上、スチレンブロック部分の
重量割合１３重量％、数平均分子量１４０，０００） ＊７ ＳＢＳ：スチレン−ブタジエン共重合体ゴム（シ
ェル化学社製 カリフレックスＴＲ１１０１、スチレン
含量３０重量％）* 5 SEPS1: hydrogenated styrene-isoprene-styrene triblock copolymer (Septon KL2104, manufactured by Kuraray Co., Ltd., the hydrogenated ratio of double bonds in the isoprene block portion is 97% or more, and the weight ratio of the styrene block portion is 65%). % By weight, number average molecular weight 60,
000) * 6 SEPS2: hydrogenated styrene-isoprene-styrene triblock copolymer (Kuraray Septon)
KL2003, hydrogenated ratio of double bond of isoprene block portion is 97% or more, weight ratio of styrene block portion is 13% by weight, number average molecular weight 140,000) * 7 SBS: styrene-butadiene copolymer rubber (shell chemistry (Calibrex TR1101, styrene content 30% by weight)
【００２３】[0023]
【発明の効果】以上説明したとおり、本発明により、耐
衝撃吸収性、剛性及び耐油性に優れ、かつ発泡性及び二
次加工性に特に優れたポリスチレン系樹脂発泡体を提供
することができた。As described above, according to the present invention, it is possible to provide a polystyrene resin foam which is excellent in impact absorption resistance, rigidity and oil resistance, and particularly excellent in foamability and secondary processability. .
───────────────────────────────────────────────────── 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 23/04 ＬＣＨ 7107−4Ｊ ＬＣＭ 7107−4Ｊ ＬＣＮ 7107−4Ｊ Ｃ０８Ｌ 25:00 ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location // C08L 23/04 LCH 7107-4J LCM 7107-4J LCN 7107-4J C08L 25:00
Claims (2)
成物を発泡させて得られるポリスチレン系樹脂発泡体。 （Ａ）ポリスチレン系樹脂 ３５〜７５重量％ （Ｂ）ポリエチレン系樹脂 １０〜５０重量％ （Ｃ）スチレンブロック−イソプレンブロック−スチレ
ンブロックからなるトリブロック共重合体のイソプレン
ブロック部分の二重結合の７０％以上が水素添加された
水素添加トリブロック共重合体であって、その数平均分
子量が１０，０００〜４００，０００であり、スチレン
ブロック部分の重量割合が４０〜７０重量％である水素
添加トリブロック共重合体 ３〜２５重量ｗｔ％1. A polystyrene resin foam obtained by foaming a resin composition comprising the following components (A) to (C). (A) Polystyrene resin 35 to 75% by weight (B) Polyethylene resin 10 to 50% by weight (C) 70 of double bond of isoprene block portion of triblock copolymer consisting of styrene block-isoprene block-styrene block % Hydrogenated triblock copolymer having a hydrogen content of 10,000 to 400,000, and a styrene block portion weight ratio of 40 to 70% by weight. Block copolymer 3 to 25 wt%
が、密度０．９４ｇ／ｃｍ3 以上の高密度ポリエチレン
樹脂である請求項１記載のポリスチレン系樹脂発泡体。2. The polystyrene resin foam according to claim 1, wherein 5% by weight or more of the (B) polyethylene resin is a high density polyethylene resin having a density of 0.94 g / cm 3 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4206467A JP2795079B2 (en) | 1992-08-03 | 1992-08-03 | Polystyrene resin foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4206467A JP2795079B2 (en) | 1992-08-03 | 1992-08-03 | Polystyrene resin foam |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0649256A true JPH0649256A (en) | 1994-02-22 |
| JP2795079B2 JP2795079B2 (en) | 1998-09-10 |
Family
ID=16523863
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4206467A Expired - Lifetime JP2795079B2 (en) | 1992-08-03 | 1992-08-03 | Polystyrene resin foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2795079B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5733825A (en) * | 1996-11-27 | 1998-03-31 | Minnesota Mining And Manufacturing Company | Undrawn tough durably melt-bondable macrodenier thermoplastic multicomponent filaments |
| JP2009108174A (en) * | 2007-10-30 | 2009-05-21 | Sanwa Kako Co Ltd | Super-flexible polyethylene foam and process of its production |
| WO2009099482A1 (en) | 2008-02-06 | 2009-08-13 | Dow Global Technologies, Inc. | Article and method of producing a low density foam blend of styrenic polymer and polyolefin |
| IT201600080035A1 (en) * | 2016-07-29 | 2018-01-29 | Versalis Spa | Block expandable polymeric compositions |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2718001A1 (en) * | 2008-03-13 | 2009-09-17 | Basf Se | Elastic molded foam based on polyolefin/styrene polymer mixtures |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63125538A (en) * | 1986-11-14 | 1988-05-28 | Japan Styrene Paper Co Ltd | Modified expanded high-density polyethylene resin particle |
| JPH01174550A (en) * | 1987-12-28 | 1989-07-11 | Kuraray Co Ltd | Hydrogenated block copolymer composition |
| JPH02232240A (en) * | 1989-03-03 | 1990-09-14 | Jsp Corp | Low-density foam of mixed resin and its production |
| JPH0489846A (en) * | 1990-08-01 | 1992-03-24 | Sumitomo Chem Co Ltd | Pre-expanded polystyrene particle and expanded bead molding |
-
1992
- 1992-08-03 JP JP4206467A patent/JP2795079B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63125538A (en) * | 1986-11-14 | 1988-05-28 | Japan Styrene Paper Co Ltd | Modified expanded high-density polyethylene resin particle |
| JPH01174550A (en) * | 1987-12-28 | 1989-07-11 | Kuraray Co Ltd | Hydrogenated block copolymer composition |
| JPH02232240A (en) * | 1989-03-03 | 1990-09-14 | Jsp Corp | Low-density foam of mixed resin and its production |
| JPH0489846A (en) * | 1990-08-01 | 1992-03-24 | Sumitomo Chem Co Ltd | Pre-expanded polystyrene particle and expanded bead molding |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5733825A (en) * | 1996-11-27 | 1998-03-31 | Minnesota Mining And Manufacturing Company | Undrawn tough durably melt-bondable macrodenier thermoplastic multicomponent filaments |
| JP2009108174A (en) * | 2007-10-30 | 2009-05-21 | Sanwa Kako Co Ltd | Super-flexible polyethylene foam and process of its production |
| WO2009099482A1 (en) | 2008-02-06 | 2009-08-13 | Dow Global Technologies, Inc. | Article and method of producing a low density foam blend of styrenic polymer and polyolefin |
| IT201600080035A1 (en) * | 2016-07-29 | 2018-01-29 | Versalis Spa | Block expandable polymeric compositions |
| WO2018019995A1 (en) * | 2016-07-29 | 2018-02-01 | Versalis S.P.A. | Block expandable polymeric compositions |
| CN109476894A (en) * | 2016-07-29 | 2019-03-15 | 维尔萨利斯股份公司 | Block expandable polymer compositions |
| CN109476894B (en) * | 2016-07-29 | 2021-05-25 | 维尔萨利斯股份公司 | Block expandable polymer composition |
| US11078342B2 (en) | 2016-07-29 | 2021-08-03 | Versalis S.P.A. | Block expandable polymeric compositions |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2795079B2 (en) | 1998-09-10 |
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