JPH04220439A - Polystyrene resin foam - Google Patents
Polystyrene resin foamInfo
- Publication number
- JPH04220439A JPH04220439A JP40431890A JP40431890A JPH04220439A JP H04220439 A JPH04220439 A JP H04220439A JP 40431890 A JP40431890 A JP 40431890A JP 40431890 A JP40431890 A JP 40431890A JP H04220439 A JPH04220439 A JP H04220439A
- Authority
- JP
- Japan
- Prior art keywords
- polystyrene
- block copolymer
- resin
- conjugated diene
- vinyl
- 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.)
- Pending
Links
- 229920005990 polystyrene resin Polymers 0.000 title claims abstract description 21
- 239000006260 foam Substances 0.000 title abstract description 13
- 229920001400 block copolymer Polymers 0.000 claims abstract description 27
- 229920013716 polyethylene resin Polymers 0.000 claims abstract description 20
- 150000001993 dienes Chemical class 0.000 claims abstract description 16
- 239000004793 Polystyrene Substances 0.000 claims abstract description 14
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 229920002223 polystyrene Polymers 0.000 claims abstract description 13
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 4
- 125000004185 ester group Chemical group 0.000 claims abstract description 4
- 150000001491 aromatic compounds Chemical class 0.000 claims description 16
- 238000005187 foaming Methods 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 229920001577 copolymer Polymers 0.000 claims description 9
- 229920001903 high density polyethylene Polymers 0.000 claims description 9
- 239000004700 high-density polyethylene Substances 0.000 claims description 9
- 229920006327 polystyrene foam Polymers 0.000 claims description 9
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 6
- 239000004088 foaming agent Substances 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 4
- 229920002554 vinyl polymer Polymers 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 239000011342 resin composition Substances 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 claims description 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 claims description 2
- 229920001112 grafted polyolefin Polymers 0.000 claims description 2
- 229920005669 high impact polystyrene Polymers 0.000 claims description 2
- 239000004797 high-impact polystyrene Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 239000004711 α-olefin Substances 0.000 claims description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims 1
- 229920001893 acrylonitrile styrene Polymers 0.000 claims 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims 1
- 238000010097 foam moulding Methods 0.000 abstract description 9
- 229920005672 polyolefin resin Polymers 0.000 abstract description 7
- 238000004132 cross linking Methods 0.000 abstract description 4
- 229920000098 polyolefin Polymers 0.000 abstract description 4
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 239000004604 Blowing Agent Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 description 9
- -1 polypropylene Polymers 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000035939 shock Effects 0.000 description 7
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- 229920001684 low density polyethylene Polymers 0.000 description 3
- 239000004702 low-density polyethylene Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000008188 pellet Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 2
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 description 2
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 description 1
- FALRKNHUBBKYCC-UHFFFAOYSA-N 2-(chloromethyl)pyridine-3-carbonitrile Chemical compound ClCC1=NC=CC=C1C#N FALRKNHUBBKYCC-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000805 composite resin Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005629 polypropylene homopolymer Polymers 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229940014800 succinic anhydride Drugs 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000010215 titanium dioxide Nutrition 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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、耐衝撃吸収性に優れ、
かつ剛性を持ち合わせるポリスチレン系発泡体に関する
。[Industrial Application Field] The present invention has excellent shock absorption properties,
The present invention relates to a polystyrene foam that also has rigidity.
【０００２】0002
【従来の技術】ポリスチレン系樹脂は剛性があり寸法安
定性が良く、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やわら
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せまいため架橋が必要とな
り用途が限られている。また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、剛性も持ち合わせている。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、ポリエチレン系樹脂
の発泡に比べて、製造コストが高くなる。[Prior Art] Polystyrene resin is widely used in molding applications because it is rigid, has good dimensional stability, and is inexpensive, but its lack of impact resistance has hindered the expansion of its applications. ing. In particular, foam molded products lack softness and shock absorption properties. On the other hand, foamed molded products made of polyethylene resin are flexible but lack rigidity, and the range of melt viscosity suitable for foaming is narrow, requiring crosslinking, which limits their uses. In addition, foamed molded products made of polypropylene resin have excellent flexibility and shock absorption properties, and are also more rigid than polyethylene foamed products. However, the foaming process of polypropylene resin requires steps such as pretreatment, and the manufacturing cost is higher than that of foaming polystyrene or polyethylene resin.
【０００３】前記ポリエチレン系樹脂の欠点を補うため
にポリスチレン系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、発泡成形体が提案され
ている。例えば特公昭５２−３３１５６公報、特公昭５
８−５７４５３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およびスチレン改質ポリエ
チレン系樹脂の発泡を開示している。しかしポリエチレ
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、より製造コストも高くなる。[0003] In order to compensate for the drawbacks of the polyethylene resin, attempts have been made to combine it with a polystyrene resin. In bead foam molding, composite resin compositions, pre-expanded particles, and foam molded products have been proposed in which a polyethylene resin is impregnated with a styrene monomer and then graft polymerized to form a composite. For example, Special Publication No. 52-33156, Special Publication No. 52-33156,
8-57453 discloses a method for graft polymerizing a styrene monomer in a polyethylene resin and foaming a styrene-modified polyethylene resin. However, not only is the graft polymerization process of polyethylene resin complicated;
Crosslinking is also required, which increases manufacturing costs.
【０００４】一方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特公昭６
３−３８０５８公報や特公平２−１８６９２公報に開示
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、両者を機械的に溶融
混合しても剛性、耐衝撃性の乏しい物しか得られない。On the other hand, the technology for extrusion foam molding of a mixture of polystyrene resin and polyethylene resin was developed in
This method is disclosed in Japanese Patent Publication No. 3-38058 and Japanese Patent Publication No. 2-18692. However, since polystyrene resins and polyolefin resins have poor compatibility, even if they are mechanically melted and mixed, only a product with poor rigidity and impact resistance can be obtained.
【０００５】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、またはエチレン−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。例えば特公昭６２−１２
８１２公報や特公昭６２−３４７８２公報、特開平１−
１７４５５０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添物あるいは（スチレン−ブタジエ
ン）ｎブロック共重合体水添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を
開示している。In order to improve the compatibility between the two, a specific styrene-conjugated diene block copolymer, its hydrogenated block copolymer, or ethylene-vinyl acetate copolymer is added to the polystyrene resin and polyolefin resin. A composition has been proposed. For example, special public service
812 Publication, Japanese Patent Publication No. 62-34782, Japanese Patent Publication No. 1999-1-
Publication No. 174550 discloses a technique of using a hydrogenated styrene-butadiene-styrene block copolymer or a hydrogenated (styrene-butadiene) n-block copolymer as a compatibilizer for polystyrene resin and polyolefin resin. There is.
【０００６】しかしながら発泡成形に関する技術は開示
されておらず、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良く持つ発泡成形体は未だ得られ
ていない。However, no technology regarding foam molding has been disclosed, and a foam molded article having a well-balanced property of polystyrene resin and polyolefin resin has not yet been obtained.
【０００７】[0007]
【発明が解決しようとする課題】かかる情況下において
本発明の目的は、通常用いられるポリスチレンおよびポ
リエチレン用発泡成形機を用い、かつ架橋工程なしで発
泡可能で、衝撃吸収性、耐油性に優れ、かつある程度の
剛性を持つポリスチレン系発泡成形品を得ることにある
。SUMMARY OF THE INVENTION Under such circumstances, the object of the present invention is to produce a foam that can be foamed using a commonly used foam molding machine for polystyrene and polyethylene without a crosslinking process, has excellent shock absorption properties and oil resistance, and has excellent shock absorption and oil resistance. The object of the present invention is to obtain a polystyrene foam molded product having a certain degree of rigidity.
【０００８】[0008]
【課題を解決するための手段】本発明は、 （Ａ）ポリ
スチレン系樹脂、（Ｂ）ポリエチレン系樹脂、 （Ｃ）
第三成分よりなり、かつ当該第三成分が、
（ｉ）ビニル置換芳香族化合物重合体ブロックと共役ジ
エン系重合体ブロックを少なくとも１個有するビニル置
換芳香族化合物−共役ジエンブロック共重合体、（ｉｉ
） （ｉ）のビニル置換芳香族化合物−共役ジエンブロ
ック共重合体中の二重結合の一部または全部が水素で飽
和した水素添加ビニル置換芳香族化合物−共役ジエンブ
ロック共重合体、
（ｉｉｉ） （ｉ）または （ｉｉ） のビニル置換芳
香族化合物−共役ジエンブロック共重合体中に有機酸あ
るいは酸無水物あるいはエステル基を０．５ｗｔ％以上
含むビニル置換芳香族化合物−共役ジエンブロック共重
合体、（ｉｖ） ポリスチレン含量２０ｗｔ％ 以上で
かつグラフト率７１％ 以上であるポリスチレングラフ
トポリオレフィンから選ばれる少なくとも１種である樹
脂組成物を揮発性発泡剤により発泡させたことを特徴と
するポリスチレン系発泡体であり、好ましくは、
（Ａ）ポリスチレン系樹脂 ７０ 〜３０重量％（
Ｂ）ポリエチレン系樹脂 １０ 〜６５重量％（Ｃ
）第三成分 ５ 〜２０重
量％よりなり、かつ、（Ｂ） ポリエチレン系樹脂 １
００重量部の中に密度 ０．９４ ｇ／ｃｍ３ 以上の
高密度ポリエチレンを少なくとも５重量部を含有する樹
脂組成物を揮発性発泡剤により発泡させたことを特徴と
するポリスチレン系発泡体である。[Means for Solving the Problems] The present invention comprises: (A) polystyrene resin, (B) polyethylene resin, (C)
(i) a vinyl-substituted aromatic compound-conjugated diene block copolymer having at least one vinyl-substituted aromatic compound polymer block and a conjugated diene polymer block; ii
) a hydrogenated vinyl-substituted aromatic compound-conjugated diene block copolymer in which some or all of the double bonds in the vinyl-substituted aromatic compound-conjugated diene block copolymer of (i) are saturated with hydrogen; (iii) (i) or (ii) Vinyl substituted aromatic compound-conjugated diene block copolymer containing 0.5 wt% or more of an organic acid, acid anhydride, or ester group in the vinyl substituted aromatic compound-conjugated diene block copolymer , (iv) A polystyrene foam characterized by foaming a resin composition of at least one type selected from polystyrene-grafted polyolefins having a polystyrene content of 20 wt% or more and a grafting rate of 71% or more using a volatile foaming agent. and preferably (A) polystyrene resin 70 to 30% by weight (
B) Polyethylene resin 10 to 65% by weight (C
) third component 5 to 20% by weight, and (B) polyethylene resin 1
This is a polystyrene foam characterized by foaming a resin composition containing at least 5 parts by weight of high-density polyethylene having a density of 0.94 g/cm3 or more in 00 parts by weight using a volatile foaming agent.
【０００９】以下本発明を詳細に説明する。本発明に用
いる（Ａ） ポリスチレン系樹脂としては、ポリスチレ
ン（ 以下ＧＰＰＳと略す。） 、ゴム変性ポリスチレ
ン（ 以下ＨＩＰＳと略す。） 、アクリロニトリル−
スチレン共重合体、アクリロニトリル−ブタジエン−ス
チレン共重合体、メチルメタクリレート−スチレン共重
合体、共役ジエン−スチレン共重合体などのビニル置換
芳香族化合物等があげられる。The present invention will be explained in detail below. The polystyrene resin (A) used in the present invention includes polystyrene (hereinafter abbreviated as GPPS), rubber-modified polystyrene (hereinafter abbreviated as HIPS), acrylonitrile-
Examples include vinyl-substituted aromatic compounds such as styrene copolymer, acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-styrene copolymer, and conjugated diene-styrene copolymer.
【００１０】（Ｂ） ポリエチレン系樹脂としては、エ
チレンホモ重合体、およびエチレンとα−オレフィンま
たは、酢酸ビニルの共重合体、あるいはこれらの混合物
である。例えば、低密度ポリエチレン（以下 ＬＤＰＥ
と略す。）、高密度ポリエチレン（以下ＨＤＰＥと略
す。）、直鎖状低密度ポリエチレン（以下ＬＬＤＰＥ
と略す。）、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（ 以下ＥＶＡ と略す。） 等
が挙げられる。(B) The polyethylene resin is an ethylene homopolymer, a copolymer of ethylene and α-olefin or vinyl acetate, or a mixture thereof. For example, low density polyethylene (LDPE)
It is abbreviated as ), high-density polyethylene (hereinafter abbreviated as HDPE), linear low-density polyethylene (hereinafter LLDPE)
It is abbreviated as ), ethylene-propylene copolymer, ethylene-vinyl acetate copolymer (hereinafter abbreviated as EVA), and the like.
【００１１】（Ｃ） 第三成分としては、 （ｉ）ビ
ニル置換芳香族化合物重合体ブロックと共役ジエン系重
合体ブロックを少なくとも１個有する該ブロック共重合
体、
（ｉｉ） ブロック共重合体中の二重結合の一部または
全部を飽和した水素添加ブロック共重合体、（ｉｉｉ）
該ブロック共重合体 （ｉ）または （ｉｉ） 中に有
機酸あるいは酸無水物あるいはエステル基を０．５ｗｔ
％以上含むブロック共重合体、又は、（ｉｖ）ポリスチ
レン含量２０ｗｔ％ 以上でかつグラフト率７１％ 以
上であるポリスチレングラフトポリオレフィンが好まし
い。(C) The third component includes (i) the block copolymer having at least one vinyl-substituted aromatic compound polymer block and one conjugated diene polymer block; (ii) (iii) a hydrogenated block copolymer in which some or all of the double bonds are saturated;
0.5wt of organic acid, acid anhydride or ester group in the block copolymer (i) or (ii)
% or more, or (iv) a polystyrene graft polyolefin having a polystyrene content of 20 wt% or more and a graft ratio of 71% or more.
【００１２】ここでビニル置換芳香族化合物重合体ブロ
ックは、スチレン、α−メチルスチレン、ｐ−メチルス
チレン、２，４−ジメチルスチレンのホモ重合体、ある
いはそれらの共重合体でり、共役ジエン系重合体ブロッ
クは、１，３−ブタジエン、イソプレンからなるホモ重
合体またはこれらの共重合体であり、有機酸としては無
水マレイン酸、無水コハク酸、フタル酸などが例示され
る。The vinyl-substituted aromatic compound polymer block is a homopolymer of styrene, α-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, or a copolymer thereof, and is a conjugated diene-based polymer block. The polymer block is a homopolymer of 1,3-butadiene and isoprene or a copolymer thereof, and examples of the organic acid include maleic anhydride, succinic anhydride, and phthalic acid.
【００１３】上記ブロック共重合体 （ｉ）、（ｉｉ）
、（ｉｉｉ） に含有されるビニル置換芳香族化合物重
合体ブロックの分子量は５０００以上であり、該ブロッ
ク共重合体に対して１０重量％以上である。又、（ｉｖ
）ポリスチレングラフトポリオレフィンは、ポリスチレ
ン含量２０ｗｔ％ 以上でかつグラフト率７０％ 以上
のものである。ポリオレフィンとしてはＨＤＰＥ、ＬＬ
ＤＰＥ 、ＬＤＰＥ、ＥＰＤＭ、ホモポリプロピレン、
ランダムポリプロピレン、ブロックポリプロピレンを用
いたものが例示される。かかる第三成分を用いなければ
発泡時の気泡膜の破れや収縮がおこりやすく、発泡倍率
が上がらない。また発泡体の剛性、衝撃吸収性が劣り、
発泡体の圧縮による気泡膜の破れも起こりやすい。[0013] The above block copolymer (i), (ii)
The molecular weight of the vinyl-substituted aromatic compound polymer block contained in , (iii) is 5,000 or more, and is 10% by weight or more with respect to the block copolymer. Also, (iv
) The polystyrene graft polyolefin has a polystyrene content of 20 wt% or more and a grafting rate of 70% or more. HDPE, LL as polyolefin
DPE, LDPE, EPDM, homopolypropylene,
Examples include those using random polypropylene and block polypropylene. If such a third component is not used, the foam membrane tends to break or shrink during foaming, and the foaming ratio cannot be increased. In addition, the rigidity and shock absorption properties of the foam are poor,
The cell membrane is also likely to break due to compression of the foam.
【００１４】通常のポリエチレン、ポリスチレン発泡成
形温度（１００℃〜１３０ ℃） においては、ポリエ
チレン系樹脂１００重量部中には密度 ０．９４ｇ／ｃ
ｍ３以上の高密度ポリエチレンが少なくとも５重量部以
上含有されていることが好ましい。高密度ポリエチレン
を含有させることにより、溶融収縮を防止し、より高倍
率発泡が可能となる。[0014] At normal polyethylene and polystyrene foam molding temperatures (100°C to 130°C), 100 parts by weight of polyethylene resin has a density of 0.94 g/c.
It is preferable that at least 5 parts by weight of high density polyethylene of m3 or more is contained. By containing high-density polyethylene, melt shrinkage can be prevented and foaming at a higher ratio can be achieved.
【００１５】ポリエチレン系樹脂の組成が６５重量％を
越えると剛性が劣り、組成物中のブロック共重合体が５
重量％未満では耐衝撃性が改善されず、２０重量％を越
えると剛性が劣るので好ましくない。前記ブロック共重
合体の製造方法、変性方法、水素添加は特に限定される
ものではない。[0015] If the composition of the polyethylene resin exceeds 65% by weight, the rigidity will be poor, and if the block copolymer in the composition
If it is less than 20% by weight, the impact resistance will not be improved, and if it exceeds 20% by weight, the rigidity will be poor, which is not preferable. The manufacturing method, modification method, and hydrogenation of the block copolymer are not particularly limited.
【００１６】本発明の発泡成形品は、必要に応じて任意
の充填剤、例えば、ガラス繊維、チタン白、カーボン、
シリカ、タルク、マイカ、酸化亜鉛などを含むことがで
きる。さらに必要に応じて、難燃剤、酸化防止剤、熱安
定剤、紫外線吸収剤、滑剤、帯電防止剤等の添加剤を配
合することができる。本発明における発泡成形品は、（
Ａ） ポリスチレン系樹脂、（Ｂ） ポリエチレン系樹
脂および（Ｃ） 第三成分を公知の方法、例えば、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
レット化したものを発泡剤により公知のポリスチレンあ
るいはポリエチレンビーズ発泡成形機を用いてビーズ発
泡して製造できる。また公知の押出発泡成形機により押
出発泡成形することができる。発泡剤としては揮発性溶
剤型発泡剤例えばブタン、ペンタン、フレオン等を用い
ることができ、発泡体の平均発泡倍率は好ましくは５〜
６０倍である。これら成形品は耐衝撃性、耐油性に優れ
、剛性もある。[0016] The foamed molded product of the present invention may contain any filler as required, such as glass fiber, titanium white, carbon,
It can include silica, talc, mica, zinc oxide, etc. Furthermore, additives such as flame retardants, antioxidants, heat stabilizers, ultraviolet absorbers, lubricants, and antistatic agents may be added as necessary. The foam molded product in the present invention is (
A) polystyrene resin, (B) polyethylene resin, and (C) third component are melt-kneaded using a known method, such as a melt-kneader such as a single-screw extruder or a twin-screw extruder, and then pelletized. It can be produced by foaming beads using a known polystyrene or polyethylene bead foam molding machine using a foaming agent. Further, extrusion foam molding can be performed using a known extrusion foam molding machine. As the blowing agent, volatile solvent-type blowing agents such as butane, pentane, freon, etc. can be used, and the average expansion ratio of the foam is preferably 5 to 5.
It is 60 times more. These molded products have excellent impact resistance, oil resistance, and rigidity.
【００１７】[0017]
【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：ペレット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。
○：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） ２次成形性：予備発泡粒子を１００ｍｍ ×１
００ｍｍ ×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。
○：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。[Example] Examples are shown below. The present invention is not limited to these examples. The data shown in the examples were measured based on the following method. (1) Foamability: 5 g of pellets were placed in an autoclave, 15 g of n-butane was added, and the mixture was left at 60°C for 5 hours, and then foamed at 120°C to obtain pre-expanded particles. The evaluation results were displayed as shown below. ○: 5 to 60 times more free of foaming, cracks, cracks, etc. ×: No foaming, cracks or cracks. (2) Secondary moldability: Pre-expanded particles 100mm x 1
The molded product was placed in a 100 mm x 10 mm mold and heat-molded at 110° C., and the resulting molded product was broken and the percentage of pre-expanded particles peeled off at the interface on a 100 mm x 10 mm surface was determined as the fusion rate. The evaluation results were displayed as shown below. ○: 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%. ×: Unfused, shrinkage occurs, and molded product cannot be obtained.
【００１８】実施例１〜３、比較例１〜３（Ａ） ポリ
スチレン系樹脂として、ＭＩ＝６．７ 、密度 ０．９
２ のＧＰＰＳ、
（Ｂ） ポリオレフィン系樹脂として、密度 ０．９２
、ＭＩ＝１．６ 、酢酸ビニル含有量５％ のＥＶＡ
、密度 ０．９３５ 、ＭＩ＝３ のＬＬＤＰＥ
、密度 ０．９５４ 、ＭＩ＝２ のＨＤＰＥ、（Ｃ
） 水素添加ブロック共重合体として、スチレン含量２
８ｗｔ％ 、溶液粘度 ６０００ｃｐｓ（２５ ℃、２
０％ トルエン溶液） 、無水マレイン酸含量 ２ｗｔ
％ のスチレン−ブタジエン−スチレンブロック共重合
体（以下ＳＥＢＳと略す。） を使用した。これらの樹
脂をそれぞれ第１表に示した組成で、４０ｍｍ二軸混練
機にて２２０ ℃で溶融混練してペレットとし、そのペ
レットを１２０ ℃でｎ−ブタンで発泡させて得た予備
発泡粒子を１１０ ℃で成形し、１００ｍｍ×１００ｍ
ｍ ×１０ｍｍの発泡体を得、その発泡成形性を試験し
た。Examples 1 to 3, Comparative Examples 1 to 3 (A) As polystyrene resin, MI=6.7, density 0.9
2 GPPS, (B) Density 0.92 as polyolefin resin
, MI=1.6, EVA with vinyl acetate content 5%
, density 0.935, MI=3 LLDPE
, density 0.954, MI=2, HDPE, (C
) As a hydrogenated block copolymer, styrene content 2
8 wt%, solution viscosity 6000 cps (25 °C, 2
0% toluene solution), maleic anhydride content 2wt
% of styrene-butadiene-styrene block copolymer (hereinafter abbreviated as SEBS) was used. These resins each having the composition shown in Table 1 were melt-kneaded at 220°C in a 40 mm twin-screw kneader to form pellets, and the pellets were foamed with n-butane at 120°C to obtain pre-expanded particles. Molded at 110℃, 100mm x 100m
A foam of m×10 mm was obtained and its foam moldability was tested.
【００１９】
第１表 ┌──────┬─────
───┬────────┐ │
│ 実施例 │
比較例 │ │
├──┬──┬──┼──┬──┬──┤
│ │１ │２
│３ │１ │２ │３ │ ├
──┬───┼──┼──┼──┼──┼──┼──┤
│組成│ＧＰＰＳ │４０ │５０
│６０ │５０ │ ５０ │ ５０ │
│ │ＥＶＡ │３０ │３０
│２０ │５０ │ ４０ │ ０ │
│ｗｔ％ │ＬＬＤＰＥ │２０ │１０ │
１０ │ ０ │ ０ │ ４０ │
│ │ＨＤＰＥ │２０ │１０ │１
０ │ ０ │ ０ │ ０ │
│ │ＳＥＢＳ │１０ │１０ │１０
│ ０ │ １０ │ １０ │ ├
──┴───┼──┼──┼──┼──┼──┼──┤
│発泡性 │○ │○ │
○ │× │○ │○ │ │２次
成形性 │○ │○ │○ │× │×
│△ │ └──────┴──┴──┴
──┴──┴──┴──┘[0019]
Table 1 ┌──────┬──────
───┬────────┐ │
│ Examples │
Comparative example │ │
├──┬──┬──┼──┬──┬──┤
│ │1 │2
│３ │１ │２ │３ │ ├
──┬───┼──┼──┼──┼──┼──┼──┤
│Composition│GPPS │40 │50
│60 │50 │ 50 │ 50 │
│ │EVA │30 │30
│20 │50 │ 40 │ 0 │
│wt% │LLDPE │20 │10 │
10 │ 0 │ 0 │ 40 │
│ │HDPE │20 │10 │1
0 │ 0 │ 0 │ 0 │
│ │SEBS │10 │10 │10
│ 0 │ 10 │ 10 │ ├
──┴────┼──┼──┼──┼──┼──┼──┤
│Foamability │○ │○ │
○ │× │○ │○ │ │Secondary formability │○ │○ │○ │× │×
│△ │ └──────┴──┴──┴
──┴──┴──┴──┘
【００２０】[0020]
【発明の効果】本発明によって得られるポリスチレン系
発泡体は、ポリスチレン系樹脂のもつ剛性とポリオレフ
ィン系樹脂の耐衝撃性と耐油性を持ち合わせ、衝撃吸収
性と剛性のバランスに優れており広範囲な用途に使用可
能である。その利用分野は家電部品、自動車部品、食品
包装等用途などに広がっている。[Effects of the Invention] The polystyrene foam obtained by the present invention has the rigidity of polystyrene resin and the impact resistance and oil resistance of polyolefin resin, and has an excellent balance between shock absorption and rigidity, and has a wide range of uses. It can be used for Its application fields are expanding to include home appliance parts, automobile parts, food packaging, and other applications.
Claims (3)
）ポリエチレン系樹脂、 （Ｃ）第三成分よりなり、か
つ当該第三成分が、 （ｉ）ビニル置換芳香族化合物重合体ブロックと共役ジ
エン系重合体ブロックを少なくとも１個有するビニル置
換芳香族化合物−共役ジエンブロック共重合体、（ｉｉ
） （ｉ）のビニル置換芳香族化合物−共役ジエンブロ
ック共重合体中の二重結合の一部または全部が水素で飽
和した水素添加ビニル置換芳香族化合物−共役ジエンブ
ロック共重合体、 （ｉｉｉ） （ｉ）または （ｉｉ） のビニル置換芳
香族化合物−共役ジエンブロック共重合体中に有機酸あ
るいは酸無水物あるいはエステル基を０．５ｗｔ％以上
含むビニル置換芳香族化合物−共役ジエンブロック共重
合体、（ｉｖ） ポリスチレン含量２０ｗｔ％ 以上で
かつグラフト率７１％ 以上であるポリスチレングラフ
トポリオレフィンから選ばれる少なくとも１種である樹
脂組成物を揮発性発泡剤により発泡させたことを特徴と
するポリスチレン系発泡体。Claim 1: (A) polystyrene resin, (B
) a polyethylene resin, (C) a third component, and the third component is (i) a vinyl-substituted aromatic compound having at least one vinyl-substituted aromatic compound polymer block and one conjugated diene polymer block; Conjugated diene block copolymer, (ii
) a hydrogenated vinyl-substituted aromatic compound-conjugated diene block copolymer in which some or all of the double bonds in the vinyl-substituted aromatic compound-conjugated diene block copolymer of (i) are saturated with hydrogen; (iii) (i) or (ii) Vinyl substituted aromatic compound-conjugated diene block copolymer containing 0.5 wt% or more of an organic acid, acid anhydride, or ester group in the vinyl substituted aromatic compound-conjugated diene block copolymer , (iv) A polystyrene foam characterized by foaming a resin composition of at least one type selected from polystyrene-grafted polyolefins having a polystyrene content of 20 wt% or more and a grafting rate of 71% or more using a volatile foaming agent. .
０ 〜３０重量％ （Ｂ）ポリエチレン系樹脂 １０ 〜６５重量％（
Ｃ）第三成分 ５ 〜２０
重量％よりなり、かつ、（Ｂ） ポリエチレン系樹脂
１００重量部の中に密度 ０．９４ ｇ／ｃｍ３ 以上
の高密度ポリエチレンを少なくとも５重量部を含有する
請求項１記載のポリスチレン系発泡体。[Claim 2] (A) Polystyrene resin 7
0 to 30% by weight (B) Polyethylene resin 10 to 65% by weight (
C) Third component 5 to 20
(B) polyethylene resin
The polystyrene foam according to claim 1, containing at least 5 parts by weight of high-density polyethylene having a density of 0.94 g/cm3 or more in 100 parts by weight.
ともポリスチレン（ＧＰＰＳ）、ゴム変性ポリスチレン
（ＨＩＰＳ）、アクリロニトリル−スチレン共重合体、
アクリロニトリル−ブタジエン−スチレン共重合体、メ
チルメタクリレート−スチレン共重合体、共役ジエン−
スチレン共重合体から選ばれる１であり、 （Ｂ） ポリエチレン系樹脂が、少くともエチレンホモ
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から選ばれる１である請求項１記
載のポリスチレン系発泡体。3. (A) The polystyrene resin is at least polystyrene (GPPS), rubber-modified polystyrene (HIPS), acrylonitrile-styrene copolymer,
Acrylonitrile-butadiene-styrene copolymer, methyl methacrylate-styrene copolymer, conjugated diene-
1 selected from styrene copolymers, and (B) the polyethylene resin is at least 1 selected from ethylene homopolymers, ethylene-α-olefin copolymers, and ethylene-vinyl acetate copolymers. 1. The polystyrene foam according to 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40431890A JPH04220439A (en) | 1990-12-20 | 1990-12-20 | Polystyrene resin foam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP40431890A JPH04220439A (en) | 1990-12-20 | 1990-12-20 | Polystyrene resin foam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04220439A true JPH04220439A (en) | 1992-08-11 |
Family
ID=18513994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP40431890A Pending JPH04220439A (en) | 1990-12-20 | 1990-12-20 | Polystyrene resin foam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04220439A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4901541A (en) * | 1987-04-20 | 1990-02-20 | Okuma Machinery Works Ltd. | Needle selector for knitting machine |
| EP0601783A1 (en) * | 1992-12-03 | 1994-06-15 | General Electric Company | Blowing agent concentrate |
| US5726215A (en) * | 1994-11-08 | 1998-03-10 | Sumitomo Chemical Company, Limited | Styrene resin composition and shaped article thereof |
| JP2002234974A (en) * | 2001-02-08 | 2002-08-23 | Asahi Kasei Corp | Ethylene resin composition and extruded article using the same |
| WO2007138916A1 (en) * | 2006-05-26 | 2007-12-06 | Jsp Corporation | Expandable polyethylene resin particle and method for production thereof |
| JP2007321020A (en) * | 2006-05-31 | 2007-12-13 | Hitachi Chem Co Ltd | Foamable polyethylene resin particle and its manufacturing method |
| JP2007321021A (en) * | 2006-05-31 | 2007-12-13 | Hitachi Chem Co Ltd | Foamable polyethylene resin particle and its manufacturing method |
| JP2009120662A (en) * | 2007-11-13 | 2009-06-04 | Jsp Corp | Delayed combustion type foamable polyethylene-based resin particles, method for producing the same, and polyethylene-based expandable beads and resin molded article using those |
| WO2015137353A1 (en) * | 2014-03-12 | 2015-09-17 | 積水化成品工業株式会社 | Composite resin particles, foamable particles, pre-foamed particles, and foam molded body |
| JP2015172154A (en) * | 2014-03-12 | 2015-10-01 | 積水化成品工業株式会社 | Composite resin particle, expandable particle, pre-expanded particle and foam molding |
| JP2015172155A (en) * | 2014-03-12 | 2015-10-01 | 積水化成品工業株式会社 | Composite resin particle, expandable particle, pre-expanded particle and foam molding |
| JP2016500387A (en) * | 2012-12-17 | 2016-01-12 | ベルサリス、ソシエタ、ペル、アチオニＶｅｒｓａｌｉｓ Ｓ．Ｐ．Ａ． | Expandable polymer compositions with improved flexibility and related production processes |
| WO2016136460A1 (en) * | 2015-02-27 | 2016-09-01 | 積水化成品工業株式会社 | Composite resin particle, and foamable particle, foamed particle and foamed molding thereof |
-
1990
- 1990-12-20 JP JP40431890A patent/JPH04220439A/en active Pending
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4901541A (en) * | 1987-04-20 | 1990-02-20 | Okuma Machinery Works Ltd. | Needle selector for knitting machine |
| EP0601783A1 (en) * | 1992-12-03 | 1994-06-15 | General Electric Company | Blowing agent concentrate |
| US5726215A (en) * | 1994-11-08 | 1998-03-10 | Sumitomo Chemical Company, Limited | Styrene resin composition and shaped article thereof |
| JP2002234974A (en) * | 2001-02-08 | 2002-08-23 | Asahi Kasei Corp | Ethylene resin composition and extruded article using the same |
| US7964652B2 (en) | 2006-05-26 | 2011-06-21 | Jsp Corporation | Expandable polyethylene resin particle and method for production thereof |
| WO2007138916A1 (en) * | 2006-05-26 | 2007-12-06 | Jsp Corporation | Expandable polyethylene resin particle and method for production thereof |
| JP5352233B2 (en) * | 2006-05-26 | 2013-11-27 | 株式会社ジェイエスピー | Expandable polyethylene resin particles and method for producing the same |
| JP2007321020A (en) * | 2006-05-31 | 2007-12-13 | Hitachi Chem Co Ltd | Foamable polyethylene resin particle and its manufacturing method |
| JP2007321021A (en) * | 2006-05-31 | 2007-12-13 | Hitachi Chem Co Ltd | Foamable polyethylene resin particle and its manufacturing method |
| JP2009120662A (en) * | 2007-11-13 | 2009-06-04 | Jsp Corp | Delayed combustion type foamable polyethylene-based resin particles, method for producing the same, and polyethylene-based expandable beads and resin molded article using those |
| JP2016500387A (en) * | 2012-12-17 | 2016-01-12 | ベルサリス、ソシエタ、ペル、アチオニＶｅｒｓａｌｉｓ Ｓ．Ｐ．Ａ． | Expandable polymer compositions with improved flexibility and related production processes |
| JP2015172154A (en) * | 2014-03-12 | 2015-10-01 | 積水化成品工業株式会社 | Composite resin particle, expandable particle, pre-expanded particle and foam molding |
| JP2015172155A (en) * | 2014-03-12 | 2015-10-01 | 積水化成品工業株式会社 | Composite resin particle, expandable particle, pre-expanded particle and foam molding |
| WO2015137353A1 (en) * | 2014-03-12 | 2015-09-17 | 積水化成品工業株式会社 | Composite resin particles, foamable particles, pre-foamed particles, and foam molded body |
| KR20160132815A (en) * | 2014-03-12 | 2016-11-21 | 세키스이가세이힝코교가부시키가이샤 | Composite resin particles, foamable particles, pre-foamed particles, and foam molded body |
| EP3118231A4 (en) * | 2014-03-12 | 2017-11-01 | Sekisui Plastics Co., Ltd. | Composite resin particles, foamable particles, pre-foamed particles, and foam molded body |
| US9988511B2 (en) | 2014-03-12 | 2018-06-05 | Sekisui Plastics Co., Ltd. | Composite resin particles, foamable particles, pre-foamed particles, and foam molded body |
| WO2016136460A1 (en) * | 2015-02-27 | 2016-09-01 | 積水化成品工業株式会社 | Composite resin particle, and foamable particle, foamed particle and foamed molding thereof |
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