JP2000351865A - Polyolefin resin composition for crosslinking and foaming, and crosslinked foam prepared therefrom - Google Patents

Polyolefin resin composition for crosslinking and foaming, and crosslinked foam prepared therefrom

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Publication number
JP2000351865A
JP2000351865A JP16317999A JP16317999A JP2000351865A JP 2000351865 A JP2000351865 A JP 2000351865A JP 16317999 A JP16317999 A JP 16317999A JP 16317999 A JP16317999 A JP 16317999A JP 2000351865 A JP2000351865 A JP 2000351865A
Authority
JP
Japan
Prior art keywords
foaming
polyolefin resin
resin composition
crosslinking
weight
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
Application number
JP16317999A
Other languages
Japanese (ja)
Inventor
Shigeo Kamijukkoku
成夫 上拾石
Fusakichi Akimaru
房吉 秋丸
Motoi Naito
基 内藤
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Industries Inc
Original Assignee
Toray Industries Inc
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toray Industries Inc filed Critical Toray Industries Inc
Priority to JP16317999A priority Critical patent/JP2000351865A/en
Publication of JP2000351865A publication Critical patent/JP2000351865A/en
Pending legal-status Critical Current

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Abstract

PROBLEM TO BE SOLVED: To obtain a polyolefin resin composition which gives a foam excellent in resistances to heat and pressure and exhibits improved safeness and handleability in the production process by compounding a polyolefin resin with specified amounts of a dipropenyl compound and a thermally decomposable chemical blowing agent. SOLUTION: A polyolefin resin in an amount of 100 pts.wt. is compounded with 1-10 pts.wt. dipropenyl compound of the formula and 1-15 pts.wt. thermally decomposable chemical blowing agent. Preferably, the polyolefin resin comprises 30-90 wt.% PP resin having an MFR of 0.5-5 g/10 min and preferably having an m.p. of 125-155 deg.C and 10-70 wt.% PE resin having an MFR of 1-20 g/10 min and preferably having a density of 0.890-0.940 g/cm3. The composition for foaming is prepared by using a polyolefin resin composition containing 10-50 wt.% dipropenyl compound. A foam is prepared by sheeting the composition for foaming, crosslinking the resultant sheet by the irradiation with an ionizing radiation (ultraviolet rays), and thermally foaming the crosslinked sheet under normal pressure.

Description

【発明の詳細な説明】DETAILED DESCRIPTION OF THE INVENTION

【0001】[0001]

【発明の属する技術分野】本発明は架橋発泡用ポリオレ
フィン系樹脂組成物及びその架橋発泡体に関する。更に
詳しくは、耐熱性に優れ、かつ、複雑な形状への加工
性、あるいは高温下における加工特性、高温下の耐圧性
に優れ、広範囲の2次加工法に対応できるとともに、柔
軟性などを自由に制御できるタイプの架橋発泡用ポリオ
レフィン系樹脂発泡体を連続的に製造するに適した架橋
発泡用ポリオレフィン系樹脂組成物及びその組成物を架
橋、発泡して得られる架橋発泡体に関する。
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a crosslinked foamed polyolefin resin composition and a crosslinked foamed product thereof. More specifically, it is excellent in heat resistance and workability to complex shapes, excellent in processing characteristics at high temperatures, and excellent in pressure resistance under high temperatures. TECHNICAL FIELD The present invention relates to a cross-linked and foamable polyolefin-based resin composition suitable for continuously producing a cross-linked and foamable polyolefin-based resin foam of a type that can be controlled to a cross-linked foam, and a cross-linked foam obtained by cross-linking and foaming the composition.

【0002】[0002]

【従来の技術】ポリオレフィン系樹脂、たとえばポリプ
ロピレン系樹脂を主成分として用いた架橋発泡体は、そ
の優れた成形性、緩衝性、断熱性、耐熱性を活かし、塩
化ビニルシートやオレフィン系(エラストマ)樹脂シー
ト(TPOシート)と貼り合わせられて各種の加工法で
成形され、自動車のドア、インスツルメントパネル、コ
ンソールボックス、シートバックガーニッシュなどの内
装材に使用されている。
2. Description of the Related Art A crosslinked foam using a polyolefin-based resin, for example, a polypropylene-based resin as a main component, makes use of its excellent moldability, cushioning property, heat insulation property, and heat resistance, and uses a vinyl chloride sheet or an olefin (elastomer). It is laminated with a resin sheet (TPO sheet) and molded by various processing methods, and is used for interior materials such as automobile doors, instrument panels, console boxes, and seat back garnishes.

【0003】従来、ポリオレフィン系樹脂発泡体の製造
における架橋法の一つとして、発泡性樹脂組成物を連続
的にシート状に成形し、電離性放射線を照射して架橋す
る方法がある。この方法は放射線を照射することにより
架橋の進行しやすいエチレン系樹脂を用いる場合には非
常に有効であるが、放射線を照射することにより分子鎖
の切断の進行しやすいポリプロピレン系樹脂を用いる場
合には、樹脂劣化が進行するため発泡に適した架橋の付
与が困難である。
Conventionally, as one of the crosslinking methods in the production of a polyolefin resin foam, there is a method in which a foamable resin composition is continuously formed into a sheet and crosslinked by irradiation with ionizing radiation. This method is very effective when using an ethylene-based resin that is susceptible to cross-linking by irradiating radiation, but is effective when using a polypropylene-based resin that is susceptible to molecular chain breakage by irradiating radiation. However, it is difficult to provide crosslinking suitable for foaming because the resin deteriorates.

【0004】このことからポリプロピレン系樹脂を用い
る場合、特公昭46−38716号、特開昭61−69
844号、特開平5−78514号公報に例示されるよ
うに反応性ビニル基、アクリル基、メタクリル基を分子
構造中に持つ多官能モノマーを介してポリプロピレン系
樹脂が電離放射線の照射によって劣化しない、あるいは
軽度の劣化しか生じない程度の照射エネルギーで架橋さ
せた後、常圧下で加熱発泡して発泡体を得ている。
For this reason, when a polypropylene resin is used, JP-B-46-38716 and JP-A-61-69 are used.
No. 844, the polypropylene resin is not deteriorated by irradiation with ionizing radiation through a polyfunctional monomer having a reactive vinyl group, an acryl group, and a methacryl group in a molecular structure as exemplified in JP-A-5-78514. Alternatively, the foam is crosslinked with irradiation energy of such a degree that only slight deterioration occurs, and then heated and foamed under normal pressure to obtain a foam.

【0005】[0005]

【発明が解決しようとする課題】しかしながら、従来の
多官能モノマーを用いて架橋、発泡したポリオレフィン
系樹脂発泡体は、多官能モノマーの種類によって、ま
た、樹脂の配合比率によっては樹脂成分中の各樹脂に対
する相溶性が異なるため、結果的に分散不良に伴う反応
性モノマーの局在化が生じ、架橋ムラが生じる。これ
は、発泡体製造時の安定性や気泡径の不揃い、一般機械
物性の不安定化につながり、要求される加工適性や耐熱
性の低下につながるという問題があった。また、電子線
による架橋法は電子線のエネルギー分布、すなわち、デ
ィプスドーズパターンの分布を持つため、照射エネルギ
ーと多官能モノマーの反応性がリニアーな関係にあるも
のについては必然的にシートの厚さ方向に架橋度分布を
生じることになり、発泡体としたとき、発泡体の厚さ方
向に気泡形状が分布を持つようになり、従って、一般物
性にも分布を生じ、品質低下を招くという問題もあっ
た。また、通常は室温レベルでは液体状やペースト状の
ものが多く、取り扱いの点で問題があった。
However, conventional polyolefin resin foams cross-linked and foamed using a polyfunctional monomer may have various contents in the resin component depending on the type of the polyfunctional monomer and the mixing ratio of the resin. Since the compatibility with the resin is different, localization of the reactive monomer occurs as a result of poor dispersion, resulting in uneven crosslinking. This leads to irregularities in the stability and bubble diameter during foam production, destabilization of general mechanical properties, and a reduction in required workability and heat resistance. In addition, since the electron beam cross-linking method has an electron beam energy distribution, that is, a depth dose pattern distribution, if the irradiation energy and the reactivity of the polyfunctional monomer have a linear relationship, the sheet thickness is inevitable. The problem is that when a foam is formed, the shape of the cells has a distribution in the thickness direction of the foam, so that the general physical properties also have a distribution and the quality is reduced. There was also. In addition, there are usually many liquid or paste-like materials at room temperature, and there is a problem in handling.

【0006】最近では加工方法の進歩に伴い、発泡体に
対し、より高い耐熱性、耐圧性が要求され、これと相反
するが柔軟性が同時に要求されてきいる。これに対して
は、樹脂組成自身の改良も必要不可欠であるが、要求物
性に対しそれぞれに対応する樹脂組成にする必要があ
り、製品の品種数が増加して生産効率が低下するとか、
工程管理、品質管理が極めて複雑になるという問題があ
った。これまでは、できるだけ樹脂組成の近似したもの
をグループ管理し、個々のグループの中で目標とする樹
脂組成とするには、架橋度の調整で特徴を持たす手法が
採られていた。
Recently, with the progress of processing methods, foams are required to have higher heat resistance and pressure resistance, and at the same time, flexibility is required at the same time. To this end, improvement of the resin composition itself is also indispensable, but it is necessary to make the resin composition corresponding to each required physical property, and the number of product types increases and production efficiency decreases,
There was a problem that process control and quality control became extremely complicated. Heretofore, a method has been adopted in which, as much as possible, a resin composition is managed as a group, and in order to obtain a target resin composition in each group, a characteristic is obtained by adjusting the degree of crosslinking.

【0007】本発明者らは、限られた樹脂組成の配合比
率の中で、架橋鎖の安定性と反応性を検討した結果、低
毒性で原料粉体を入手できるとともに、電子線エネルギ
ーで反応するものを見いだし、それを架橋発泡体に適用
した。そして、この原料から一定の品質を保持しながら
耐熱性、成形加工性、耐圧性に優れた架橋発泡用ポリオ
レフィン系樹脂組成物及びその発泡体が得られることを
見いだし、本発明に至った。
The inventors of the present invention have studied the stability and reactivity of the crosslinked chain in a limited mixing ratio of the resin composition. As a result, the raw material powder having low toxicity can be obtained, and the reaction by electron beam energy can be performed. And applied it to the crosslinked foam. Then, it was found that a polyolefin resin composition for cross-linking and foaming and excellent in heat resistance, molding processability, and pressure resistance and a foam thereof were obtained from the raw materials while maintaining a certain quality.

【0008】すなわち、本発明の課題は、製造工程での
安全性、取り扱い性を改善でき、一定の品質を保持しな
がら耐熱性、成形加工性、耐圧性に優れた架橋発泡用ポ
リオレフィン系樹脂組成物及びその架橋発泡体を提供す
ることにある。
[0008] That is, an object of the present invention is to provide a polyolefin resin composition for cross-linked foaming which can improve the safety and handling properties in the manufacturing process, and is excellent in heat resistance, molding processability and pressure resistance while maintaining a certain quality. And a crosslinked foam thereof.

【0009】[0009]

【課題を解決するための手段】上記課題を解決するため
に、本発明の架橋発泡用ポリオレフィン系樹脂組成物
は、ポリオレフィン系樹脂100重量部に対し、下記一
般式で表されるジプロペニル化合物を1〜10重量部、
熱分解型化学発泡剤を1〜15重量部含有することを特
徴とするものからなる。
In order to solve the above-mentioned problems, a polyolefin resin composition for crosslinking and foaming of the present invention comprises a dipropenyl compound represented by the following general formula per 100 parts by weight of a polyolefin resin. -10 parts by weight,
It is characterized by containing from 1 to 15 parts by weight of a thermal decomposition type chemical foaming agent.

【0010】[0010]

【化2】 Embedded image

【0011】また、本発明に係る架橋ポリオレフィン系
樹脂発泡体は、上記架橋発泡用ポリオレフィン系樹脂組
成物をシート状に成形した後、電離性放射線あるいは紫
外線を照射し、架橋した後、常圧下で加熱発泡したもの
からなる。
Further, the crosslinked polyolefin resin foam according to the present invention is obtained by molding the above polyolefin resin composition for crosslinking and foaming into a sheet, irradiating it with ionizing radiation or ultraviolet light, crosslinking it under normal pressure. It is made by heating and foaming.

【0012】ポリオレフィン系樹脂としては、たとえば
前記ポリオレフィン系樹脂が、MFRが0.5〜5g/
10分の範囲にあるポリプロピレン系樹脂(a)30〜
90重量%とMFRが1〜20g/10分の範囲にある
ポリエチレン系樹脂(b)10〜70重量%からなる請
求項1に記載の架橋発泡用ポリオレフィン系樹脂組成物
からなる。
As the polyolefin resin, for example, the polyolefin resin has an MFR of 0.5 to 5 g / g.
Polypropylene resin (a) 30 to 10 minutes
The crosslinked foaming polyolefin resin composition according to claim 1, comprising 90% by weight and 10 to 70% by weight of a polyethylene resin (b) having an MFR in a range of 1 to 20 g / 10 minutes.

【0013】[0013]

【発明の実施の形態】本発明に用いるポリオレフィン系
樹脂とは、特に限定されるものではないが、たとえばポ
リプロピレン系樹脂の場合、好ましくはチーグラ触媒、
メタロセン触媒、不均一触媒により気相法、スラリー
法、溶液法などで重合されるプロピレンとエチレンある
いは炭素数が4〜12のαオレフィンを2〜15重量
%、共重合したもので融点が125〜155℃、MFR
が0.5〜5g/10分のものである。この共重合体で
はプロピレンに対しエチレンあるいは炭素数が4〜12
のαオレフィンのモノマーを共重合してもよいが、機械
強度、耐熱性の点では極力、炭素数の大きいものを使用
したものが好ましい。
DETAILED DESCRIPTION OF THE INVENTION The polyolefin resin used in the present invention is not particularly limited. For example, in the case of a polypropylene resin, preferably a Ziegler catalyst,
2-15% by weight of propylene and ethylene or α-olefin having 4 to 12 carbon atoms, which are polymerized by a gas phase method, a slurry method, a solution method or the like using a metallocene catalyst or a heterogeneous catalyst, and having a melting point of 125 to 155 ° C, MFR
Is 0.5 to 5 g / 10 min. In this copolymer, ethylene or carbon number is 4 to 12 with respect to propylene.
May be copolymerized, but from the viewpoint of mechanical strength and heat resistance, those having as large a carbon number as possible are preferred.

【0014】共重合するエチレンあるいは炭素数が4〜
12のαオレフィンは2〜15重量%、好ましくは3〜
8重量%であるが、2重量%未満では樹脂の結晶性が高
くなり耐熱性、機械強度の点では好ましいが、結晶性が
高くなると硬くなり緩衝性が悪化することと、低温での
耐衝撃性が低下するので好ましくない。また、2重量%
未満では、電離性放射線を照射し、架橋すると、反応性
モノマーを多量に添加しても架橋度の制御が難しく、広
範囲の、特に、耐熱、耐圧性向上に必要な40%以上の
架橋度が得られなくなるので好ましくない。一方、15
重量%を越えると、架橋制御の点、柔軟性の点では好ま
しいが、融点が低下するため耐熱性と高温下での耐圧性
が悪化するので好ましくない。
The copolymerized ethylene or carbon number of 4 to
12 alpha olefins are 2 to 15% by weight, preferably 3 to
Although it is 8% by weight, if it is less than 2% by weight, the crystallinity of the resin is high, which is preferable in terms of heat resistance and mechanical strength. However, if the crystallinity is high, the resin becomes hard and the buffering property deteriorates, and the impact resistance at low temperature It is not preferable because the property is lowered. 2% by weight
If it is less than 40%, it is difficult to control the degree of crosslinking even when a large amount of a reactive monomer is added when the composition is irradiated with ionizing radiation and crosslinked. It is not preferable because it cannot be obtained. On the other hand, 15
When the amount exceeds 10% by weight, it is preferable in terms of controlling crosslinking and flexibility, but it is not preferable because the melting point is lowered, so that heat resistance and pressure resistance at high temperatures are deteriorated.

【0015】融点は125〜155℃、好ましくは13
0〜145℃であるが、融点が125℃未満であると耐
熱性の点から用途的に制限が発生するので好ましくな
く、一方155℃を越えると融点が高くなり耐熱性が向
上し広範囲の用途に展開できるので好ましいが、発泡用
シート成形時の押出工程での剪断発熱が高くなり発泡剤
の分解が起こりやすくなるので好ましくない。
The melting point is 125 to 155 ° C., preferably 13
The melting point is from 0 to 145 ° C, but if the melting point is less than 125 ° C, it is not preferable because the application is restricted from the viewpoint of heat resistance. However, it is not preferable because the shearing heat generated in the extrusion step at the time of forming the foaming sheet is increased, and the decomposition of the foaming agent is likely to occur.

【0016】MFRは好ましくは0.5〜5g/10分
の範囲にあり、より好ましくは1〜3g/10分であ
る。MFRが0.5g/10分未満では剪断発熱により
発泡剤が分解し気泡の不揃いが発生しやすくなるので好
ましくなく、一方、5g/10分を越えると溶融粘度が
低くく成り、発泡剤の分解は抑制され気泡の不揃いは解
消されるが、シート成形時特殊な冷却装置を用いないと
平滑なシートが得られなかったり、あるいは発泡体の伸
びの低下、加熱成形時形態保持性の悪化、高温下の耐圧
性が悪化し、良好な成形品が得られなくなるので好まし
くない。
The MFR is preferably in the range of 0.5 to 5 g / 10 minutes, more preferably 1 to 3 g / 10 minutes. If the MFR is less than 0.5 g / 10 min, the foaming agent is decomposed due to heat generated by shearing, and irregularity of air bubbles is likely to occur. Is suppressed and the irregularity of bubbles is eliminated, but if a special cooling device is not used during sheet molding, a smooth sheet cannot be obtained, or the elongation of the foam decreases, the shape retention during heat molding deteriorates, high temperature This is not preferable because the lower pressure resistance deteriorates and a good molded product cannot be obtained.

【0017】本発明に用いられるポリエチレン系樹脂と
は、たとえば、エチレンと炭素数が4〜12のαオレフ
ィンをチーグラー触媒、メタロセン触媒などを用いて共
重合した密度が0.890〜0.940g/cm3 、M
FRが1〜20g/10分のものである。エチレンに共
重合されるαオレフィンの種類としては炭素数が4〜1
2の中から選定すれば特に制限はされないが好ましくは
炭素数4〜8のものを共重合したものが価格、物性の両
面から有利である。密度は0.890〜0.940g/
cm3 、好ましくは0.905〜0.930g/cm3
であるが、密度が0.890g/cm3 未満であると柔
軟性の点では好ましいが、融点が低下し耐熱性が悪化し
たり、樹脂のベタ付きが顕著となり原料の混合工程で発
泡剤などの混合不良や発泡体のブロッキングを引き起こ
すので好ましくない。また、0.940g/cm3 を越
えると機械的強度、耐熱性などの点では好ましいが、結
晶性が高く成るため硬くなり緩衝性低下するので好まし
くない。MFRは1〜20g/10分、好ましくは3〜
10g/10分である。MFRが1g/10分未満であ
ると樹脂の溶融粘度が高くなるためシート成形時に剪断
発熱により発泡剤が分解し、粗大気泡を発生しやすくな
るので好ましくない。一方、30g/10分を越えると
溶融粘度は低くなり発泡剤の分解は抑制されるので、粗
大気泡の発生の点では好ましいが、シート成形時特殊な
冷却装置を用いないと平滑なシートが得られなかった
り、あるいは発泡体の伸びが低下するので加熱成形時形
態保持性が悪化、良好な成形品が得られなくなるので好
ましくない。
The polyethylene resin used in the present invention is, for example, a copolymer of ethylene and an α-olefin having 4 to 12 carbon atoms using a Ziegler catalyst, a metallocene catalyst or the like, and has a density of 0.890 to 0.940 g /. cm 3 , M
FR of 1 to 20 g / 10 minutes. The type of α-olefin copolymerized with ethylene has a carbon number of 4-1.
There is no particular limitation as long as it is selected from 2, but those obtained by copolymerizing those having 4 to 8 carbon atoms are advantageous from the viewpoints of both price and physical properties. The density is 0.890 ~ 0.940g /
cm 3 , preferably 0.905 to 0.930 g / cm 3
However, it is preferable in terms of flexibility that the density is less than 0.890 g / cm 3 , but the melting point is lowered and the heat resistance is deteriorated, and the resin becomes sticky, and the foaming agent is used in the raw material mixing step. This is not preferred because it causes poor mixing and foam blocking. If it exceeds 0.940 g / cm 3 , it is preferable in terms of mechanical strength, heat resistance and the like, but it is not preferable because the crystallinity becomes high and it becomes hard and the buffering property decreases. MFR is 1 to 20 g / 10 min, preferably 3 to
10 g / 10 min. If the MFR is less than 1 g / 10 minutes, the melt viscosity of the resin becomes high, so that the foaming agent is decomposed due to heat generated by shearing during sheet molding, and coarse bubbles are easily generated, which is not preferable. On the other hand, if it exceeds 30 g / 10 min, the melt viscosity becomes low and the decomposition of the foaming agent is suppressed, so that it is preferable in terms of the generation of coarse bubbles, but a smooth sheet can be obtained unless a special cooling device is used during sheet forming. It is not preferred because the shape retention during heat molding is deteriorated and the molded product cannot be obtained because the elongation of the foam decreases.

【0018】本発明に用いるジプロペニル化合物は、下
記一般式で表わされる化合物である必要がある。
The dipropenyl compound used in the present invention must be a compound represented by the following general formula.

【0019】[0019]

【化3】 Embedded image

【0020】本発明に用いる上記化合物でベンゼン環に
プロペニル基が直接結合しているものが好ましい。この
間に他の元素が結合すると融点が低下し、液状になるの
でハンドリング性の点で悪化するので好ましくない。な
お、プロペニル基が良い理由としては、p体のみのもの
が容易に得られることであり、通常のジビニルベンゼン
のような異性体を含む混合物は構造によって反応性が異
なるため、均一な架橋が得られないので好ましくない。
The above compounds used in the present invention are preferably those in which a propenyl group is directly bonded to a benzene ring. If other elements are bonded during this time, the melting point is lowered and the liquid becomes liquid, which deteriorates the handling property, which is not preferable. The reason why the propenyl group is good is that the p-form alone can be easily obtained, and a mixture containing isomers such as ordinary divinylbenzene has different reactivity depending on the structure, so that a uniform crosslink is obtained. It is not preferable because it cannot be performed.

【0021】また、本発明ではこの化合物をポリオレフ
ィン系樹脂に高濃度に分散させたいわゆるマスタバッチ
を予め製造し、このマスタバッチ用樹脂組成物を用いて
本発明の発泡用樹脂組成物を製造することもできる。た
とえば、ジプロペニル化合物をポリオレフィン樹脂に混
練りさせて、樹脂組成物に対し10〜50重量%のジプ
ロペニル化合物を含有するマスタバッチ用樹脂組成物を
製造し、これをマスタバッチとして用いることができ
る。マスタ用のポリオレフィン系樹脂としては特に限定
されるものではないが、ポリエチレン系樹脂で行う方が
コスト面で有利であるとともに、低融点の共重合体から
高融点のホモのポリプロピレン樹脂まで適用できるので
好ましい。添加量としては10〜50重量%、好ましく
は15〜40重量%程度が良いと言える。すなわち、1
0重量%未満であると高度の架橋度、具体的には60%
を越えるような架橋度を得る場合、本発明に用いる化合
物の添加量が多くなるため、マスタバッチ用樹脂組成物
が多量に配合されることになり、発泡体としたときの物
性低下、具体的には伸び、成形性の低下を引き起こすの
で好ましくない。一方、50重量%を越えると、発泡体
物性への影響はなくなるので好ましいが、マスタバッチ
用樹脂組成物の保管時にブロッキングしやすくなり、逆
に取り扱い性が悪化するので好ましくない。
In the present invention, a so-called masterbatch in which this compound is dispersed in a polyolefin resin at a high concentration is prepared in advance, and the resin composition for foaming of the present invention is produced using the resin composition for a masterbatch. You can also. For example, a dipropenyl compound is kneaded with a polyolefin resin to produce a resin composition for a masterbatch containing 10 to 50% by weight of a dipropenyl compound with respect to the resin composition, which can be used as a masterbatch. The polyolefin resin for the master is not particularly limited, but it is more advantageous to use a polyethylene resin in terms of cost, and it can be applied from a low melting point copolymer to a high melting point homopolypropylene resin. preferable. It can be said that the amount of addition is 10 to 50% by weight, preferably about 15 to 40% by weight. That is, 1
If the amount is less than 0% by weight, a high degree of crosslinking, specifically 60%
When the degree of crosslinking exceeds, the amount of the compound used in the present invention is increased, so that a large amount of the masterbatch resin composition is blended, and the physical properties of the foam are deteriorated. Is not preferred because it causes elongation and a reduction in moldability. On the other hand, when the content exceeds 50% by weight, it is not preferable because the influence on the physical properties of the foam is eliminated, but the resin composition for the masterbatch tends to be blocked during storage, and conversely, the handleability deteriorates.

【0022】本発明による発泡体用樹脂組成物及び発泡
体は、ポリプロピレン系樹脂30〜90重量%、好まし
くは50〜80重量%にポリエチレン系樹脂10〜70
重量%、好ましくは20〜50重量%で混合した混合物
100重量部に下記一般式で表されるジプロペニル化合
物を1〜10重量部、好ましくは2〜7重量部配合され
たものである。
The resin composition for a foam and the foam according to the present invention may contain 30 to 90% by weight, preferably 50 to 80% by weight of a polypropylene resin and 10 to 70% by weight of a polyethylene resin.
The dipropenyl compound represented by the following general formula is blended in an amount of 1 to 10 parts by weight, preferably 2 to 7 parts by weight, to 100 parts by weight of a mixture mixed at 20% by weight, preferably 20 to 50% by weight.

【0023】[0023]

【化4】 Embedded image

【0024】本発明による樹脂組成物から得られた架橋
発泡体は耐熱性、各種成形性、伸び、柔軟性に優れたも
のとなり、特に高温下での成形、あるいは高圧成形(ス
タンピング、インジェクション)に好適なものである。
The crosslinked foam obtained from the resin composition according to the present invention has excellent heat resistance, various moldability, elongation and flexibility, and is particularly suitable for molding at high temperature or high pressure molding (stamping, injection). It is suitable.

【0025】本発明ではポリプロピレン系樹脂が30重
量%未満では発泡体としたときの柔軟性の点では好まし
いが、耐熱性が低下するので好ましくなく、一方、90
重量%を越えると耐熱性の点では好ましいが、硬くなり
緩衝性が悪化するので好ましくない。
In the present invention, if the content of the polypropylene resin is less than 30% by weight, it is preferable in terms of flexibility when formed into a foam, but it is not preferable because the heat resistance is lowered.
Exceeding the weight percentage is preferable in terms of heat resistance, but is not preferable because it becomes hard and the buffering property deteriorates.

【0026】本発明ではポリエチレン系樹脂が10重量
%未満では耐熱性の点では好ましいが、硬くなり緩衝性
が悪化したり、加熱成形性が悪化するので好ましくな
く、一方、70重量%を越えると緩衝性や成形性の点で
は好ましいが、耐熱性が悪化するので好ましくない。
In the present invention, if the content of the polyethylene resin is less than 10% by weight, it is preferable in terms of heat resistance, but it is not preferable because it becomes hard and the buffering property deteriorates, and the heat moldability deteriorates. Although it is preferable in terms of cushioning property and moldability, it is not preferable because heat resistance deteriorates.

【0027】本発明によるジプロペニル化合物の添加量
が1重量部未満では、架橋に関与する2重結合基量が不
足し、広範囲の架橋度の設定ができなくなるので好まし
くなく、一方、10重量部を越えると広範囲の架橋度設
定の点では好ましいが、融点が溶融押出温度以下である
ため押出工程において可塑剤的な効果が過大となり、押
出機内での溶融状態が見掛け上低く成るため押し出しが
困難となるので好ましくない。また、見掛けの架橋度以
上に架橋点が増加すると考えられるが伸びが低下し、結
果的に成形性が低下するので好ましくない。
If the addition amount of the dipropenyl compound according to the present invention is less than 1 part by weight, the amount of double bond groups involved in crosslinking becomes insufficient, and it becomes impossible to set a wide range of crosslinking degree. Exceeding the above is preferable in terms of setting a wide degree of crosslinking, but the melting point is lower than the melt extrusion temperature, so that the effect of a plasticizer in the extrusion process becomes excessive, and the melt state in the extruder becomes apparently low, so that extrusion is difficult. Is not preferred. Further, it is considered that the number of cross-linking points is increased beyond the apparent degree of cross-linking, but the elongation is lowered, and consequently the moldability is lowered, which is not preferable.

【0028】本発明で用いる熱分解型化学発泡剤として
はアゾジカルボンアミド、アゾジカルボン酸エステル化
合物、アゾジカルボン酸塩、テトラゾール系化合物、
N,N’−ジニトロソペンタメチレンテトラミンなどが
例示されるが、これらについては単独でも混合して用い
てもよく、また、亜鉛化合物、アミン系化合物などと併
用し、発泡の調整を行うこともできる。添加量として
は、1〜20重量部の範囲内が好ましい。
The thermal decomposition type chemical blowing agent used in the present invention includes azodicarbonamide, azodicarboxylic acid ester compound, azodicarboxylate, tetrazole compound,
N, N'-dinitrosopentamethylenetetramine and the like are exemplified. These may be used alone or as a mixture, or may be used in combination with a zinc compound, an amine compound or the like to adjust foaming. it can. The addition amount is preferably in the range of 1 to 20 parts by weight.

【0029】本発明においてはその目的に応じてヒンダ
ードフェノール系、チオ系などに代表される酸化防止
剤、加工安定剤、難燃剤、無機充填剤、顔料などを添加
し、所望の品位のものとすることができる。
In the present invention, antioxidants represented by hindered phenols, thios, etc., processing stabilizers, flame retardants, inorganic fillers, pigments, etc. are added according to the purpose to obtain desired quality. It can be.

【0030】本発明においては本発明の樹脂組成物を溶
融押出し、シート状に成形した後、このシートの段階で
架橋を施す必要があるが、架橋方法としては電離性放射
線や紫外線、具体的には電子線を照射するすることが工
業的に好ましく、その照射エネルギーとしては0.5〜
20Mradが適当であるが、極力10Mrad以下で
架橋する方が望ましい。この照射エネルギーによって生
じる架橋、すなわちゲル分率は20〜70%で、このゲ
ル分率が20%未満では高温下での耐圧性が低下し、プ
レス成形が出来なくなるので好ましくなく、70%を越
えると耐圧性は向上するが硬くなり、低温下での衝撃性
が悪化し割れが生じやすくなるので好ましくない。
In the present invention, after the resin composition of the present invention is melt-extruded and formed into a sheet, it is necessary to carry out crosslinking at the stage of this sheet. Is preferably industrially irradiated with an electron beam, and the irradiation energy is 0.5 to
Although 20 Mrad is appropriate, it is desirable to crosslink with 10 Mrad or less as much as possible. The crosslinking caused by the irradiation energy, that is, the gel fraction is 20 to 70%. If the gel fraction is less than 20%, the pressure resistance at high temperatures is reduced, and press molding cannot be performed. However, the pressure resistance is improved but the hardness is increased, and the impact resistance at low temperatures is deteriorated, so that cracks are likely to occur.

【0031】本発明の発泡体は各種の発泡法、具体的に
は縦(横)型熱風発泡法、薬液浴上発泡法などに例示さ
れる方法にて製造されるが、好ましくは薬液浴上発泡法
による方が発泡体の長手方向、幅方向の各方向の物性バ
ランスのとれたものが得られるので望ましい。
The foam of the present invention is produced by various foaming methods, specifically, a method exemplified by a vertical (horizontal) type hot air foaming method, a foaming method in a chemical bath, etc., and preferably a foaming method in a chemical bath. The foaming method is preferable because a good balance of physical properties in each of the longitudinal direction and the width direction of the foam can be obtained.

【0032】次に本発明による架橋発泡用ポリオレフィ
ン系樹脂組成物及び架橋発泡体シートの製造方法の一態
様について説明する。
Next, one embodiment of a method for producing a polyolefin resin composition for cross-linked foaming and a cross-linked foam sheet according to the present invention will be described.

【0033】プロピレンにエチレンを4.2重量%ラン
ダム共重合したMFRが1.8g/10分、融点が13
9℃のポリプロピレン系樹脂の粉体128kgとエチレ
ンに炭素数が6のαオレフィンを共重合したMFRが8
g/10分、融点が125℃のポリエチレン系樹脂の粉
体32kg、安定剤として”イルガノックス1010”
0.95kg、発泡剤としてアゾジカルボンアミド1
7.7kg、架橋助剤としてp,p’−ジプロペニルベ
ンゼン5.5kgを準備し、ポリプロピレン系樹脂、ポ
リエチレン系樹脂、発泡剤、安定剤、架橋助剤を有効容
積750リットルのヘンシェルミキサーに投入し、20
0〜400rpmの低速回転で約3分混合し、次いで8
00〜1000rpmの高速回転とし、3分間混合の発
泡用樹脂組成物とする。この発泡用樹脂組成物を発泡剤
の分解しない温度、具体的には160〜190℃に加熱
したベント付きの押出機に導入してTダイから押し出
し、厚みが1.55mm、幅560mmの架橋発泡用シ
ートに成形した。このシートに5Mradの電子線を照
射し、架橋せしめた後、発泡剤の分解温度より20〜5
0℃高い温度に設定した薬液浴上発泡装置に連続的に導
入、加熱発泡して連続シート状架橋発泡体として巻き取
った。このようにして得られた発泡体は厚み2.95m
m、幅1450mm、架橋度は51%、発泡体の厚さ方
向の架橋度分布は表層と中心層の差が1%、発泡倍率2
0倍のものであった。
MFR obtained by random copolymerization of propylene with 4.2% by weight of ethylene has an MFR of 1.8 g / 10 min and a melting point of 13
MFR of 128 kg of 9 ° C. polypropylene resin powder and ethylene copolymerized with α-olefin having 6 carbon atoms is 8
g / 10 minutes, 32 kg of polyethylene resin powder having a melting point of 125 ° C., and “Irganox 1010” as a stabilizer.
0.95 kg, azodicarbonamide 1 as blowing agent
Prepare 7.7 kg, 5.5 kg of p, p'-dipropenylbenzene as a crosslinking aid, and put a polypropylene resin, a polyethylene resin, a foaming agent, a stabilizer, and a crosslinking aid into a Henschel mixer having an effective volume of 750 liters. Then 20
Mix at low speed of 0-400 rpm for about 3 minutes, then
The resin composition for foaming is mixed at a high speed of 00 to 1000 rpm and mixed for 3 minutes. This foaming resin composition is introduced into a vented extruder heated to a temperature at which the foaming agent does not decompose, specifically, heated to 160 to 190 ° C., extruded from a T-die, and crosslinked foamed with a thickness of 1.55 mm and a width of 560 mm. Molded into a sheet for use. After irradiating the sheet with 5 Mrad of electron beam to crosslink the sheet, the temperature of the sheet is increased by 20 to 5 from the decomposition temperature of the foaming agent.
It was continuously introduced into a foaming device on a chemical bath set at a temperature higher by 0 ° C., heated and foamed, and wound up as a continuous sheet-like crosslinked foam. The foam thus obtained has a thickness of 2.95 m.
m, width 1450 mm, degree of crosslinking 51%, distribution of degree of crosslinking in the thickness direction of the foam, 1% difference between surface layer and center layer, expansion ratio 2
It was 0 times.

【0034】前述したように、従来、架橋助剤として脂
肪族ジ(メタ)アクリレート、具体的には1・9ノナン
ジ(メタ)アクリレート、異性体含有ジビニルベンゼン
などの使用は知られてはいたが、本発明では、安全性と
ハンドリング、架橋特性などを考慮して初めて、架橋発
泡体の架橋助剤としてジプロペニル化合物を適用した結
果、本発明による樹脂組成物から得られた架橋発泡体は
製造上の安全性が確保され、かつ、耐熱性、各種成形
性、伸び、柔軟性に優れたものとなり、特に高温下での
成形、あるいは高圧成形(スタンピング、インジェクシ
ョン)に好適なものが得られたものである。
As described above, the use of aliphatic di (meth) acrylate, specifically 1.9 nonanedi (meth) acrylate, isomer-containing divinylbenzene, etc. as a crosslinking aid has been known. In the present invention, for the first time in consideration of safety and handling, cross-linking characteristics, etc., as a result of applying a dipropenyl compound as a cross-linking aid for a cross-linked foam, a cross-linked foam obtained from the resin composition according to the present invention is produced. Which has excellent heat resistance, various moldability, elongation, and flexibility. Suitable for molding under high temperature or high pressure molding (stamping, injection). It is.

【0035】[評価方法及び評価基準]本発明による評
価方法及び評価基準は次の通りである。 (1)架橋度 発泡体を細断し、0.2g精秤する。このものを溶媒と
してキシレン、温度100℃下のソックスレイ抽出器で
8時間抽出後、不溶分を取り出し、純粋で洗浄後、更に
アセトンで洗浄、更にこのものを80℃に加熱した真空
乾燥機で1時間加熱し、揮発分を完全に除去後、室温で
自然冷却する。このものの重量(W1)gを測定し、次
式で架橋度を求める。なお、通常の架橋度用サンプルは
切り出した発泡体の厚さ方向全体を用いるが、両表層と
中心層の架橋度差を測定するサンプルは発泡体の厚さ方
向に0.5mmの厚さでスライスし、その両表層、中心
層のサンプルを用いて架橋度を測定する。 架橋度=(W1/0.2)×100(%) 両表層と中心層の架橋度差は両表層架橋度平均から中心
部架橋度を差し引き、下記の範囲を合格とする。±3%
を合格とする
[Evaluation Method and Evaluation Criteria] The evaluation method and evaluation criteria according to the present invention are as follows. (1) Degree of Crosslinking The foam is shredded and precisely weighed at 0.2 g. This was used as a solvent and extracted with xylene at a temperature of 100 ° C for 8 hours using a Soxhlet extractor. The insolubles were taken out, washed with pure water, further washed with acetone, and further dried with a vacuum dryer heated to 80 ° C. After heating for 1 hour to completely remove volatile components, the mixture is naturally cooled at room temperature. The weight (W 1 ) g of this product is measured, and the degree of crosslinking is determined by the following equation. In addition, the normal cross-linking degree sample uses the whole thickness direction of the cut out foam, but the sample for measuring the cross-linking degree difference between both the surface layer and the center layer has a thickness of 0.5 mm in the thickness direction of the foam. The slices are sliced, and the degree of cross-linking is measured using the samples of both the surface layer and the center layer. Degree of crosslinking = (W 1 /0.2)×100(%) The difference in the degree of crosslinking between both surface layers and the center layer is determined by subtracting the degree of crosslinking in the center from the average degree of crosslinking between both surface layers, and the following range is considered acceptable. ± 3%
To pass

【0036】(2)成形性 直径(D)に対し深さ(L)のカップ状の成形金型を備
えた真空成形機で加熱成形し、発泡体が破れることなく
カップ状に成形されたL/D比を成形性とする。通常は
L/D0.2刻みで1.0までの金型を並べて破れる深
さを見ておき、その後その周辺のL/D0.02刻みで
0.1までの金型を使用して詳細な成形性を測定する。 L/D :0.5以上を合格とする
(2) Formability Heat-formed by a vacuum forming machine equipped with a cup-shaped forming die having a depth (L) with respect to the diameter (D), and the L was formed into a cup without breaking the foam. The / D ratio is defined as moldability. Normally, molds of up to 1.0 are arranged side by side in L / D 0.2 increments, and the depth to which the mold is torn is observed. Measure moldability. L / D: Pass 0.5 or more

【0037】(3)機械強度、伸び JIS−K−6767に準じて測定する。 機械強度は(発泡倍率×(−1.5)+45))以上を
合格 伸びは250%以上を合格とする。
(3) Mechanical strength and elongation Measured according to JIS-K-6767. Mechanical strength passes (expansion ratio x (-1.5) + 45)) or more. Elongation passes 250% or more.

【0038】(4)耐熱性 発泡体シートから15×15cmを切り出し、シート長
手方向(MD)、幅方向(TD)に10cm間隔の測定
用標線を書き込み、厚さ(T)を測定する。炭酸カルシ
ュウムを散布した耐熱板上にこのサンプルを置き、12
0℃に加熱した熱風オーブンに入れ、2時間加熱後、取
り出し、室温となるまで自然冷却する。このサンプルの
標線間隔(MDx,TDx,Tx)を測定し、次式で寸
法変化率を算出し、次の基準で耐熱性を評価する。 MD:((100−MDx)/100)×100(%) TD:((100−TDx)/100)×100(%) T :((T−Tx)/T)×100(%) 耐熱性:MD,TDは±5%以内を合格とする。 Tは±7%以内を合格とする。
(4) Heat Resistance A 15 × 15 cm piece is cut out from the foam sheet, and measurement marks are drawn at intervals of 10 cm in the sheet longitudinal direction (MD) and width direction (TD), and the thickness (T) is measured. Place this sample on a heat-resistant plate on which calcium carbonate was sprayed.
Place in a hot air oven heated to 0 ° C., heat for 2 hours, remove, and cool naturally to room temperature. The mark interval (MDx, TDx, Tx) of this sample is measured, the dimensional change rate is calculated by the following equation, and the heat resistance is evaluated based on the following criteria. MD: ((100−MDx) / 100) × 100 (%) TD: ((100−TDx) / 100) × 100 (%) T: (((T−Tx) / T) × 100 (%) Heat resistance : MD and TD are acceptable within ± 5%. T is acceptable within ± 7%.

【0039】(5)融点 示査走査熱量計(パーキンエルマ社製:DSCIII)
で測定した溶融吸熱スペクトルでもっとも大きなピーク
を融点とする。
(5) Melting point scanning calorimeter (Perkin Elmer: DSCIII)
The largest peak in the melting endothermic spectrum measured in step is defined as the melting point.

【0040】(6)MFR ポリプロピレン系樹脂はJIS−K−6758、ポリエ
チレン系樹脂はJIS−K−6760に準じて測定し
た。
(6) MFR The polypropylene resin was measured according to JIS-K-6758, and the polyethylene resin was measured according to JIS-K-6760.

【0041】(7)密度 ポリエチレン系樹脂はJIS−K−6760に準じて測
定した。
(7) Density The polyethylene resin was measured according to JIS-K-6760.

【0042】[0042]

【実施例】次に本発明を実施例に基づいて説明する。 実施例1 プロピレンにエチレンを3.6重量%ランダム共重合し
た融点が142℃MFRが2.5g/10分、のポリプ
ロピレン系樹脂の粉体96kgとエチレンに炭素数が4
のαオレフィンを共重合したMFRが5g/10分、融
点が125℃のポリエチレン系樹脂の粉体64kg、安
定剤として”イルガノックス1010”0.95kg、
発泡剤としてアゾジカルボンアミド7.4kg、架橋助
剤としてp,p’−ジプロペニルベンゼン3.2kgを
準備し、ポリプロピレン系樹脂、ポリエチレン系樹脂、
発泡剤、安定剤、架橋助剤を有効容積750リットルの
ヘンシェルミキサーに投入し、200〜400rpmの
低速回転で約3分混合し、ついで800〜1000rp
mの高速回転とし、3分間混合して50℃になった時点
で排出して発泡用樹脂組成物とする。
Next, the present invention will be described based on embodiments. Example 1 96 kg of a polypropylene resin powder obtained by random copolymerization of 3.6% by weight of ethylene with propylene at a melting point of 142 ° C. and an MFR of 2.5 g / 10 min, and ethylene having 4 carbon atoms
MFR obtained by copolymerizing α-olefin of 5 g / 10 min, melting point of 125 ° C., 64 kg of polyethylene resin powder, 0.95 kg of “Irganox 1010” as a stabilizer,
Prepare 7.4 kg of azodicarbonamide as a foaming agent and 3.2 kg of p, p'-dipropenylbenzene as a cross-linking aid.
A blowing agent, a stabilizer and a crosslinking assistant are charged into a Henschel mixer having an effective volume of 750 liters, and mixed at a low speed of 200 to 400 rpm for about 3 minutes, and then 800 to 1000 rpm.
m, and the mixture is mixed for 3 minutes and discharged when the temperature reaches 50 ° C. to obtain a foaming resin composition.

【0043】この発泡用樹脂組成物を発泡剤の分解しな
い温度、具体的には160〜190℃に加熱したベント
付きの押出機に導入、Tダイから押し出し、厚みが1.
2mm、幅56mmの架橋発泡用シートに成形した。こ
のシートに3.2Mradの電子線を照射し、架橋せし
めた後、発泡剤の分解温度より20〜100℃高い温度
に設定した縦型熱風発泡装置に連続的に導入、加熱発泡
して連続シート状架橋発泡体として巻き取った。
The foaming resin composition is introduced into a vented extruder heated to a temperature at which the foaming agent does not decompose, specifically, heated to 160 to 190 ° C., and extruded from a T-die.
It was molded into a crosslinked foaming sheet having a width of 2 mm and a width of 56 mm. The sheet is irradiated with a 3.2 Mrad electron beam and crosslinked, and then continuously introduced into a vertical hot-air foaming apparatus set at a temperature 20 to 100 ° C. higher than the decomposition temperature of the foaming agent, heated and foamed to form a continuous sheet. And wound up as a crosslinked foam.

【0044】このようにして得られた発泡体のは厚み
2.5mm、幅1350mm、架橋度は50%、両表層
と中心部の架橋度差は0.8%、発泡倍率15倍のもの
であった。
The foam thus obtained has a thickness of 2.5 mm, a width of 1350 mm, a degree of crosslinking of 50%, a difference in the degree of crosslinking between both surface layers and the central portion of 0.8%, and an expansion ratio of 15 times. there were.

【0045】この樹脂組成物を表1に、製品の特性を表
2に示した。
The resin composition is shown in Table 1, and the characteristics of the product are shown in Table 2.

【0046】表のごとく本発明による樹脂組成物とし、
架橋発泡体としたため成形性、伸び、耐熱性に優れたポ
リプロピレン系架橋発泡体である。
As shown in the table, the resin composition according to the present invention was
Since it is a crosslinked foam, it is a polypropylene-based crosslinked foam excellent in moldability, elongation and heat resistance.

【0047】比較例1 表1に示したような成分、樹脂組成のものを用い、架橋
発泡体とし、得られた発泡体特性を表2に示した。
Comparative Example 1 Using the components and resin compositions shown in Table 1 as a crosslinked foam, the properties of the obtained foam are shown in Table 2.

【0048】このように実施例1に示した本発明による
樹脂組成物から得られた架橋発泡体は耐熱性、各種成形
性、伸び、柔軟性に優れたものとなり、特に高温下での
高圧成形(スタンピング、インジェクション)に好適な
ものである。
As described above, the crosslinked foam obtained from the resin composition of the present invention shown in Example 1 has excellent heat resistance, various moldability, elongation, and flexibility, and particularly high-pressure molding under high temperature. (Stamping, injection).

【0049】一方、比較例1に示した物は本発明外にあ
るため伸びや成形性、耐熱性のいずれかが不足する不満
足な架橋発泡体であった。
On the other hand, since the product shown in Comparative Example 1 was outside the scope of the present invention, it was an unsatisfactory crosslinked foam having insufficient elongation, moldability or heat resistance.

【0050】[0050]

【表1】 [Table 1]

【0051】[0051]

【表2】 [Table 2]

【0052】[0052]

【発明の効果】以上説明したように、本発明の架橋発泡
用ポリオレフィン系樹脂組成物及びその架橋発泡体によ
れば、製造工程での安全性、取り扱い性を改善できると
ともに、架橋度、発泡倍率等について一定の品質を保持
しながら耐熱性、成形性、機械強度、伸び等に優れた発
泡体を得ることができる。
As described above, according to the polyolefin resin composition for cross-linking and foaming of the present invention and the cross-linked foam thereof, it is possible to improve the safety and handleability in the production process, as well as the degree of cross-linking and expansion ratio. It is possible to obtain a foam excellent in heat resistance, moldability, mechanical strength, elongation and the like while maintaining a certain quality.

───────────────────────────────────────────────────── フロントページの続き (72)発明者 内藤 基 滋賀県大津市園山1丁目1番1号 東レ株 式会社滋賀事業場内 Fターム(参考) 4F074 AA17 AA24 AA98 AB05 AD01 BA12 BA13 BA16 BB28 CA21 CA25 CC02X CC04X CC04Y CC06X CC48 CC50 DA35 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Motoi Naito 1-1-1, Sonoyama, Otsu-shi, Shiga F-term in Shiga Plant of Toray Industries, Inc. (reference) 4F074 AA17 AA24 AA98 AB05 AD01 BA12 BA13 BA16 BB28 CA21 CA25 CC02X CC04X CC04Y CC06X CC48 CC50 DA35

Claims (4)

【特許請求の範囲】[Claims] 【請求項1】 ポリオレフィン系樹脂100重量部に対
し、下記一般式 【化1】 で表されるジプロペニル化合物を1〜10重量部、熱分
解型化学発泡剤を1〜15重量部含有することを特徴と
する架橋発泡用ポリオレフィン系樹脂組成物。
1. A polyolefin-based resin (100 parts by weight) based on the following general formula: 1 to 10 parts by weight of a dipropenyl compound represented by the formula (1) and 1 to 15 parts by weight of a thermal decomposition type chemical blowing agent.
【請求項2】 前記ポリオレフィン系樹脂が、MFRが
0.5〜5g/10分の範囲にあるポリプロピレン系樹
脂(a)30〜90重量%とMFRが1〜20g/10
分の範囲にあるポリエチレン系樹脂(b)10〜70重
量%からなる請求項1に記載の架橋発泡用ポリオレフィ
ン系樹脂組成物。
2. The polyolefin-based resin has a MFR in the range of 0.5 to 5 g / 10 minutes, 30 to 90% by weight of a polypropylene-based resin (a), and an MFR of 1 to 20 g / 10.
The polyolefin resin composition for crosslinking and foaming according to claim 1, comprising 10 to 70% by weight of the polyethylene resin (b) in the range of 1 minute.
【請求項3】 ジプロペニル化合物を10〜50重量%
含有するポリオレフィン系樹脂組成物を用いて請求項1
または2に記載の架橋発泡用ポリオレフィン系樹脂組成
物を製造することを特徴とする架橋発泡用ポリオレフィ
ン系樹脂組成物の製造方法。
3. A dipropenyl compound in an amount of 10 to 50% by weight.
2. The method according to claim 1, wherein the polyolefin resin composition is used.
Or a method for producing a polyolefin resin composition for crosslinking and foaming, which comprises producing the polyolefin resin composition for crosslinking and foaming according to (2).
【請求項4】 請求項1または2に記載の架橋発泡用ポ
リオレフィン系樹脂組成物をシート状に成形した後、電
離放射線を照射あるいは紫外線を照射して架橋した後、
常圧下で加熱発泡した架橋ポリオレフィン系樹脂発泡
体。
4. After forming the polyolefin resin composition for cross-linking and foaming according to claim 1 or 2 into a sheet, the cross-linking is performed by irradiating with ionizing radiation or irradiating ultraviolet rays.
Crosslinked polyolefin resin foam foamed by heating under normal pressure.
JP16317999A 1999-06-10 1999-06-10 Polyolefin resin composition for crosslinking and foaming, and crosslinked foam prepared therefrom Pending JP2000351865A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP16317999A JP2000351865A (en) 1999-06-10 1999-06-10 Polyolefin resin composition for crosslinking and foaming, and crosslinked foam prepared therefrom

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP16317999A JP2000351865A (en) 1999-06-10 1999-06-10 Polyolefin resin composition for crosslinking and foaming, and crosslinked foam prepared therefrom

Publications (1)

Publication Number Publication Date
JP2000351865A true JP2000351865A (en) 2000-12-19

Family

ID=15768756

Family Applications (1)

Application Number Title Priority Date Filing Date
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Country Status (1)

Country Link
JP (1) JP2000351865A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003105114A (en) * 2001-09-28 2003-04-09 Nitto Denko Corp Porous film
JP2006169404A (en) * 2004-12-16 2006-06-29 Sekisui Chem Co Ltd Foamed sheet of crosslinked polyolefinic resin
EP1752485A1 (en) 2005-08-08 2007-02-14 Alveo AG Soft polyolefin foams with high heat resistance
US9260577B2 (en) 2009-07-14 2016-02-16 Toray Plastics (America), Inc. Crosslinked polyolefin foam sheet with exceptional softness, haptics, moldability, thermal stability and shear strength

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003105114A (en) * 2001-09-28 2003-04-09 Nitto Denko Corp Porous film
JP4659308B2 (en) * 2001-09-28 2011-03-30 日東電工株式会社 Porous film
JP2006169404A (en) * 2004-12-16 2006-06-29 Sekisui Chem Co Ltd Foamed sheet of crosslinked polyolefinic resin
EP1752485A1 (en) 2005-08-08 2007-02-14 Alveo AG Soft polyolefin foams with high heat resistance
US9260577B2 (en) 2009-07-14 2016-02-16 Toray Plastics (America), Inc. Crosslinked polyolefin foam sheet with exceptional softness, haptics, moldability, thermal stability and shear strength
US10301447B2 (en) 2009-07-14 2019-05-28 Toray Plastics (America), Inc. Crosslinked polyolefin foam sheet with exceptional softness, haptics, moldability, thermal stability and shear strength

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