JPS59221347A - Thermoplastic elastomer composition having excellent injection weldability - Google Patents

Thermoplastic elastomer composition having excellent injection weldability

Info

Publication number
JPS59221347A
JPS59221347A JP58095074A JP9507483A JPS59221347A JP S59221347 A JPS59221347 A JP S59221347A JP 58095074 A JP58095074 A JP 58095074A JP 9507483 A JP9507483 A JP 9507483A JP S59221347 A JPS59221347 A JP S59221347A
Authority
JP
Japan
Prior art keywords
crystalline
butene
thermoplastic elastomer
organic peroxide
elastomer composition
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
Application number
JP58095074A
Other languages
Japanese (ja)
Other versions
JPH0410505B2 (en
Inventor
Katsuyoshi Yonekura
米倉　克佳
Akira Uchiyama
晃 内山
Akira Matsuda
松田　昭
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.)
Mitsui Petrochemical Industries Ltd
Original Assignee
Mitsui Petrochemical Industries Ltd
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 Mitsui Petrochemical Industries Ltd filed Critical Mitsui Petrochemical Industries Ltd
Priority to JP58095074A priority Critical patent/JPS59221347A/en
Priority to CA000455409A priority patent/CA1246268A/en
Priority to US06/615,244 priority patent/US4650830A/en
Priority to EP84303657A priority patent/EP0132931B1/en
Priority to DE8484303657T priority patent/DE3484608D1/en
Publication of JPS59221347A publication Critical patent/JPS59221347A/en
Priority to US07/201,254 priority patent/US4906694A/en
Priority to US07/774,144 priority patent/US5128413A/en
Publication of JPH0410505B2 publication Critical patent/JPH0410505B2/ja
Granted legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C66/00—General aspects of processes or apparatus for joining preformed parts
    • B29C66/70—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material
    • B29C66/71—General aspects of processes or apparatus for joining preformed parts characterised by the composition, physical properties or the structure of the material of the parts to be joined; Joining with non-plastics material characterised by the composition of the plastics material of the parts to be joined

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Lining Or Joining Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

PURPOSE:To provide a composition suitable for the injection welding of molded articles with each other without preheating, by carrying out the dynamic heat treatment of a mixture of a polyolefin decomposable with organic peroxide and an amorphous ethylene-alpha-olefin copolymer in the presence of an organic peroxide. CONSTITUTION:A mixture of (A) a crystalline polyolefin decomposable with organic peroxide and containing crystalline poly-1-butene and (B) an amorphous ethylene-alpha-olefin copolymer, is subjected to the dynamic heat-treatment in the presence of (C) an organic peroxide. The component A is a mixture of crystalline poly-1-butene and a low-crystalline propylene-1-butene copolymer, etc., and the component C is preferably bisperoxide compound. The weight ratio of A/B is 60/40-5/95, preferably 40/60-10/90, and the amount of the component C is preferably 0.1-1pt.wt.per 100pts.wt. of A+B.

Description

【発明の詳細な説明】 本発明は有機過酸化物分解型ポリオレフィンとエチレン
−α−オレフィン系非晶質共重合体との混合物を有機過
酸化物の存在下で動的に熱処理して得られる射出融着性
の良好な熱可塑性エラストマー組成物に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention is obtained by dynamically heat-treating a mixture of an organic peroxide-decomposed polyolefin and an ethylene-α-olefin amorphous copolymer in the presence of an organic peroxide. The present invention relates to a thermoplastic elastomer composition with good injection fusion properties.

オレフィン系熱可塑性エラストマーは加硫ゴムと類似の
エラストマー性を示す一方、ポリエチレン、ポリプロピ
レン等の熱可塑性樹脂と同等の成形性を示すことを利用
して通常の樹脂と同様に成形され、成形物は主と１−で
エラストマー性が要求される用途である自動車のバンパ
ー、外装モール、ウィンドシールドガスケット、エンブ
レムや内装用の表皮材シートとして、また建材用のガス
ケット等に使用され始めている。Olefinic thermoplastic elastomers exhibit elastomer properties similar to those of vulcanized rubber, while exhibiting moldability equivalent to thermoplastic resins such as polyethylene and polypropylene. Utilizing this fact, they are molded in the same way as ordinary resins, and molded products are It has begun to be used mainly for applications that require elastomer properties, such as automobile bumpers, exterior moldings, windshield gaskets, emblems and interior covering sheets, and gaskets for building materials.

上記用途の中、特に加硫ゴムに類似の性質が要求される
自動車のウィンドシールドガスケットや建材用の各種ガ
スケット等の分野に使用されるべきオレフィン系熱可塑
性エラストマーは通常のオレフィン系熱可塑性エラスト
マー中のエチレン−α−オレフィン系共重合体エラスト
マー成分の含有量を増すことにより得られる。Among the above applications, olefinic thermoplastic elastomers to be used in fields such as automobile windshield gaskets and various gaskets for building materials, which require properties similar to those of vulcanized rubber, are among ordinary olefinic thermoplastic elastomers. It can be obtained by increasing the content of the ethylene-α-olefin copolymer elastomer component.

しかし、この様にして得られた柔軟性に富む熱可塑性エ
ラストマーは融解時の流動性に乏しく、複雑な形状が要
求される自動車のウィンドシールガスケットや建材用の
ガスケット等の成形物を射出成形によって直接に成形す
ることは難かしい。However, the highly flexible thermoplastic elastomer obtained in this way has poor fluidity when melted, and can be used to make molded products such as automobile wind seal gaskets and building material gaskets that require complex shapes by injection molding. It is difficult to mold directly.

一方、この軟質の熱可塑性エラストマーは良好な異形成
形性を備えているので、その性質を利用して押出成形に
より上記物品を成形する方策が考えられるが、この場合
には異形押出された成形物の端部同志の接合が必要にな
る。On the other hand, since this soft thermoplastic elastomer has good shapeability, it is conceivable to use this property to mold the above article by extrusion molding, but in this case, it is possible to mold the above-mentioned article by extrusion molding. It is necessary to join the ends of each other.

この接合を行なうには、２以上の接合されるべき押出成
形品を割型内に設置し、両成形品の端部間に融着性の良
好な熱可塑性エラストマーを射出注入Ｉ７て両者を融着
することが好ましい。この場合、割型は射出成形法を適
用１〜得る構造のものであることが好ましい。To perform this joining, two or more extruded products to be joined are placed in a split mold, and a thermoplastic elastomer with good fusion properties is injected between the ends of both molded products to fuse them. It is preferable to wear it. In this case, it is preferable that the split mold has a structure to which the injection molding method can be applied.

処が、多くの場合に、熱可塑性エラストマーの押出成形
品を上記方法によって接合しても、実用に供し得る強度
で接合を行なうことは難かしい。However, in many cases, even if extrusion molded products of thermoplastic elastomer are joined by the above method, it is difficult to perform the joining with a strength that can be used for practical purposes.

この問題を解決する方策として、本出願人は接合される
べき上記押出成形品の端部を割型内で予熱することによ
る接合強度の向上法を既に出願１．た（特願昭５５−１
０５６７０号）。As a measure to solve this problem, the present applicant has already proposed a method for improving the bonding strength by preheating the ends of the extruded products to be bonded in a split mold in Application No. 1. (Special application 1986-1)
No. 05670).

本発明者等は上記の様な予備加熱を行なわずとも、熱可
塑性エラストマー製押出成形品の端部同志を射出融着し
得る方法に関して鋭意研究の結果、次に例示する組成物
を割型内の２個以上の熱可塑性エラストマー製押出成形
品の端部間に装入することにより、実用に供し得る強度
で接合された成形品が得られることを見出し、本発明を
完成した。As a result of extensive research into a method for injection fusing the ends of thermoplastic elastomer extrusion products without preheating as described above, the present inventors prepared the following composition in a split mold. The present invention has been completed based on the discovery that a molded article joined with a strength suitable for practical use can be obtained by inserting the extruded molded article between the ends of two or more thermoplastic elastomer extrusion molded articles.

本発明の熱可塑性エラストマー組成物の（α）成分を構
成する結晶質ポリ−１−ブテンとは、例えば次の（１）
〜位）に掲げるものをいう。The crystalline poly-1-butene constituting the component (α) of the thermoplastic elastomer composition of the present invention is, for example, the following (1).
Refers to the items listed in (~).

（１）１−ブテンの結晶質単独重合体、（＋＋）　　１
−ブテンと通常、１０モルチ以下の他のα−オレフィン
又はジオレフィンとの結晶質共重合体、 （ＩＤ　１−ブテンと通常、１０モルチ以下の共重合性
ビニルモノマーとの結晶質共重合体（共重合性ビニルモ
ノマーとは、例えば酢酸ビニル、アクリル酸、その誘導
体を挙げることができる）、 （ＩＶ）　　前記（１）べｍ）の中の２以上の混合物、
（ψ　前記（１）〜４ＶＩにスチレン、その誘導体、不
飽和カルボン酸もしくはその誘導体をグラフト重合させ
てなる結晶質変性重合体又は前記（１）〜４Ｖｌを部分
的にハロゲン化してなる重合体５− （Ｖｔ）　前記（１）〜（Ｖ）の中の２以上の混合物。(1) Crystalline homopolymer of 1-butene, (++) 1
-Crystalline copolymers of butene and other α-olefins or diolefins, usually up to 10 molar; Examples of the copolymerizable vinyl monomer include vinyl acetate, acrylic acid, and derivatives thereof), (IV) a mixture of two or more of the above (1) b)
(ψ Crystalline modified polymer obtained by graft polymerizing styrene, its derivative, unsaturated carboxylic acid or its derivative to the above (1) to 4VI, or a polymer 5 formed by partially halogenating the above (1) to 4Vl) - (Vt) A mixture of two or more of the above (1) to (V).

本発明組成物の（ａ）成分は上記（１）〜（ｖｔ）ｔｃ
例示１−。Component (a) of the composition of the present invention is the above (1) to (vt)tc
Example 1-.

た成分の他にも、次の様な有機過酸化物により分解（減
成）される型のオレフィン重合体もしくは共重合体又は
それらの混合物を含有することができる。In addition to the above components, the following olefin polymers or copolymers, or mixtures thereof, which are decomposed (degraded) by organic peroxides can be contained.

（Ｖ＋＋）プロピレン、１−ブテン、４−メチル−１−
ペンテン、１−オクテン、１−デセン等の単独重合体、
共重合体であって、結晶質又は非晶質のもの、中でも、
プロピレンと１−ブテンとをモル比で通常４０７６０〜
９０／１０に含有する低結晶質ランダム共重合体（ＰＢ
Ｒ）が好ましい（例、特公昭５７−１１３２２号参照）
０ 上記結晶質重合体に要求される物性としては、ＭＦＲＣ
メルトフローレート）（２３０Ｃ）通常、０．０１〜２
００　ｆ／　１０ｍｍ、好ましくは１〜８０ｒ７１０−
であり、ｐＢＨに対しては、ＭＦＲ（２５０℃）通常０
．１〜２００ｆ／１０順、好ましくは１〜４０１／關で
あ６一 る。前記（＋Ｖλ（ｖｌ）及び（Ｖｊｌ）における各重
合体の配合比は通常、（α）成分中の１−ブテン単位の
含有量が通常、５〜１００モルチ、好ましくけ２５〜１
００モルチになる様に選ぶ。なお、（ｖｌｌ）において
、非晶質重合体も配合される場合には、（α）成分中の
その含有量を５０〜重量％以下に設定することが好まし
い。(V++) Propylene, 1-butene, 4-methyl-1-
Homopolymers such as pentene, 1-octene, 1-decene, etc.
Copolymers, crystalline or amorphous, among others:
The molar ratio of propylene and 1-butene is usually 40,760~
Low crystalline random copolymer (PB) containing 90/10
R) is preferred (for example, see Japanese Patent Publication No. 11322/1983)
0 The physical properties required for the above crystalline polymer include MFRC
Melt flow rate) (230C) Usually 0.01-2
00 f/10mm, preferably 1~80r710-
For pBH, MFR (250°C) is usually 0.
．． 1 to 200f/10, preferably 1 to 401/61. The blending ratio of each polymer in the above (+Vλ(vl) and (Vjl) is usually such that the content of 1-butene units in the (α) component is usually 5 to 100 molt, preferably 25 to 1
Choose so that it will be 0.00 morchi. In addition, in (vll), when an amorphous polymer is also blended, it is preferable to set the content in the (α) component to 50 to 50% by weight or less.

本発明組成物の（ｂ）成分を構成するエチレン−α−オ
レフィン非晶質、共重合体とは、エチレンとα−オレフ
ィンとの二元共重合体及びこれらに更に非共役ジエンを
含有する三元以上の共重合体を包含する。The ethylene-α-olefin amorphous copolymer constituting component (b) of the composition of the present invention refers to a binary copolymer of ethylene and α-olefin and a tertiary copolymer containing a non-conjugated diene to these. It includes copolymers of more than the original.

α−オレフィンとは、炭素数３以上の脂肪族モノオレフ
ィン、例えばプロピレン、１−ブテン、１−ペンテン、
４−メチル−１−ペンテン、１−オクテン、１−デセン
等であり、非共役ジエンとは、例えば１，４−へキサジ
エン、ジシクロペンタジェン、５−エチリデンノルボル
ネン、５−ビニルノルボルネン等が実用化されている。α-olefin is an aliphatic monoolefin having 3 or more carbon atoms, such as propylene, 1-butene, 1-pentene,
4-methyl-1-pentene, 1-octene, 1-decene, etc., and non-conjugated dienes include, for example, 1,4-hexadiene, dicyclopentadiene, 5-ethylidenenorbornene, 5-vinylnorbornene, etc. has been made into

共重合体中おけるこれらモノマ一単位の含有量はエチレ
ン−α−オレフィンの二元共重合体において通常、エチ
レン３０〜９５モルチ、残部がα−オレフィンでアリ、
エチレン−α−オレフィン−非共役ジエンの三元共重合
体において通常、エチレン６０〜９５モルチ、α−オレ
フィン７０〜５モルチ、共重合体１００モルチに対して
、非共役ジエン通常３〜１０モルチ、好ましくは３〜８
モルチである。The content of one unit of these monomers in the copolymer is usually 30 to 95 moles of ethylene in the ethylene-α-olefin binary copolymer, with the remainder being α-olefin.
In the terpolymer of ethylene-α-olefin-nonconjugated diene, usually 60 to 95 molt of ethylene, 70 to 5 molt of α-olefin, and 3 to 10 molt of nonconjugated diene per 100 molt of the copolymer. Preferably 3-8
It's morchi.

共重合体が備えるべき物性と１−ては、Ｘ線回折法によ
り測定した結晶化度通常３５％以下、好ましくは２０％
以下、軟質物においては、ムーニー粘度〔ＭＬｌ刊（１
００）：）通常５〜２００、好ましくは４０〜１２０、
硬質物においては、メルトインデックス（ＡｆＩ（１９
０Ｃ））通常０．１〜１２０、好ましくは０．１〜２０
、［ＭＩ（２３０Ｃ））　　通常０．１〜２００、好ま
しくは０．１〜５０を挙げることができる。Physical properties that the copolymer should have include: crystallinity measured by X-ray diffraction, usually 35% or less, preferably 20%;
In the following, for soft materials, Mooney viscosity [published by MLl (1
00):) Usually 5-200, preferably 40-120,
For hard materials, the melt index (AfI(19
0C)) Usually 0.1-120, preferably 0.1-20
, [MI(230C)) Usually 0.1 to 200, preferably 0.1 to 50.

非共役ジエン含有の三元共重合体においては、ヨウ素価
１〜５０、好ましくは５〜３０の条件が付は加わる。In the case of a terpolymer containing a non-conjugated diene, the condition that the iodine value is 1 to 50, preferably 5 to 30 is added.

共重合体は２種以上の三元共重合体の混合物であっても
よく、共重合体の水素の一部分が塩素又は臭素等のハロ
ゲンで置換されたもの、重合体鎖に酢酸ビニル、アクリ
ル酸も！−〈はその誘導体例えば、メチル（メタ）アク
リレート、グリシジルメタアクリレート又はマレイン酸
もしくはその誘導体例えば、無水マレイン酸、マレイミ
ド、マレイン酸ジメチル等がグラフト重合されたものを
も包含する。中でも好ましいのは無水マレイン酸グラフ
ト物である。The copolymer may be a mixture of two or more types of terpolymers, such as one in which a portion of the hydrogen in the copolymer is replaced with a halogen such as chlorine or bromine, or one in which vinyl acetate or acrylic acid is added to the polymer chain. too! -< also includes derivatives thereof, such as methyl (meth)acrylate, glycidyl methacrylate, or maleic acid, or derivatives thereof, such as maleic anhydride, maleimide, dimethyl maleate, etc., which are graft-polymerized. Among them, maleic anhydride grafted products are preferred.

本発明組成物の（Ｃ）成分である有機過酸化物とは、（
α）成分の軟化点以上の温度域において分解するもので
あれば本発明の目的には十分である。The organic peroxide which is component (C) of the composition of the present invention is (
Any material that decomposes in a temperature range equal to or higher than the softening point of component α) is sufficient for the purpose of the present invention.

有機過酸化物としては、例えば次のものを挙げることが
できる。Examples of organic peroxides include the following.

芳香族系化合物としては、ジベンゾイルペルオキシド、
ジクミルペルオキシド、 １．６−ビス（ｔ−ブチルペルオキシインプロビル）ベ
ンゼン（商品名パーカドツクス１４）、脂肪族系化合物
としては、ジーｔ−プチルベルオ９− キシド、ジラウロイルペルオキシド、 ２．５−ジメチル−２，５−ビス（ｔ−ブチルペルオキ
シ）ヘキサン（商品名バーへキサ２５Ｂ〕、２．５−ジ
メチル−２，５−ビス（ｔ−ブチルペルオキシ）ヘキセ
ン−６，２，５−ジメチル−２゜５−ジメチル−２，５
−ビス（ｌ−ブチルペルオキシ）ヘキシン−６（商品名
バーヘキンン）、芳香族と脂肪族との双方に属するもの
として、ジ（＋！−ブチルパーオキシ）パーベンゾエー
ト、脂環族化合物としては、ρ−メンタンペルオキシド
等。Aromatic compounds include dibenzoyl peroxide,
Dicumyl peroxide, 1,6-bis(t-butylperoxyimprovil)benzene (trade name Percadox 14), and aliphatic compounds include di-t-butylbero-9-oxide, dilauroyl peroxide, 2,5-dimethyl- 2,5-bis(t-butylperoxy)hexane (trade name Barhexa 25B), 2,5-dimethyl-2,5-bis(t-butylperoxy)hexene-6,2,5-dimethyl-2° 5-dimethyl-2,5
-bis(l-butylperoxy)hexyne-6 (trade name Verhequin), di(+!-butylperoxy)perbenzoate as a compound that belongs to both aromatic and aliphatic groups, and ρ as an alicyclic compound. - Menthane peroxide etc.

これらの中でも好ましいものはビスペルオキシド系化合
物である。Among these, preferred are bisperoxide compounds.

本発明組成物の各成分間の配合比は通常、次の範囲に選
ぶ。（ｃＬ）成分対（ｈ）成分の重量比は通常、６０／
４０〜５／９５、好ましくは４０／＜Ｓ　Ｃ１〜１０／
９０、（Ｃ）成分は重合体成分〔（α）＋（Ａ）　’Ｉ
ｔ　１００重量部に対して、通常０．０５〜２、好まし
くけ０１〜１重量部。The blending ratio between each component of the composition of the present invention is usually selected within the following range. The weight ratio of (cL) component to (h) component is usually 60/
40-5/95, preferably 40/<S C1-10/
90, component (C) is a polymer component [(α) + (A) 'I
Usually 0.05 to 2, preferably 01 to 1 part by weight, per 100 parts by weight.

動的に熱処理するとは剪断力を加えた状態下に−１［１
− 熱処理を行なうことをいう。加えられる剪断力はずり速
度で通常、１０〜１０４池−１、好ま］−くは１０２〜
１０３就−１、熱処理の温度は通常、１５０〜２８０Ｃ
，好ましくは１７０〜２４Ｏｒ、熱処理の時間は通常、
１〜２Ｑｍｒｎ、好ましくは３〜１０ｍ１ｎに選ぶ。Dynamic heat treatment means -1 [1
- Refers to heat treatment. The shearing force applied is usually from 10 to 104, preferably from 10 to 10, at a shear rate.
103-1, the temperature of heat treatment is usually 150-280C
, preferably 170 to 24 Or, and the heat treatment time is usually
It is selected to be 1-2Qmrn, preferably 3-10m1n.

本発明の組成物は必要に応じて、酸化防止剤、老化防止
剤、耐光安定剤、耐候安定剤、熱安定剤、帯電防止剤、
顔料、充填剤、伸展油等の軟化剤又は可塑剤、カーボン
ブラック等の各種添加剤を含有し得る。The composition of the present invention may optionally contain antioxidants, anti-aging agents, light stabilizers, weather stabilizers, heat stabilizers, antistatic agents,
It may contain various additives such as pigments, fillers, softeners or plasticizers such as extender oil, and carbon black.

酸化防止剤としては、２，６−シーーープチルーρ−ク
レゾール、４，４′−チオビス（３，５−ジ−ｔ−ブチ
ルフェノール）、テトラキス〔メチレン（３，５−ジ−
ｔ−ブチル−４−ヒドロキシフェニル）グロビオネート
〕メタン、ジラウリルチオジグロピオネート、ビタミン
Ｅ等を挙げることができる。その配合量は重合体組成物
１００重量部当り通常０５０１〜１．０重量部、好まし
くは０．１〜０．８重世部に選ぶ。Examples of antioxidants include 2,6-se-butyl-ρ-cresol, 4,4'-thiobis(3,5-di-t-butylphenol), and tetrakis[methylene(3,5-di-t-butylphenol)].
Examples include t-butyl-4-hydroxyphenyl)globionate]methane, dilaurylthiodiglopionate, and vitamin E. The amount incorporated is usually 0.501 to 1.0 parts by weight, preferably 0.1 to 0.8 parts by weight, per 100 parts by weight of the polymer composition.

耐光安定剤として好捷しいものけビス（口、ろ。Monoke bis (mouth, ro) is good as a light stabilizer.

５．５−テトラメチルピペリジニル）セバケートであり
、その配合量は重合体組成物１００爪量部当り通常０．
Ｏｎ１〜１．０重量部、好ましくは０．０５〜０．５重
量部に選ぶ。5.5-tetramethylpiperidinyl) sebacate, and its amount is usually 0.5-tetramethylpiperidinyl) sebacate per 100 parts of the polymer composition.
On1 to 1.0 parts by weight, preferably 0.05 to 0.5 parts by weight.

上記添加剤を２種以上併用することもできる。Two or more of the above additives can also be used in combination.

動的熱処理の手段としては、剪断力と加熱とを同時に行
ない得るものであれば、用いることができる。例えば、
−軸又は二軸押出機、インテンシフミキサー例えば、パ
ンバリーミキサー、その他ミキンングロール（二本ロー
ル、三本ロール等）等のものを用い得る。As a means for dynamic heat treatment, any method that can simultaneously perform shearing force and heating can be used. for example,
- A shaft or twin-screw extruder, an intensive mixer such as a Panbury mixer, and other mixing rolls (two-roll, three-roll, etc.) can be used.

本発明組成物の調製には、２以上の重合性基を含有する
ラジカル重合性単量体（ｄ）を動的熱処理の際に共存さ
せることが好ましい。In preparing the composition of the present invention, it is preferable to allow a radically polymerizable monomer (d) containing two or more polymerizable groups to coexist during the dynamic heat treatment.

この様な単量体としては、例えばジビニルベンゼン（Ｄ
ＶｆＪ）、イソプロペニルスチレン及ｒ）−ジイソプロ
ペニルスチレンを挙げることができる。Examples of such monomers include divinylbenzene (D
VfJ), isopropenylstyrene and r)-diisopropenylstyrene.

中でも好ま［７いものはジビニルベンゼンである。Among them, divinylbenzene is preferred.

ラジカル重合性単量体の添加量は（α）成分と（ｈ）成
分との和１００重隈部に対して、通常０１〜３重量部、
好ましくは、０．６〜１重量部に選ぶ。The amount of the radically polymerizable monomer added is usually 01 to 3 parts by weight per 100 parts by weight of the sum of the (α) component and the (h) component.
Preferably, the amount is selected to be 0.6 to 1 part by weight.

以下の実験例においては、特に指定しない限り各成分量
を表わす「部」は重量部である。In the following experimental examples, "parts" representing the amount of each component are parts by weight unless otherwise specified.

参考例１゜ エチレン含有率７８モルチ、沃素価１５、ムーニー粘度
ＭＬ　１＋１１（１００ｔｒ）　７０のエチレン−プロ
ピレン−２−エチリデン、５−ノルボルネン共重合体ゴ
ム（以下ＥＰＤＭと略す）７５部、ＭＦＲ（２３０Ｃ１
２，１６に９）１１、密度０．９１の結晶質ポリプロピ
レン（以下ＰＰと略す）１５部、イソブチン−イソプレ
ン共重合ゴム（以下ＦＩＲと略す）１０部、酸化防止剤
として、テトラキス〔メチレン（３，５−ジ−ｔ−ブチ
ル−４−ヒドロキシフェニル）グロピオネート〕メタン
０．６部をバンバリーミキサ−により窒素雰囲気下で、
１８０ｔＴ、５分間混練した後、ロールを通し、シート
カッターによりペレットを製造［７た。次に当該ペレッ
トと１，３ビス（第三ブチルペルオキシイソプロビル）
ベンゼン０．３重量部をジビニルベ１３− ンゼン０．５重量部に溶解分散させた溶液とをヘンシェ
ルミキサーにより混合し、溶液をペレット表面に均一に
付着させた。次いでこのペレットを押出機で窒素雰囲気
下２１０ｔｌ：’、滞留時間５分間で押出し、動的に熱
処理し、熱可塑性エラストマーを得た。Reference Example 1 Ethylene content 78 molt, iodine number 15, Mooney viscosity ML 1+11 (100 tr) 70 ethylene-propylene-2-ethylidene, 5-norbornene copolymer rubber (hereinafter abbreviated as EPDM) 75 parts, MFR (230C1)
2,16 9) 11, 15 parts of crystalline polypropylene (hereinafter abbreviated as PP) with a density of 0.91, 10 parts of isobutyne-isoprene copolymer rubber (hereinafter abbreviated as FIR), tetrakis[methylene (3 , 5-di-t-butyl-4-hydroxyphenyl)gropionate] 0.6 part of methane was added using a Banbury mixer under a nitrogen atmosphere.
After kneading at 180 tT for 5 minutes, the mixture was passed through a roll to produce pellets using a sheet cutter [7]. Next, the pellet and 1,3-bis(tert-butylperoxyisopropyl)
A solution prepared by dissolving and dispersing 0.3 parts by weight of benzene in 0.5 parts by weight of divinylbenzene was mixed using a Henschel mixer, and the solution was uniformly adhered to the pellet surface. The pellets were then extruded using an extruder under a nitrogen atmosphere at 210 tl:' with a residence time of 5 minutes and dynamically heat treated to obtain a thermoplastic elastomer.

この熱可塑性エラストマーを射出成形機を用いて成形し
１２０Ｘ　１　［］０Ｘ２ｒＩｖｎのシートを得た。This thermoplastic elastomer was molded using an injection molding machine to obtain a sheet of 120X 1 []0X2rIvn.

次いでこのシートより幅２５ｍｍの試験片を切り出し長
さ方向に引張り破断時の応力を測定した処、４０　Ｋｑ
　／　ｃｒｌであった。Next, a test piece with a width of 25 mm was cut out from this sheet, and the stress at breakage was measured by tensile in the length direction, which was 40 Kq.
/crl.

実施例１゜ エチレン含有率７８モルチ、沃素価１５、ムーニー粘度
ＭＬ、＋１ｌ（１００ｒ）７０のＥｐＤＭ７０部、ＭＦ
Ｒ（２５０ｔＺ’、　２．１６にり）１１、密度０．９
１の結晶質２．２１０部、ＭＦＲ（１９０Ｃ１２，１６
Ｋｇ）２．０のポリ−１−ブテン樹脂（以下ＰＢ−’＋
と略す）２０部、参考例１の酸化防止剤０．６部をバン
バリーミキサ−により窒素雰囲気下で、１８０ｔＴ、５
分間混練した後、ロールを通し、１４− シートカッターによりペレットを製造した。次に当該ペ
レットと１，６ビス（第三ブチルペルオキシイソプロビ
ル）ベンゼン０．６重量部をジビニルベンゼン０．５重
量部に溶解分散させた溶液とをヘンシェルミキサーによ
り混合し、溶液をペレット表面に均一に付着させた。次
いでこのペレットを押出機で窒素雰囲気下２１０Ｃ１滞
留時間５分間で押出し、動的に熱処理し、熱可塑性エラ
ストマーを得た。この破断時強度を参考例１の方法によ
って測定した処、７３．５　Ｋ９／　ｃｌｆｌであった
。Example 1 70 parts of EpDM with ethylene content 78 molt, iodine number 15, Mooney viscosity ML, +1l (100r) 70, MF
R (250tZ', 2.16 ri) 11, density 0.9
1 crystalline 2.210 parts, MFR (190C12,16
Kg) 2.0 poly-1-butene resin (hereinafter referred to as PB-'+
) and 0.6 parts of the antioxidant of Reference Example 1 were mixed in a Banbury mixer in a nitrogen atmosphere at 180 tT, 5
After kneading for a minute, the pellets were passed through a roll and made into pellets using a 14-sheet cutter. Next, the pellets were mixed with a solution prepared by dissolving and dispersing 0.6 parts by weight of 1,6-bis(tertiary-butylperoxyisopropyl)benzene in 0.5 parts by weight of divinylbenzene using a Henschel mixer, and the solution was applied to the surface of the pellets. It adhered evenly. The pellets were then extruded using an extruder under a nitrogen atmosphere at a residence time of 210C1 for 5 minutes and dynamically heat treated to obtain a thermoplastic elastomer. The strength at break was measured by the method of Reference Example 1 and was 73.5 K9/clfl.

参考例１で得られた射出成形シートを半分に切断し、当
該シートを成形した割型に装填した後実施例１の熱可塑
性エラストマーを射出溶着１−両者間の接合強度を測定
した。結果を表２に示す。The injection molded sheet obtained in Reference Example 1 was cut in half, and the sheet was loaded into a split mold, and then the thermoplastic elastomer of Example 1 was injection-welded and the bonding strength between the two was measured. The results are shown in Table 2.

比較例１゜ 実施例１において参考例１で得られた熱可塑性エラスト
マーを射出溶着ｉ〜接合強度を測定した。Comparative Example 1 In Example 1, the thermoplastic elastomer obtained in Reference Example 1 was subjected to injection welding i to joint strength measurement.

結果を表２に示す。The results are shown in Table 2.

実施例２゜ 参考例１で得られた熱可塑性エラストマー８０重量部と
ＭＦＲ（１９０Ｃ）２０の低結晶質ＰＢ−１２０重量部
とをヘンシェルミキサーにより混合し、次いでこのペレ
ットを押出機で９素雰囲気下２１０ｔＺ’、滞留時間５
分間で押出し、目的とする組成物を得た。参考例１で得
られた射出成形シートを半分に切断し、当該シートを成
形した割型に装填した後実施例２の熱可塑性エラストマ
ー組成物を射出溶着し接合強度を測定した。結果を表２
に示す。Example 2 80 parts by weight of the thermoplastic elastomer obtained in Reference Example 1 and 120 parts by weight of low-crystalline PB-1 with an MFR (190C) of 20 were mixed in a Henschel mixer, and then the pellets were heated in an extruder in a 9-element atmosphere. Lower 210tZ', residence time 5
The desired composition was obtained by extrusion for 1 minute. The injection molded sheet obtained in Reference Example 1 was cut in half, the sheet was loaded into a split mold, and then the thermoplastic elastomer composition of Example 2 was injection welded and the joint strength was measured. Table 2 shows the results.
Shown below.

比較例２゜ 実施例２においてＰＢ−１２０部の代わりに、ＭＦＲ（
１９０ｒ、　２．１６Ｋｙ）　１５、密度０，９ろ、酢
ビコンテン）１４１ｖｔｑ６　のエチレン−酢酸ビニル
共重合樹脂（以下ＥＶＡと略す）２０部を使用して当該
熱可塑性エラストマーを得た。参考例１で得られた射出
成形シートを半分に切断し、当該シートを成形した割型
に装填した後、比較例２の熱可塑性エラストマー組成物
を射出溶着ｌ〜接合強度を測定した。結果を表２に示す
。Comparative Example 2 In place of 120 parts of PB in Example 2, MFR (
The thermoplastic elastomer was obtained using 20 parts of an ethylene-vinyl acetate copolymer resin (hereinafter abbreviated as EVA) having a density of 190r, 2.16Ky) 15, a density of 0.9Ky, and 141vtq6 of bicontene acetate. The injection molded sheet obtained in Reference Example 1 was cut in half, and the sheet was loaded into a split mold, and then the thermoplastic elastomer composition of Comparative Example 2 was measured for injection welding and bonding strength. The results are shown in Table 2.

表　　　　２ 表２から、本発明組成物は熱可塑性エラストマーからな
る成形体に強固に射出溶着し得ることが判る。Table 2 Table 2 shows that the composition of the present invention can be firmly injection-welded to a molded article made of a thermoplastic elastomer.

すなわち、実施例１及び２における接合強度はシートの
破断時強度で評価して、それぞれろ５　Ｋｙ／ｃｒｌ及
びろＯＫｇ　／　ｃａであり、比較例１及び２における
破断時応力それぞれ１０Ｋｇ／ｃＪ及び１５に９／ｃｒ
／１の２倍以上に達しているばかりでなく、その破断状
態も一部材料破壊であることから、接合が単なる粘着に
留らず、接合部の両材料の融合にまで到っていることが
解る。That is, the bonding strength in Examples 1 and 2 was evaluated by the strength at break of the sheet, and was 5 Ky/crl and OKg/ca, respectively, and the stress at break in Comparative Examples 1 and 2 was 10 Kg/cJ and 15 Kg/cJ, respectively. 9/cr
Not only is it more than twice as high as /1, but the state of the rupture is also partially material failure, indicating that the bonding is not just adhesion, but also a fusion of the two materials at the joint. I understand.

なお、参考例は単板の破断強度であるから、各１７− 実施例の破断強度が単板の当該値のそれぞれ９０チ弱及
び７５％に達［２ていることは驚く程強固な融着が異種
材料間に形成されたことを示す証拠である。Furthermore, since the reference example is the breaking strength of the veneer, the breaking strength of each of the 17-examples reached a little less than 90 degrees and 75% of the corresponding value of the veneer [2], which indicates a surprisingly strong fusion bond. This is evidence that this was formed between different materials.

特許出願人　　　三井石油化学工業株式会社代理人　弁
理土鈴木郁男 １８−Patent applicant Mitsui Petrochemical Industries Co., Ltd. Attorney Ikuo Tsuchi Suzuki 18-

Claims (4)

【特許請求の範囲】[Claims] （１）結晶質ポリ−１−ブテンを含有する有機過酸化物
分解型結晶質ポリオレフィン（α）とエチレン−α−オ
レフィン系非晶性共重合体（６）との混合物を有機過酸
化物（Ｃ）の存在下で動的に熱処理して得られることを
特徴とする射出融着性良好な熱可塑性エラストマー組成
物。(1) Organic peroxide ( A thermoplastic elastomer composition with good injection and fusion properties, characterized in that it is obtained by dynamic heat treatment in the presence of C). （２）結晶質ポリ−１−ブテンを含有する有機過酸化物
分解型結晶質ポリオレフィンが結晶質ポリ−１−ブテン
と低結晶質プロピレン−１−ブテン共重合体との混合物
であることを特徴とする特許請求の範囲第１項に記載の
射出融着性良好な熱可塑性エラストマー組成物。(2) The organic peroxide-decomposed crystalline polyolefin containing crystalline poly-1-butene is a mixture of crystalline poly-1-butene and a low-crystalline propylene-1-butene copolymer. A thermoplastic elastomer composition with good injection and fusion properties according to claim 1. （３）結晶質ポリ−１−ブテンを含有する有機過酸化物
分解型結晶質ポリオレフィンが結晶質ポリ−１−ブテン
、結晶質ポリプロピレン及び低結晶質プロピレン−１−
ブテン共重合体の混合物であることを特徴とする特許請
求の範囲第１項又は第２項に記載の射出融着性良好な熱
可塑性エラストマー組成物。(3) The organic peroxide-decomposed crystalline polyolefin containing crystalline poly-1-butene is crystalline poly-1-butene, crystalline polypropylene, and low crystalline propylene-1-butene.
3. The thermoplastic elastomer composition with good injection fusion properties according to claim 1 or 2, which is a mixture of a butene copolymer. （４）結晶質ボリル１−ブテンを除く有機過酸化物分解
型結晶質ポリオｌ／フィン（α）とエチレン−α−オレ
フィン系非晶質共重合体（ｂ）との混合物を有機過酸化
物（ｃ）の存在下で動的に熱処理して得られる熱可塑性
エラストマー組成物（ｄ）と結晶質ポリ−１−ブテンと
を融解混練して得られることを特徴とする射出融着性良
好な熱可塑性エラストマー組成物。(4) A mixture of an organic peroxide-decomposed crystalline polyol/fin (α) excluding crystalline boryl-1-butene and an ethylene-α-olefin amorphous copolymer (b) The thermoplastic elastomer composition (d) obtained by dynamic heat treatment in the presence of (c) and crystalline poly-1-butene are melt-kneaded. Thermoplastic elastomer composition.
JP58095074A 1983-05-31 1983-05-31 Thermoplastic elastomer composition having excellent injection weldability Granted JPS59221347A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP58095074A JPS59221347A (en) 1983-05-31 1983-05-31 Thermoplastic elastomer composition having excellent injection weldability
CA000455409A CA1246268A (en) 1983-05-31 1984-05-30 Thermoplastic elastomer composition and process for preparation thereof
US06/615,244 US4650830A (en) 1983-05-31 1984-05-30 Thermoplastic elastomer composition and process for preparation thereof
EP84303657A EP0132931B1 (en) 1983-05-31 1984-05-31 Thermoplastic elastomer composition and process for preparation thereof
DE8484303657T DE3484608D1 (en) 1983-05-31 1984-05-31 THERMOPLASTIC ELASTOMERS COMPOSITION AND METHOD FOR THE PRODUCTION THEREOF.
US07/201,254 US4906694A (en) 1983-05-31 1988-05-09 Thermoplastic elastomer composition and process for preparation thereof
US07/774,144 US5128413A (en) 1983-05-31 1991-10-15 Thermoplastic elastomer composition and process for preparation thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58095074A JPS59221347A (en) 1983-05-31 1983-05-31 Thermoplastic elastomer composition having excellent injection weldability

Publications (2)

Publication Number Publication Date
JPS59221347A true JPS59221347A (en) 1984-12-12
JPH0410505B2 JPH0410505B2 (en) 1992-02-25

Family

ID=14127827

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58095074A Granted JPS59221347A (en) 1983-05-31 1983-05-31 Thermoplastic elastomer composition having excellent injection weldability

Country Status (1)

Country Link
JP (1) JPS59221347A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0735091A2 (en) * 1995-03-31 1996-10-02 Japan Synthetic Rubber Co., Ltd. Thermoplastic elastomer composition excellent in fusion bondability with an olefinic rubber, and bonded article
US6696516B2 (en) 2000-04-21 2004-02-24 Jsr Corporation Thermoplastic elastomer composition
JP2007070387A (en) * 2005-09-05 2007-03-22 Mitsui Chemicals Inc Thermoplastic elastomer composition and its molding
US7300980B2 (en) 2001-09-18 2007-11-27 Jsr Corporation Thermoplastic elastomer composition and process for producing the same
DE112008000757T5 (en) 2007-03-23 2010-01-28 Sumitomo Chemical Co., Ltd. Composite molding and process for its preparation
JP5631589B2 (en) * 2007-06-14 2014-11-26 三井化学株式会社 Thermoplastic elastomer composition

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5334210A (en) * 1976-09-09 1978-03-30 Mitsui Eng & Shipbuild Co Ltd Device for adjusting load of wheel
JPS5571738A (en) * 1978-11-24 1980-05-30 Mitsui Petrochem Ind Ltd Thermoplastic elastomer
JPH0223062A (en) * 1988-07-08 1990-01-25 Nec Corp Switching power supply controlling circuit

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5334210A (en) * 1976-09-09 1978-03-30 Mitsui Eng & Shipbuild Co Ltd Device for adjusting load of wheel
JPS5571738A (en) * 1978-11-24 1980-05-30 Mitsui Petrochem Ind Ltd Thermoplastic elastomer
JPH0223062A (en) * 1988-07-08 1990-01-25 Nec Corp Switching power supply controlling circuit

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0735091A2 (en) * 1995-03-31 1996-10-02 Japan Synthetic Rubber Co., Ltd. Thermoplastic elastomer composition excellent in fusion bondability with an olefinic rubber, and bonded article
KR100411550B1 (en) * 1995-03-31 2004-04-21 제이에스알 가부시끼가이샤 Thermoplastic Elastomer Composition Excellent in Fusion Bondability with an Olefinic Rubber, and Its Bonded Article
US6696516B2 (en) 2000-04-21 2004-02-24 Jsr Corporation Thermoplastic elastomer composition
US7300980B2 (en) 2001-09-18 2007-11-27 Jsr Corporation Thermoplastic elastomer composition and process for producing the same
EP2130861A2 (en) 2001-09-18 2009-12-09 JSR Corporation Thermoplastic elastomer composition and method for producing the same
EP2135895A1 (en) 2001-09-18 2009-12-23 JSR Corporation Thermoplastic elastomer composition and method for producing the same
JP2007070387A (en) * 2005-09-05 2007-03-22 Mitsui Chemicals Inc Thermoplastic elastomer composition and its molding
DE112008000757T5 (en) 2007-03-23 2010-01-28 Sumitomo Chemical Co., Ltd. Composite molding and process for its preparation
US8399104B2 (en) 2007-03-23 2013-03-19 Sumitomo Chemical Company, Limited Composite molded article and process for producing the same
JP5631589B2 (en) * 2007-06-14 2014-11-26 三井化学株式会社 Thermoplastic elastomer composition

Also Published As

Publication number Publication date
JPH0410505B2 (en) 1992-02-25

Similar Documents

Publication Publication Date Title
EP0132931B1 (en) Thermoplastic elastomer composition and process for preparation thereof
US4634735A (en) Polypropylene compositions with high impact strength
BRPI0814878B1 (en) rheology-modified modified grafts and adhesive mixtures
JP3322066B2 (en) Thermoplastic elastomer composition with excellent injection fusion property
US20030040582A1 (en) Mixtures of thermoplastic elastomers and polar polymers
CZ293765B6 (en) Articles made of one or several parts consisting of EPDM vulcanized rubber or EPM vulcanized rubber and process for preparing adhesive thermoplastic composition
JPS59221347A (en) Thermoplastic elastomer composition having excellent injection weldability
JP2002212349A (en) Flexible resin composition for injection molding and use thereof
JPH0446296B2 (en)
JPS6259139B2 (en)
KR101135699B1 (en) Resin composition including high melt strength polyolefin
JP2020503908A (en) Strengthening adhesive strength of medical devices
JPS6185462A (en) Production of polypropylene resin composition
JPS60173032A (en) Thermoplastic elastomer composition good in injection weldability and gloss
JPH05222214A (en) Waterproof sheet
JP2006265367A (en) Waterproof sheet
JPH05295180A (en) Thermoplastic elastomer composition excellent in surface gloss and fusion bondability in injection molding
JP2655899B2 (en) Thermoplastic elastomer composition
JP2582856B2 (en) Method for producing thermoplastic elastomer sheet
JP4705711B2 (en) Ionomer composition and use thereof
JPH02113045A (en) Thermoplastic elastomer composition
JP2000319455A (en) Water barrier sheet
JPH11140248A (en) Thermoplastic elastomer composition and sheet
JPH0557297B2 (en)
JPH0251387B2 (en)