JPH06287223A - Production of ionomer composition - Google Patents
Production of ionomer compositionInfo
- Publication number
- JPH06287223A JPH06287223A JP9878393A JP9878393A JPH06287223A JP H06287223 A JPH06287223 A JP H06287223A JP 9878393 A JP9878393 A JP 9878393A JP 9878393 A JP9878393 A JP 9878393A JP H06287223 A JPH06287223 A JP H06287223A
- Authority
- JP
- Japan
- Prior art keywords
- copolymer
- ethylene
- ionomer
- carboxylic acid
- unsaturated carboxylic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、エチレン共重合体アイ
オノマー組成物を、工業的に有利に製造する方法に関す
る。FIELD OF THE INVENTION The present invention relates to a method for industrially producing an ethylene copolymer ionomer composition.
【０００２】[0002]
【従来の技術】エチレンと、不飽和カルボン酸と、任意
に他の重合成分とから構成される共重合体が、部分的又
は完全に中和された構造を有するエチレン共重合体アイ
オノマーは、イオン架橋に基づく特徴ある性質を示し、
単味で、あるいは他の重合体と複合して広く使用されて
いる。このようなアイオノマーは通常はスクリュー押出
機中でエチレン・不飽和カルボン酸共重合体を溶融混練
しつつ、イオン源となる金属化合物と反応させることに
よって、工業的に有利に製造することができる。しかる
に原料共重合体における不飽和カルボン酸重合単位が増
加するにつれ、金属への接着性が増すため、溶融混練時
にスクリューに融着して、押し出し不能になることがあ
り、またサージング等の現象が見られ生産性にも問題が
あった。このようなトラブルは、スクリュー回転数、温
度、滞留時間等を調節することによって回避することは
可能であるが、イオン化反応を阻害する方向となり、未
反応金属化合物が反応生成物中に少なからず混入する結
果となり、実用上採用しうる方法ではなかった。2. Description of the Related Art An ethylene copolymer ionomer having a structure in which a copolymer composed of ethylene, an unsaturated carboxylic acid, and optionally other polymerization component is partially or completely neutralized is an ionic compound. Shows characteristic properties based on crosslinking,
Widely used alone or in combination with other polymers. Such an ionomer can be industrially advantageously produced by reacting with an ethylene / unsaturated carboxylic acid copolymer while being melt-kneaded with a metal compound serving as an ion source in a screw extruder. However, as the number of unsaturated carboxylic acid polymer units in the raw material copolymer increases, the adhesiveness to the metal increases, so that the screw may be fused to the screw during melt kneading, and extrusion may not be possible. There was a problem with productivity as well. Such troubles can be avoided by adjusting the screw rotation speed, temperature, residence time, etc., but this tends to hinder the ionization reaction, and unreacted metal compounds are mixed in the reaction product to a large extent. As a result, the method was not practically applicable.
【０００３】さらにまた、不飽和カルボン酸重合単位の
多い及び／又は高イオン化度のエチレン共重合体アイオ
ノマーは、吸湿性が大きいため、押出加工時や他樹脂と
の溶融ブレンド時に発泡し易いという欠点があった。高
イオン化度のエチレン共重合体アイオノマーはまた一般
に溶融粘度が高いため円滑な溶融押出しが難かしく、他
樹脂と溶融ブレンドする際に均一なブレンドを行うこと
は容易でなかった。Furthermore, the ethylene copolymer ionomer having a large number of unsaturated carboxylic acid polymerized units and / or a high ionization degree has a large hygroscopic property, and therefore, it is liable to foam during extrusion processing or melt blending with another resin. was there. In general, an ethylene copolymer ionomer having a high ionization degree has a high melt viscosity, so that it is difficult to smoothly perform melt extrusion, and it is not easy to perform uniform blending with another resin.
【０００４】[0004]
【発明が解決しようとする課題】そこで、本発明者ら
は、エチレン共重合体アイオノマーが他のオレフィン重
合体とブレンドして用いられる分野が多いことに着目
し、予め原料共重合体にこのようなオレフィン重合体の
一部又は全部を配合した状態で同様のイオン化反応を試
みたところ、前述したスクリューへの融着トラブルが回
避できるのみならず、均一なブレンドと共にイオン化反
応も円滑に進行し、結果として物性良好なアイオノマー
組成物が発泡トラブルもなく容易に得られることを見出
すに至り、本発明に到達した。従って、本発明の目的
は、イオン化反応操作が困難な不飽和カルボン酸含有量
の多いエチレン共重合体から、工業的に有用なエチレン
共重合体アイオノマー組成物を簡単な操作で製造しうる
方法を提供するにある。本発明の他の目的は、不飽和カ
ルボン酸含有量の多い、及び／又はイオン化度の高いエ
チレン共重合体アイオノマーとオレフィン重合体からな
る組成物を工業的に有利に、かつ均一なブレンド品とし
て製造する方法を提供するにある。Therefore, the present inventors have paid attention to the fact that ethylene copolymer ionomers are used in many cases by blending with other olefin polymers, and the above When a similar ionization reaction was attempted in a state in which a part or all of the olefin polymer was blended, not only the fusion problem to the screw described above can be avoided, but also the ionization reaction proceeds smoothly with a uniform blend, As a result, they have found that an ionomer composition having good physical properties can be easily obtained without causing foaming troubles, and reached the present invention. Therefore, an object of the present invention is to provide a method capable of producing an industrially useful ethylene copolymer ionomer composition by a simple operation from an ethylene copolymer having a large unsaturated carboxylic acid content which is difficult to ionize. To provide. Another object of the present invention is to provide a composition comprising an ethylene copolymer ionomer having a high unsaturated carboxylic acid content and / or a high ionization degree and an olefin polymer as an industrially advantageous and uniform blend product. It is to provide a manufacturing method.
【０００５】[0005]
【課題を解決するための手段】本発明は、スクリュー押
出機中で、エチレン・不飽和カルボン酸共重合体を溶融
混練しながらイオン源となる金属化合物と反応させてア
イオノマーを製造するに際し、前記共重合体以外のオレ
フィン重合体を共存させること特徴とするアイオノマー
組成物の製造方法に関する。Means for Solving the Problems The present invention provides a method for producing an ionomer by reacting an ethylene / unsaturated carboxylic acid copolymer with a metal compound serving as an ion source in a screw extruder while melt-kneading. The present invention relates to a method for producing an ionomer composition, which is characterized by allowing an olefin polymer other than a copolymer to coexist.
【０００６】本発明のエチレン・不飽和カルボン酸共重
合体における不飽和カルボン酸としては、アクリル酸、
メタクリル酸、無水マレイン酸、マレイン酸モノメチル
などを例示することができるが、とくにアクリル酸又は
メタクリル酸が好ましい。該共重合体には他の重合成
分、例えばアクリル酸やメタクリル酸のエステル、具体
的にはアクリル酸メチル、アクリル酸エチル、アクリル
酸ｎ−ブチル、アクリル酸イソブチル、メタクリル酸メ
チル、メタクリル酸イソブチルなど、あるいは酢酸ビニ
ルなどが共重合されたものであってもよい。As the unsaturated carboxylic acid in the ethylene / unsaturated carboxylic acid copolymer of the present invention, acrylic acid,
Examples thereof include methacrylic acid, maleic anhydride, and monomethyl maleate, with acrylic acid or methacrylic acid being particularly preferred. The copolymer may have other polymerization components such as esters of acrylic acid and methacrylic acid, specifically, methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, methyl methacrylate, isobutyl methacrylate and the like. Alternatively, it may be a copolymer of vinyl acetate or the like.
【０００７】本発明においてはこのような共重合体の中
でイオン化反応操作の困難な不飽和カルボン酸含有量の
多い共重合体、例えば、不飽和カルボン酸単位が１５〜
３５重量％、とくに１７〜３０重量％の共重合体に適用
した場合に効果的である。また前記他の重合成分を、例
えば３５重量％以下、とくに３０重量％以下の如き量で
共重合された共重合体を用いることができる。In the present invention, among such copolymers, a copolymer having a large unsaturated carboxylic acid content which is difficult to operate in an ionization reaction, for example, an unsaturated carboxylic acid unit having a content of 15 to 15 is used.
It is effective when applied to a copolymer of 35% by weight, particularly 17 to 30% by weight. Further, a copolymer obtained by copolymerizing the above other polymerization component in an amount of, for example, 35% by weight or less, particularly 30% by weight or less can be used.
【０００８】前記共重合体としてはまた１９０℃、２１
６０ｇ荷重におけるメルトフローレートが、例えば１〜
１０００ｇ／１０分、好ましくは５〜７００ｇ／１０分
の如きものを使用するのがよい。As the above-mentioned copolymer, 190 ° C., 21
The melt flow rate under a load of 60 g is, for example, 1 to
It is preferable to use one such as 1000 g / 10 minutes, preferably 5 to 700 g / 10 minutes.
【０００９】本発明においてアイオノマー製造の際に共
存させて使用されるオレフィン重合体は、前記したエチ
レン・不飽和カルボン酸共重合体及びそのアイオノマー
以外の重合体であって、オレフィンの単独重合体、オレ
フィン同志の共重合体あるいはオレフィンと他の重合成
分、例えば不飽和エステルとの共重合体である。より具
体的には低密度ポリエチレン、線状低密度ポリエチレ
ン、中高密度ポリエチレン、ポリプロピレン、ポリ−１
−ブテン、ポリ−４−メチル−１−ペンテン、１，２−
ポリブタジエン、エチレン・酢酸ビニル共重合体、エチ
レン・アクリル酸エステル共重合体、エチレン・メタク
リル酸エステル共重合体などを例示することができる。
このようなオレフィン重合体は、スクリュー押出可能な
溶融粘度を有するものであれば種々の性状のものを使用
することができる。例えばエチレンを主体とする重合体
にあっては１９０℃、２１６０ｇ荷重におけるメルトフ
ローレートが０．１〜２００ｇ／１０分、プロピレンを
主体とする重合体にあっては、２３０℃、２１６０ｇ荷
重におけるメトルフローレートが０．１〜２００ｇ／１
０分程度のものを使用することができる。In the present invention, the olefin polymer coexistently used in the production of the ionomer is a polymer other than the above-mentioned ethylene / unsaturated carboxylic acid copolymer and its ionomer, and is an olefin homopolymer, It is a copolymer of olefins or a copolymer of an olefin and another polymerization component such as an unsaturated ester. More specifically, low density polyethylene, linear low density polyethylene, medium and high density polyethylene, polypropylene, poly-1.
-Butene, poly-4-methyl-1-pentene, 1,2-
Examples thereof include polybutadiene, ethylene / vinyl acetate copolymer, ethylene / acrylic acid ester copolymer, and ethylene / methacrylic acid ester copolymer.
As such an olefin polymer, those having various properties can be used as long as they have a melt viscosity that allows screw extrusion. For example, a polymer containing ethylene as a main component has a melt flow rate of 0.1 to 200 g / 10 min at 190 ° C. and a load of 2160 g, and a polymer mainly containing propylene has a melt flow rate at 230 ° C. and a load of 2160 g. Flow rate 0.1-200g / 1
The thing of about 0 minutes can be used.
【００１０】本発明において使用されるイオン源となる
金属化合物は、リチウム、ナトリウム、カリウムなどの
アルカリ金属；マグネシウム、カルシウム、バリウムな
どのアルカリ土類金属；亜鉛、コバルト、クロム、銅な
どの遷移金属、アルミニウムなどの各種金属の酸化物、
水酸化物、炭酸塩、重炭酸塩、酢酸塩、ギ酸塩などであ
る。The metal compound used as an ion source in the present invention includes alkali metals such as lithium, sodium and potassium; alkaline earth metals such as magnesium, calcium and barium; transition metals such as zinc, cobalt, chromium and copper. , Oxides of various metals such as aluminum,
Examples include hydroxides, carbonates, bicarbonates, acetates and formates.
【００１１】本発明の反応は、前記したエチレン・不飽
和カルボン酸共重合体、オレフィン重合体及び金属化合
物をスクリュー押出機に供給し、各重合体が溶融する温
度で混練することによって行なわれる。エチレン・不飽
和カルボン酸共重合体とオレフィン重合体の使用比率は
広い範囲で選択することができるが、スクリューへの融
着性や生成するアイオノマー組成物の有用性を考慮する
と前者１〜９９重量部、とくに１０〜９０重量部に対
し、後者９９〜１重量部、とくに９０〜１０重量部の割
合で使用するのが好ましい。イオン源となる金属化合物
の使用量は、エチレン・不飽和カルボン酸共重合体を所
望の中和度にするための化学量論的量であればよい。す
なわち前記中和度として、例えば１０〜９０％になるよ
うな量で用いるのがよい。本発明は高イオン化度アイオ
ノマー組成物の製造に用いた場合においても均一なブレ
ンドが得られるので、特に効果的である。金属化合物は
直接スクリュー押出機に供給してもよいが、反応を円滑
に進めるために、エチレン・不飽和カルボン酸共重合体
やオレフィン重合体をベースポリマーとするマスターバ
ッチを作って使用するのが好ましい。The reaction of the present invention is carried out by feeding the above-mentioned ethylene / unsaturated carboxylic acid copolymer, olefin polymer and metal compound to a screw extruder and kneading at a temperature at which each polymer melts. The use ratio of the ethylene / unsaturated carboxylic acid copolymer and the olefin polymer can be selected in a wide range, but in consideration of the fusion property to the screw and the usefulness of the resulting ionomer composition, the former 1 to 99% by weight. It is preferable to use the latter in an amount of 99 to 1 parts by weight, particularly 90 to 10 parts by weight, relative to parts, especially 10 to 90 parts by weight. The amount of the metal compound used as the ion source used may be a stoichiometric amount for achieving the desired degree of neutralization of the ethylene / unsaturated carboxylic acid copolymer. That is, it is preferable to use an amount such that the degree of neutralization is, for example, 10 to 90%. The present invention is particularly effective because it gives a uniform blend even when used in the production of a high ionization degree ionomer composition. The metal compound may be directly supplied to the screw extruder, but in order to smoothly proceed the reaction, it is preferable to prepare and use a masterbatch having an ethylene / unsaturated carboxylic acid copolymer or an olefin polymer as a base polymer. preferable.
【００１２】イオン化反応は、例えば共重合体の融点か
ら３００℃までの温度範囲で滞留時間が６０秒以上の如
き条件で行えばよい。またスクリュー押出機としては、
相当の混練能力を有し、上記滞留時間をとれるものであ
れば種々のタイプのものを使用することができる。また
イオン化反応によって生ずる副生物を除去するため、ベ
ント機構を有するものを使用するのが好ましい。The ionization reaction may be carried out, for example, in the temperature range from the melting point of the copolymer to 300 ° C. under the condition that the residence time is 60 seconds or more. As a screw extruder,
Various types can be used as long as they have a considerable kneading ability and can maintain the above-mentioned residence time. Further, in order to remove by-products generated by the ionization reaction, it is preferable to use one having a vent mechanism.
【００１３】[0013]
【実施例】以下に実施例を挙げて本発明を具体的に説明
する。なお、実施例および比較例で用いた原料樹脂の組
成、物性、組成物の調製法および生産性の評価方法は次
のとおりである。EXAMPLES The present invention will be specifically described below with reference to examples. The composition and physical properties of the raw material resins used in the examples and comparative examples, the method for preparing the composition, and the method for evaluating the productivity are as follows.
【００１４】１．原料 （１）酸共重合体 表１に示す組成及び物性を有するエチレン・メタクリル
酸ランダム共重合体。1. Raw Materials (1) Acid Copolymer An ethylene / methacrylic acid random copolymer having the composition and physical properties shown in Table 1.
【００１５】[0015]
【表１】 [Table 1]
【００１６】（２）アイオノマー 上記酸共重合体１を亜鉛にてメタクリル酸を４０モル％
中和したもの。(2) Ionomer 40% by mol of methacrylic acid is added to the above acid copolymer 1 with zinc.
Neutralized.
【００１７】（３）高圧法低密度ポリエチレン ＭＦＲ１０ｇ／１０分、密度０．９１７ｇ／ｃｍ3 (3) High pressure method low density polyethylene MFR 10 g / 10 min, density 0.917 g / cm 3
【００１８】（４）イオン化マスターバッチ イオン源金属化合物粉末を配合したエチレン・メタクリ
ル酸共重合体を使用した。その組成は表２の通りであ
る。(4) Ionization masterbatch An ethylene / methacrylic acid copolymer blended with an ion source metal compound powder was used. Its composition is shown in Table 2.
【００１９】[0019]
【表２】 [Table 2]
【００２０】 ２．アイオノマー組成物の調製法及び生産性の評価 ６５ｍｍφのベント装置付きスクリュー押出機に、各原
料樹脂ペレットをブレンドして供給し、これにイオン化
マスターバッチを供給し、樹脂温度２４０〜２５０℃、
押出量１５ｋｇ／ｈにて押し出した。ベント部分では発
生するガス及び水を真空ポンプにて除去した。2. Preparation Method of Ionomer Composition and Evaluation of Productivity A raw material resin pellet is blended and supplied to a screw extruder with a vent device of 65 mmφ, an ionization masterbatch is supplied thereto, and a resin temperature is 240 to 250 ° C.
It was extruded at an extrusion rate of 15 kg / h. Gas and water generated at the vent were removed by a vacuum pump.
【００２１】上記方法にてアイオノマー組成物を調製し
た時の、ポリマーのスクリューへの融着、サージング現
象及びダイから出てくるストランドの発泡性を観察し
た。また、得られたポリマーを熱プレスして２ｍｍ厚の
シートとし外観のムラを観察し、混練性の評価とした。When the ionomer composition was prepared by the above-mentioned method, the fusion of the polymer to the screw, the surging phenomenon, and the foamability of the strand emerging from the die were observed. Further, the obtained polymer was hot-pressed into a sheet having a thickness of 2 mm, and the unevenness of the appearance was observed to evaluate the kneading property.
【００２２】［実施例１］酸共重合体１、酸共重合体２
及び高圧法低密度ポリエチレンを表３に示す配合割合で
ブレンドし、更にイオン化マスターバッチ１を供給し、
上記２の方法により、表３に示すイオン濃度のアイオノ
マー／高圧法低密度ポリエチレン組成物を調製した。結
果を表３に示す。[Example 1] Acid copolymer 1 and acid copolymer 2
And high-pressure method low-density polyethylene were blended in the blending ratio shown in Table 3, and ionized masterbatch 1 was further supplied,
The ionomer / high-pressure low-density polyethylene composition having the ion concentration shown in Table 3 was prepared by the above method 2. The results are shown in Table 3.
【００２３】［実施例２］酸共重合体１、高圧法低密度
ポリエチレンとイオン化マスターバッチ２とを表３に示
す配合割合で実施例１と同様の方法でブレンドして表３
に示すイオン濃度のアイオノマー／高圧法低密度ポリエ
チレン組成物を得た。結果を表３に示す。Example 2 Acid copolymer 1, high-pressure low density polyethylene and ionized masterbatch 2 were blended in the same proportions as shown in Table 3 in the same manner as in Example 1 to obtain Table 3
An ionomer / high-pressure low-density polyethylene composition having the ion concentration shown in Table 1 was obtained. The results are shown in Table 3.
【００２４】［比較例１］高圧法低密度ポリエチレンを
添加せず、酸共重合体１、酸共重合体２及びイオン化マ
スターバッチ２とをブレンドして表３に示す配合割合で
ブレンドして表３に示すイオン濃度のアイオノマーを製
造した。ポリマーのスクリューへの融着、サージング、
発泡等の現象が見られた。結果を表３に示す。[Comparative Example 1] The high-pressure low density polyethylene was not added, and the acid copolymer 1, the acid copolymer 2 and the ionized masterbatch 2 were blended and blended at the blending ratio shown in Table 3. An ionomer having an ion concentration shown in 3 was produced. Fusion of polymer to screw, surging,
A phenomenon such as foaming was observed. The results are shown in Table 3.
【００２５】［比較例２］高圧法低密度ポリエチレン６
０ｗｔ％と、別に製造されたアイオノマー４０ｗｔ％と
をブレンドしてアイオノマー／高圧法低密度ポリエチレ
ン組成物を調製した。得られた組成物のイオン濃度は実
施例１、２と同等であるにも拘らず、ブレンド時に発泡
が生じ、また混練性不良で均一なブレンドが得られなか
った。結果を表３に示す。[Comparative Example 2] High-pressure method low-density polyethylene 6
An ionomer / high pressure method low density polyethylene composition was prepared by blending 0 wt% and separately produced ionomer 40 wt%. Although the ionic concentration of the obtained composition was the same as in Examples 1 and 2, foaming occurred during blending, and kneading was poor, and a uniform blend could not be obtained. The results are shown in Table 3.
【００２６】[0026]
【表３】 [Table 3]
【００２７】[0027]
【発明の効果】本発明によれば、不飽和カルボン酸含有
量の大きいエチレン・不飽和カルボン酸共重合体を原料
に用いても、スクリュー押出機中で円滑にイオン化反応
を行うことができる。押出機から得られる生成物は、エ
チレン共重合体アイオノマーとオレフィン重合体の均一
なブレンドであり、押出条件を選ぶことにより、未反応
の金属化合物量を痕跡程度に抑えることができる。かく
して得られる上記ブレンドはそのままで、あるいはさら
にオレフィン重合体や他の重合体にブレンドして用いる
ことができる。According to the present invention, even if an ethylene / unsaturated carboxylic acid copolymer having a large unsaturated carboxylic acid content is used as a raw material, the ionization reaction can be smoothly carried out in the screw extruder. The product obtained from the extruder is a homogeneous blend of the ethylene copolymer ionomer and the olefin polymer, and the amount of unreacted metal compound can be suppressed to a trace level by selecting the extrusion conditions. The above-obtained blend may be used as it is, or may be further blended with an olefin polymer or another polymer for use.
Claims (1)
和カルボン酸共重合体を溶融混練しながらイオン源とな
る金属化合物と反応させてアイオノマーを製造するに際
し、前記共重合体以外のオレフィン重合体を共存させる
ことを特徴とするアイオノマー組成物の製造方法。1. When producing an ionomer by reacting an ethylene / unsaturated carboxylic acid copolymer with a metal compound serving as an ion source while melt-kneading in an extruder, an olefin polymer other than the above-mentioned copolymer is used. A method for producing an ionomer composition, characterized in that:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09878393A JP3469605B2 (en) | 1993-04-01 | 1993-04-01 | Method for producing ionomer composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09878393A JP3469605B2 (en) | 1993-04-01 | 1993-04-01 | Method for producing ionomer composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06287223A true JPH06287223A (en) | 1994-10-11 |
| JP3469605B2 JP3469605B2 (en) | 2003-11-25 |
Family
ID=14228970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09878393A Expired - Lifetime JP3469605B2 (en) | 1993-04-01 | 1993-04-01 | Method for producing ionomer composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3469605B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002143656A (en) * | 2000-08-28 | 2002-05-21 | Du Pont Mitsui Polychem Co Ltd | Moisture permeable material |
| JP2002234975A (en) * | 2001-02-09 | 2002-08-23 | Du Pont Mitsui Polychem Co Ltd | Ionomer resin composition and its use |
| WO2006024579A1 (en) | 2004-08-31 | 2006-03-09 | Basell Poliolefine Italia S.R.L. | Thermoplastic polyolefin composition |
| WO2009072600A1 (en) * | 2007-12-07 | 2009-06-11 | Du Pont-Mitsui Polychemicals Co., Ltd. | Ionomer, resin composition containing the ionomer, unstretched film, sheet or molded body each made from the composition, and laminate having layer of the unstretched film |
| US7803874B2 (en) * | 2006-07-18 | 2010-09-28 | Bridgestone Sports Co., Ltd. | Golf ball material, golf ball and method for preparing golf ball material |
| JP2011042809A (en) * | 2010-12-02 | 2011-03-03 | Du Pont Mitsui Polychem Co Ltd | Method for producing ionomer resin composition |
| US8106115B2 (en) * | 2004-08-05 | 2012-01-31 | Bridgestone Sports Co., Ltd. | Golf ball material, golf ball and method for preparing golf ball material |
| WO2019044784A1 (en) * | 2017-08-28 | 2019-03-07 | 三井・デュポンポリケミカル株式会社 | Resin composition, molded object, and production method for resin composition |
| JP2019166796A (en) * | 2018-03-26 | 2019-10-03 | 三井・ダウポリケミカル株式会社 | Three-dimensional molding |
-
1993
- 1993-04-01 JP JP09878393A patent/JP3469605B2/en not_active Expired - Lifetime
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002143656A (en) * | 2000-08-28 | 2002-05-21 | Du Pont Mitsui Polychem Co Ltd | Moisture permeable material |
| JP2002234975A (en) * | 2001-02-09 | 2002-08-23 | Du Pont Mitsui Polychem Co Ltd | Ionomer resin composition and its use |
| US8106115B2 (en) * | 2004-08-05 | 2012-01-31 | Bridgestone Sports Co., Ltd. | Golf ball material, golf ball and method for preparing golf ball material |
| US8461268B2 (en) | 2004-08-05 | 2013-06-11 | Bridgestone Sports Co., Ltd. | Golf ball material, golf ball and method for preparing golf ball material |
| US20120095148A1 (en) * | 2004-08-05 | 2012-04-19 | Bridgestone Sports Co., Ltd. | Golf ball material, golf ball and method for preparing golf ball material |
| WO2006024579A1 (en) | 2004-08-31 | 2006-03-09 | Basell Poliolefine Italia S.R.L. | Thermoplastic polyolefin composition |
| US7629404B2 (en) | 2004-08-31 | 2009-12-08 | Basell Polioefine Italia S.R.L. | Thermoplastic polyolefin composition |
| US8450419B2 (en) | 2006-07-18 | 2013-05-28 | Bridgestone Sports Co., Ltd. | Golf ball material, golf ball, and method for preparing golf ball material |
| US20100324172A1 (en) * | 2006-07-18 | 2010-12-23 | Bridgestone Sports Co., Ltd. | Golf ball material, golf ball, and method for preparing golf ball material |
| US7803874B2 (en) * | 2006-07-18 | 2010-09-28 | Bridgestone Sports Co., Ltd. | Golf ball material, golf ball and method for preparing golf ball material |
| JPWO2009072600A1 (en) * | 2007-12-07 | 2011-04-28 | 三井・デュポンポリケミカル株式会社 | Ionomer, resin composition containing the ionomer, unstretched film formed from the composition, sheet or molded body, and laminate having the unstretched film layer |
| JP4584349B2 (en) * | 2007-12-07 | 2010-11-17 | 三井・デュポンポリケミカル株式会社 | Ionomer, resin composition containing the ionomer, unstretched film formed from the composition, sheet or molded body, and laminate having the unstretched film layer |
| WO2009072600A1 (en) * | 2007-12-07 | 2009-06-11 | Du Pont-Mitsui Polychemicals Co., Ltd. | Ionomer, resin composition containing the ionomer, unstretched film, sheet or molded body each made from the composition, and laminate having layer of the unstretched film |
| JP2011042809A (en) * | 2010-12-02 | 2011-03-03 | Du Pont Mitsui Polychem Co Ltd | Method for producing ionomer resin composition |
| WO2019044784A1 (en) * | 2017-08-28 | 2019-03-07 | 三井・デュポンポリケミカル株式会社 | Resin composition, molded object, and production method for resin composition |
| CN111065680A (en) * | 2017-08-28 | 2020-04-24 | 三井—陶氏聚合化学株式会社 | Resin composition, molded article, and method for producing resin composition |
| JPWO2019044784A1 (en) * | 2017-08-28 | 2020-08-06 | 三井・ダウポリケミカル株式会社 | Resin composition, molded article and method for producing resin composition |
| JP2019166796A (en) * | 2018-03-26 | 2019-10-03 | 三井・ダウポリケミカル株式会社 | Three-dimensional molding |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3469605B2 (en) | 2003-11-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6518365B1 (en) | High melt swell polymer | |
| CA1039429A (en) | Process for preparing ionically crosslinked copolymers | |
| US5260371A (en) | Process for making melt stable ethylene vinyl alcohol polymer compositions | |
| US3437718A (en) | Polymer blends | |
| JP3469605B2 (en) | Method for producing ionomer composition | |
| US5003001A (en) | Ionic crosslinking of an ethylene copolymer in twin-screw extruder | |
| JP2010509411A (en) | Manufacturing method of high quality ionomer | |
| WO2018061694A1 (en) | Resin composition and support material for laminate shaping | |
| US5189113A (en) | Preparation of homogeneous ionically crosslinked ethylene copolymer in twin screw extruder | |
| JP3179253B2 (en) | Purge agent and purge method | |
| JPS58134137A (en) | Thermoplastic resin composition | |
| JPH093124A (en) | Modified amorphous polyolefin and its continuous production | |
| JP3236328B2 (en) | Method for producing ethylene copolymer composition | |
| JPS6032844A (en) | Ethylene-vinyl alcohol copolymer composition | |
| JP3481289B2 (en) | Method for producing ionically crosslinked copolymer | |
| JP3100711B2 (en) | Method for producing ionomer and composition thereof | |
| JPH0211621B2 (en) | ||
| JP2790318B2 (en) | Resin composition and molded article using the same | |
| JP2599630B2 (en) | Polyolefin-polyester graft copolymer and method for producing the same | |
| JPH057635A (en) | Golf ball | |
| JP3300004B2 (en) | Ionomer composition | |
| JP3133439B2 (en) | Polyolefin resin composition and method for producing the same | |
| JP2001335671A (en) | Purging agent and method of purging | |
| JP3641286B2 (en) | Propylene resin composition | |
| JPS627947B2 (en) |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20030826 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20070905 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080905 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20080905 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090905 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20090905 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100905 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20100905 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20110905 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20120905 Year of fee payment: 9 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130905 Year of fee payment: 10 |