JP2997898B2 - Ultra high molecular weight polyethylene molding method - Google Patents
Ultra high molecular weight polyethylene molding methodInfo
- Publication number
- JP2997898B2 JP2997898B2 JP32103890A JP32103890A JP2997898B2 JP 2997898 B2 JP2997898 B2 JP 2997898B2 JP 32103890 A JP32103890 A JP 32103890A JP 32103890 A JP32103890 A JP 32103890A JP 2997898 B2 JP2997898 B2 JP 2997898B2
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- Prior art keywords
- molecular weight
- low
- weight polyethylene
- molding
- compound
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、超高分子量ポリエチレンの成形方法に関す
るものである。The present invention relates to a method for molding ultra-high molecular weight polyethylene.
超高分子量ポリエチレンは、その分子量が大であるが
故に、溶融時の粘度が極めて高く、押出成形については
特定の条件下でのみ可能であり、また射出成形について
は不可能な状態であった。従って、通常は、圧縮成形し
た単純形状物を機械加工して各種の部品を製作している
ため、生産性が悪く、コストが高くなるという問題があ
った。Ultrahigh molecular weight polyethylene has a very high viscosity at the time of melting because of its high molecular weight, so that extrusion molding is possible only under specific conditions, and injection molding is impossible. Therefore, usually, since various parts are manufactured by machining a simple-shaped object formed by compression molding, there is a problem that productivity is low and cost is high.
この問題を解決する方法、すなわち、超高分子量ポリ
エチレンの溶融粘度、流動性を改善し、押出成形や射出
成形を可能とする方法として、各種の低分子化合物を添
加する方法が提案されている。例えば、特開昭60−1245
号公報には、分子量100万以上の超高分子量ポリエチレ
ンに芳香族化合物、芳香族化合物誘導体、及びそれれら
のハロゲン化合物の群よりなる化合物のうち少なくとも
１種類と脂肪族のC12〜C32カルボン酸塩とが配されてな
る超高分子量ポリエチレン組成物が開示されており、ま
た、特開昭62−96547号公報には平均分子量100万以上の
超高分子量ポリエチレン及び1,4−ジフェニルブタジエ
ンを含有する超高分子量ポリエチレン組成物が開示され
ている。As a method for solving this problem, that is, a method for improving the melt viscosity and fluidity of ultra-high molecular weight polyethylene and enabling extrusion molding and injection molding, a method of adding various low-molecular compounds has been proposed. For example, JP-A-60-1245
In the publication, an ultra-high molecular weight polyethylene having a molecular weight of 1,000,000 or more is mixed with at least one compound selected from the group consisting of aromatic compounds, aromatic compound derivatives, and halogen compounds thereof, and aliphatic C 12 to C 32. An ultra-high molecular weight polyethylene composition comprising a carboxylate and a salt thereof is disclosed, and JP-A-62-96547 discloses an ultra-high-molecular-weight polyethylene having an average molecular weight of 1,000,000 or more and 1,4-diphenylbutadiene. An ultra high molecular weight polyethylene composition containing is disclosed.
前記した従来技術では、溶融粘度、流動性の改善に主
眼が置かれており、確かに低分子化合物を添加すること
により溶融粘度、流動性が改善され、押し出しや射出の
成形性は向上するが、物性の低下は避けられなかった。
逆に、物性を保持しようとすると、低分子化合物の添加
量が少量に限定され、成形性はほとんど改善されないと
いう問題があった。In the prior art described above, the main focus is on the improvement of melt viscosity and fluidity, and the addition of a low-molecular compound certainly improves the melt viscosity and fluidity, but improves the extrusion and injection moldability. However, deterioration of physical properties was inevitable.
Conversely, when trying to maintain physical properties, the amount of the low-molecular compound added is limited to a small amount, and there is a problem that moldability is hardly improved.
従って、本発明の目的は、この成形性と物性の両方を
満足する超高分子量ポリエチレンの成形方法を提供する
ことにある。Accordingly, an object of the present invention is to provide a method for molding ultra-high molecular weight polyethylene that satisfies both moldability and physical properties.
本発明によれば、前記目的を達成するために、平均分
子量100万以上の超高分子量ポリエチレンに反応性を有
する低分子化合物を添加して均一に混合したブレンド物
を成形し、次いで、得られた成形品に電磁波又は電子線
を照射することにより低分子化合物間又は低分子化合物
と超高分子量ポリエチレンとの間に反応を起こさせ、最
終的に優れた物性を有する成形品を得ることを特徴とす
る超高分子量ポリエチレンの成形方法が提供される。According to the present invention, in order to achieve the above object, a low molecular weight compound having reactivity is added to ultra-high molecular weight polyethylene having an average molecular weight of 1,000,000 or more, and a uniformly mixed blend is formed. By irradiating the molded article with electromagnetic waves or electron beams, a reaction occurs between the low molecular weight compounds or between the low molecular weight compound and the ultra high molecular weight polyethylene, and finally a molded article having excellent physical properties is obtained. Is provided.
なお、前記したように本発明の目的達成には、電子線
の照射も有効であるので、発明の詳細な説明においては
参考までに記載しているものの、これは本願の特許請求
の範囲を構成するものではない。As described above, electron beam irradiation is also effective for achieving the object of the present invention, and therefore, although described in the detailed description of the invention for reference, this constitutes the scope of the claims of the present application. It does not do.
本発明の超高分子量ポリエチレンの成形方法は、従来
技術の問題点、すなわち、唯単に低分子化合物を添加し
ただけでは、確かに溶融粘度、流動性が改善され、押出
成形性や射出成形性は向上するが、物性の低下は避けら
れないという問題を解決したものである。The method for molding ultra-high molecular weight polyethylene of the present invention has the problems of the prior art, that is, melt viscosities and fluidity are certainly improved by simply adding a low-molecular compound, and extrudability and injection moldability are improved. It solves the problem that the physical property is unavoidable, although it improves.
すなわち、反応性を有する低分子化合物を超高分子量
ポリエチレンに添加し、均一に混合して溶融粘度、流動
性を改善したブレンド物を得、これを用いて成形した成
形品に電磁波又は電子線を照射して、低分子化合物間又
は低分子化合物と超高分子量ポリエチレンとの間に反応
を起こさせ、これにより物性の低下を防ぐものである。That is, a low molecular compound having reactivity is added to ultra-high molecular weight polyethylene, and a homogeneous mixture is obtained to obtain a blend having improved melt viscosity and fluidity, and an electromagnetic wave or an electron beam is applied to a molded article molded using this. Irradiation causes a reaction between the low molecular weight compounds or between the low molecular weight compound and the ultra-high molecular weight polyethylene, thereby preventing a decrease in physical properties.
本発明の超高分子量ポリエチレンの成形方法は、ブレ
ンド物の調製、成形及び成形品の後処理の３つの工程か
らなっている。The ultrahigh molecular weight polyethylene molding method of the present invention comprises three steps: preparation of a blend, molding, and post-treatment of a molded article.
Ａ）ブレンド物の調製 まず、ブレンド物は、市販の粉末状の超高分子量ポリ
エチレンに反応性を有する低分子化合物を所定量添加し
た後、均一に混練して調製する。この反応性を有する低
分子化合物は、後の成形工程で高温にさらされるため、
熱により重合、架橋反応を起こすものは成形性を著しく
低下させるので好ましくなく、むしろ電磁波や電子線の
照射により反応を起こすものが望ましい。また、溶融粘
度や流動性を改善し、押し出しや射出の成形性を向上さ
せる必要があるため、基本構造はポリオレフィン系であ
ることが望ましい。もちろん、界面活性剤をさらに添加
することにより、超高分子量ポリエチレンと低分子化合
物の相溶性を向上させることも可能である。このように
して選定された低分子化合物は、超高分子量ポリエチレ
ンと均一に混練されてブレンド物となる混練方法として
は、ロール、ニーダー、バンバリーミキサー等の一般的
な混練装置の使用が可能であり、必要により、超高分子
量ポリエチレンの熱分解、劣化が起こらない範囲の温度
に加熱して相溶性をさらに向上させることが可能であ
る。このようにして、望ましくは通常の汎用プラスチッ
ク又はエンジニアリングプラスチックの押し出し又は射
出の最適成形粘度相当の粘度、例えば200℃でそれぞれ1
03〜106ポアズ（押出成形の場合）、106〜109ポアズ
（射出成形の場合）（いずれも剪断応力５×105dyne/cm
2の場合）のブレンド物を調製する。ここまでは、反応
性を有する低分子化合物を用いる以外は従来の成形方法
と同じである。A) Preparation of Blend First, a blend is prepared by adding a predetermined amount of a reactive low molecular weight compound to a commercially available powdered ultrahigh molecular weight polyethylene, and then kneading the mixture uniformly. Since the low-molecular compound having this reactivity is exposed to a high temperature in a later molding step,
Those which cause a polymerization or cross-linking reaction by heat are not preferred because they significantly lower the moldability, but rather those which cause a reaction by irradiation with an electromagnetic wave or an electron beam. In addition, since it is necessary to improve the melt viscosity and fluidity and to improve the extrusion and injection moldability, it is preferable that the basic structure be a polyolefin-based material. Of course, by further adding a surfactant, the compatibility between the ultrahigh molecular weight polyethylene and the low molecular weight compound can be improved. The low molecular compound selected in this manner is kneaded uniformly with the ultrahigh molecular weight polyethylene, and as a kneading method, a general kneading apparatus such as a roll, a kneader, and a Banbury mixer can be used. If necessary, the compatibility can be further improved by heating to a temperature within a range where thermal decomposition and deterioration of the ultrahigh molecular weight polyethylene do not occur. In this way, it is desirable to have a viscosity corresponding to the optimum molding viscosity for extrusion or injection of ordinary general-purpose plastics or engineering plastics, for example 1
0 3 to 10 6 poise (in the case of extrusion molding), 10 6 to 10 9 poise (in the case of injection molding) (both shear stress 5 × 10 5 dyne / cm
2 ) is prepared. Up to this point, it is the same as the conventional molding method except that a reactive low molecular weight compound is used.
Ｂ）成形 次に、前工程で得られたブレンド物を用いて成形を行
うが、これは、前工程において押出成形及び射出成形に
それぞれ対応した最適粘度のブレンド物が既に調製され
ているので、超高分子量ポリエチレンの耐熱劣化性が低
いことに注意する以外は、ポリエチレン等汎用プラスチ
ックの通常の押出成形及び射出成形それぞれの成形条件
と同様の条件で行なうことができる。B) Molding Next, molding is performed using the blend obtained in the previous step. This is because a blend having an optimum viscosity corresponding to each of extrusion molding and injection molding has already been prepared in the previous step. Except for the fact that the ultra-high molecular weight polyethylene has low heat deterioration resistance, the molding can be performed under the same conditions as those of ordinary extrusion molding and injection molding of general-purpose plastics such as polyethylene.
Ｃ）成形品の後処理 最後の後処理工程は、成形品に電磁波又は電子線を照
射することにより反応性を有する低分子化合物に単独重
合を起こさせるか、あるいは、この反応性を有する低分
子化合物と超高分子量ポリエチレンとの間に反応を起こ
させるものであり、これによって、成形したままの状態
では低分子化合物の添加により低下した物性を上記反応
により補強する。すなわち、物性を改善するための反応
は３種類あり、より具体的には、まず１つは、反応性を
有する低分子化合物が単独重合する場合である。すなわ
ち、反応終了後は２つのポリマーがランダムに混合した
状態になる。２つ目は、低分子化合物が１個の官能基を
有しており、外部から活性エネルギー線を照射すること
により、超高分子量ポリエチレンの主鎖又は側鎖と反応
してグラフト化する場合である。そして３つ目は、低分
子化合物が２個以上の官能基を有しており、外部から活
性エネルギー線を照射することにより、低分子化合物を
なかだちとして超高分子量ポリエチレン間に架橋が形成
される場合である。これらの３種類の方法のいずれで
も、単純に低分子化合物を添加しただけのものに比べて
成形品の物性は向上する。C) Post-treatment of the molded article The final post-treatment step is to irradiate the molded article with an electromagnetic wave or an electron beam to cause homopolymerization of the reactive low-molecular compound, or the reactive low-molecular compound. A reaction is caused between the compound and the ultrahigh molecular weight polyethylene, whereby the physical properties which have been reduced by the addition of the low molecular compound in the as-molded state are reinforced by the reaction. That is, there are three types of reactions for improving the physical properties, and more specifically, one is a case where a low-molecular compound having reactivity is homopolymerized. That is, after the reaction is completed, the two polymers are mixed at random. The second is a case where the low molecular weight compound has one functional group and reacts with the main chain or side chain of ultra-high molecular weight polyethylene to graft by irradiating an active energy ray from the outside. is there. Third, the low-molecular compound has two or more functional groups, and by irradiating active energy rays from the outside, a cross-link is formed between the ultra-high molecular weight polyethylene and the low-molecular compound. Is the case. In any of these three methods, the physical properties of the molded article are improved as compared with those obtained by simply adding a low molecular compound.
成形品の後処理は、押出成形では、成形品の冷却中あ
るいは冷却後に処理装置を押出成形機とライン接続して
行なう。また、射出成形の場合は、個々に行ってもよい
し、型から取り出した後、まとめて多数個同時に行って
もよい。なお、後処理装置は電磁波又は電子線を照射で
きる炉タイプのものが望ましいが、押出成形では押出成
形機のライン末端に組み込んでもよい。また、照射には
波長が10-15〜10-4cmの範囲にある電磁波（γ線、Ｘ
線、紫外線、可視光線）のいずれか又は電子線を用い
る。In the extrusion molding, post-processing of the molded article is performed during or after cooling of the molded article by connecting a processing apparatus to the extruder in a line. In the case of injection molding, it may be performed individually, or may be performed simultaneously after taking out from the mold. The post-processing apparatus is preferably a furnace type capable of irradiating an electromagnetic wave or an electron beam, but may be incorporated at the end of a line of an extruder in extrusion molding. For irradiation, electromagnetic waves (γ-rays, X-rays) having a wavelength in the range of 10 −15 to 10 −4 cm are used.
Ray, ultraviolet light, visible light) or an electron beam.
以下、実施例及び比較例を示して本発明について具体
的に説明するが、本発明が下記実施例に限定されるもの
でないことはもとよりである。Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples. However, it goes without saying that the present invention is not limited to the following Examples.
実施例１ 分子量100万以上の超高分子量ポリエチレン100重量部
と液状ゴム100重量部とをＶ型ミキサーで100℃にて撹拌
混練した組成物をサンプルとして、高化式フローテスタ
（200℃、剪断応力５×105dyne/cm2）を用いて粘度測定
を行い、さらにノズルから押し出された糸状物及びこれ
に放射線処理（γ線、10KeV）をしたものの引張強度を
測定した。Example 1 A composition obtained by stirring and kneading 100 parts by weight of ultrahigh molecular weight polyethylene having a molecular weight of 1,000,000 or more and 100 parts by weight of a liquid rubber at 100 ° C. with a V-type mixer was used as a sample, and a Koka type flow tester (200 ° C., shearing) was used. The viscosity was measured using a stress of 5 × 10 5 dyne / cm 2 ), and the tensile strength of the filament extruded from the nozzle and the radiation-treated (γ-ray, 10 KeV) was measured.
比較例１ 液状ゴムを低分子量ポリエチレンに変えた以外は実施
例１と同様にして行い、組成物の粘度測定及び押出成形
した糸状物の引張強度を測定した。Comparative Example 1 The procedure of Example 1 was repeated except that the liquid rubber was changed to low molecular weight polyethylene, and the viscosity of the composition and the tensile strength of the extruded thread were measured.
結果を表−１に示す。なお、使用した超高分子量ポリ
エチレンの引張強度（カタログ値）も参考として示す。The results are shown in Table 1. The tensile strength (catalog value) of the ultra-high molecular weight polyethylene used is also shown for reference.
上記表−１に示す結果から明らかなように、超高分子
量ポリエチレンに液状ゴムの添加混練して成形した段階
では引張強度は低下したが、これに放射線処理を施すこ
とにより、超高分子量ポリエチレン単独の引張強度に近
い値まで向上した。なお、上記実施例では超高分子量ポ
リエチレンに対して低分子化合物を1:1の割合で配合し
たが、低分子量化合物の配合割合は最終成形品の所望の
物性値に応じて適宜選定することができる。 As is evident from the results shown in Table 1, the tensile strength was reduced at the stage where the liquid rubber was added to the ultra-high molecular weight polyethylene and kneaded, and then molded. To a value close to the tensile strength. In the above example, the low molecular weight compound was blended at a ratio of 1: 1 with respect to the ultra high molecular weight polyethylene, but the blending ratio of the low molecular weight compound may be appropriately selected according to the desired physical property values of the final molded article. it can.
以上のように、本発明の超高分子量ポリエチレンの成
形方法によれば、まず、超高分子量ポリエチレンに反応
性を有する低分子化合物を添加して均一に混合し、溶融
粘度及び流動性を改善したブレンド物を得、これを用い
て所望の形状に成形する。従って、押出成形や射出成形
により容易に成形することができ、成形品の生産性が向
上する。この段階では低分子化合物の添加により成形品
の物性は超高分子量ポリエチレンのそれよりも低下する
が、本発明の形成方法によれば、その後さらに、得られ
た成形品に電磁波又は電子線を照射し、低分子化合物間
又は低分子化合物と超高分子量ポリエチレンとの間に反
応を起こさせることにより、最終的に引張強度、耐摩耗
性、耐衝撃性などの物性に優れた成形品を得ることがで
きる。すなわち、本発明の成形方法によれば、優れた物
性を有する超高分子量ポリエチレン成形品を成形性よく
製造することができる。As described above, according to the ultrahigh molecular weight polyethylene molding method of the present invention, first, a low molecular compound having reactivity is added to the ultrahigh molecular weight polyethylene and uniformly mixed to improve the melt viscosity and fluidity. A blend is obtained, which is used to form the desired shape. Therefore, molding can be easily performed by extrusion molding or injection molding, and the productivity of molded products is improved. At this stage, the physical properties of the molded article are lower than those of the ultra-high molecular weight polyethylene due to the addition of the low molecular compound, but according to the forming method of the present invention, the obtained molded article is further irradiated with electromagnetic waves or electron beams. Finally, by causing a reaction between the low-molecular compound or between the low-molecular compound and the ultra-high-molecular-weight polyethylene, it is possible to finally obtain a molded article having excellent physical properties such as tensile strength, abrasion resistance and impact resistance. Can be. That is, according to the molding method of the present invention, it is possible to produce an ultra-high molecular weight polyethylene molded article having excellent physical properties with good moldability.
フロントページの続き (56)参考文献 特開 昭58−65732（ＪＰ，Ａ) 特開 昭56−133134（ＪＰ，Ａ) 特開 昭51−145555（ＪＰ，Ａ) 特開 昭52−840（ＪＰ，Ａ) 特開 昭52−92258（ＪＰ，Ａ) 特開 昭52−151364（ＪＰ，Ａ) 特開 昭55−27353（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C08F 2/54,8/00,110/02 C08J 7/00 Continuation of the front page (56) References JP-A-58-65732 (JP, A) JP-A-56-133134 (JP, A) JP-A-51-145555 (JP, A) JP-A-52-840 (JP) JP-A-52-92258 (JP, A) JP-A-52-151364 (JP, A) JP-A-55-27353 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB Name) C08F 2 / 54,8 / 00,110 / 02 C08J 7/00
Claims (3)
チレンに反応性を有する低分子化合物を添加して均一に
混合したブレンド物を成形し、次いで、得られた成形品
に波長10-15〜10-4cmの範囲にあるγ線、Ｘ線、紫外線
又は可視光線のいずれかである電磁波を照射することに
より低分子化合物間又は低分子化合物と超高分子量ポリ
エチレンとの間に反応を起こさせ、最終的に優れた物性
を有する成形品を得ることを特徴とする超高分子量ポリ
エチレンの成形方法。1. A molding the average molecular weight of 1,000,000 or more low-molecular compound blend was then uniformly mixed with reactive ultra high molecular weight polyethylene, then the wavelength 10 -15 in the molded article obtained ~ Irradiation of γ-rays, X-rays, ultraviolet light or visible light in the range of 10 -4 cm causes a reaction between the low molecular weight compounds or between the low molecular weight compounds and the ultra high molecular weight polyethylene. A method for molding ultra-high molecular weight polyethylene, which finally obtains a molded article having excellent physical properties.
いる請求項１に記載の方法。2. The method according to claim 1, wherein extrusion or injection molding is used as a molding method.
分子化合物と超高分子量ポリエチレンとの間に起こる反
応が、低分子化合物の単独重合反応、低分子化合物の超
高分子量ポリエチレンへのグラフト化反応、低分子化合
物による超高分子量ポリエチレン間の架橋反応のいずれ
かである請求項１乃至２のいずれか一項に記載の方法。3. The reaction between low-molecular compounds or between a low-molecular compound and ultrahigh-molecular-weight polyethylene caused by irradiation with electromagnetic waves includes a homopolymerization reaction of low-molecular compounds and grafting of low-molecular compounds to ultrahigh-molecular-weight polyethylene. The method according to any one of claims 1 to 2, which is any one of a reaction and a cross-linking reaction between ultrahigh molecular weight polyethylenes by a low molecular weight compound.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32103890A JP2997898B2 (en) | 1990-11-27 | 1990-11-27 | Ultra high molecular weight polyethylene molding method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP32103890A JP2997898B2 (en) | 1990-11-27 | 1990-11-27 | Ultra high molecular weight polyethylene molding method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04198201A JPH04198201A (en) | 1992-07-17 |
| JP2997898B2 true JP2997898B2 (en) | 2000-01-11 |
Family
ID=18128110
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP32103890A Expired - Lifetime JP2997898B2 (en) | 1990-11-27 | 1990-11-27 | Ultra high molecular weight polyethylene molding method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2997898B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100293587B1 (en) * | 1994-09-21 | 2001-09-17 | 겐죠오바이 | Ultra high molecular weight polyethylene molding block for artificial joint sliding member and method of manufacturing the same |
| US5879723A (en) * | 1996-03-26 | 1999-03-09 | United States Brass Corporation | Automated tube reforming apparatus |
| US5756023A (en) * | 1996-05-30 | 1998-05-26 | United States Brass Corporation | Method of producing reformed crosslinked polyethylene articles |
| US6284178B1 (en) | 1999-06-18 | 2001-09-04 | United States Brass Corporation | Methods of producing crosslinked polyethylene products |
| US7344672B2 (en) | 2004-10-07 | 2008-03-18 | Biomet Manufacturing Corp. | Solid state deformation processing of crosslinked high molecular weight polymeric materials |
| US8641959B2 (en) | 2007-07-27 | 2014-02-04 | Biomet Manufacturing, Llc | Antioxidant doping of crosslinked polymers to form non-eluting bearing components |
| US9586370B2 (en) | 2013-08-15 | 2017-03-07 | Biomet Manufacturing, Llc | Method for making ultra high molecular weight polyethylene |
-
1990
- 1990-11-27 JP JP32103890A patent/JP2997898B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04198201A (en) | 1992-07-17 |
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