JPH05301971A - Production of polyethylene cross-linked with electron beam - Google Patents
Production of polyethylene cross-linked with electron beamInfo
- Publication number
- JPH05301971A JPH05301971A JP12987992A JP12987992A JPH05301971A JP H05301971 A JPH05301971 A JP H05301971A JP 12987992 A JP12987992 A JP 12987992A JP 12987992 A JP12987992 A JP 12987992A JP H05301971 A JPH05301971 A JP H05301971A
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- JP
- Japan
- Prior art keywords
- polyethylene
- electron beam
- cross
- linked
- irradiation
- 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.)
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- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は電子線架橋ポリエチレン
の製造方法に関する。詳しくは、特定の方法で製造され
たポリエチレンに、特定の条件下で電子線を照射するこ
とを特徴とする機械的、熱的および化学的性質の優れた
電子線架橋ポリエチレンを製造する方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing electron beam crosslinked polyethylene. More specifically, the present invention relates to a method for producing electron beam crosslinked polyethylene having excellent mechanical, thermal and chemical properties, which comprises irradiating a polyethylene produced by a particular method with an electron beam under particular conditions.
【０００２】[0002]
【従来の技術】従来、ポリエチレンを所望の形状に成形
加工した後、得られた成形体に60Ｃｏ−γ線や電子線等
の放射線を照射することにより、電力ケーブル、中空パ
イプなどの架橋ポリエチレン成形体を製造することが行
われている。しかしながら、高圧法により製造された低
密度ポリエチレンを放射線照射して得られる架橋ポリエ
チレンは、耐熱性や機械的強度が不充分であるなど種々
の欠点を有しており改善が望まれていた。2. Description of the Related Art Conventionally, after molding polyethylene into a desired shape, the resulting molded body is irradiated with radiation such as 60 Co-γ rays and electron beams to crosslink polyethylene such as power cables and hollow pipes. BACKGROUND ART Manufacturing of molded bodies is performed. However, cross-linked polyethylene obtained by irradiating low-density polyethylene produced by the high-pressure method with radiation has various drawbacks such as insufficient heat resistance and mechanical strength, and improvement has been desired.
【０００３】また、低圧法により製造された高密度ポリ
エチレンを放射線照射して得られる架橋ポリエチレンに
ついても種々の検討がなされており、一般的には、上記
低密度ポリエチレンを放射線照射して得られる架橋ポリ
エチレンよりも機械的強度や耐熱性の点で優れたものが
得られている。しかしながら、従来の方法である60Ｃｏ
−γ線照射装置や比較的低エネルギー型の電子線照射装
置を用いて高密度ポリエチレンを照射した場合、得られ
る架橋ポリエチレンの耐熱性は向上するものの、衝撃強
度（ＩＺＯＤ衝撃強度や引張衝撃強度）の著しい低下を
招く為、材料としての利用範囲が狭く、改善を必要とし
ていた。Various studies have also been conducted on cross-linked polyethylene obtained by irradiating high-density polyethylene produced by the low-pressure method with radiation. Generally, cross-linking polyethylene obtained by irradiating the low-density polyethylene with radiation is cross-linked. It is superior to polyethylene in terms of mechanical strength and heat resistance. However, the conventional method, 60 Co
-When high density polyethylene is irradiated using a gamma ray irradiation device or a relatively low energy type electron beam irradiation device, the heat resistance of the obtained crosslinked polyethylene is improved, but the impact strength (IZOD impact strength or tensile impact strength) Therefore, the range of utilization as a material is narrow, and improvement is needed.
【０００４】又、ポリエチレンは通常品質の劣化を防ぐ
ために酸化防止剤等の安定剤を配合させるが、このよう
な安定剤類を配合させたポリエチレンに従来の方法で電
子線架橋を行うと、架橋反応が著しく阻害されるばかり
でなく、得られる架橋ポリエチレンの性質も損われる
為、この点の改良も望まれていた。Polyethylene is usually blended with a stabilizer such as an antioxidant in order to prevent deterioration of quality. When polyethylene blended with such stabilizers is subjected to electron beam cross-linking by a conventional method, it is cross-linked. Not only the reaction is significantly hindered, but also the properties of the crosslinked polyethylene obtained are impaired, and therefore improvement in this respect has been desired.
【０００５】[0005]
【発明が解決しようとする課題】本発明者らは、従来法
のこのような問題点を解決するために鋭意研究の結果、
特定の方法で製造されたポリエチレンを用い、特定の条
件下で電子線を照射することにより、耐熱性と衝撃強度
の両方の性質に優れた架橋ポリエチレンが得られること
を見出し、本発明を完成するに至ったものである。さら
には又、本発明の方法を用いて架橋を行った場合には、
架橋反応を行なう前に予め酸化防止剤等の安定剤を練り
込んだ樹脂を用いても架橋反応が速やかに行われる為、
架橋ポリエチレンの上記性質が損われることがなく、産
業上極めて有用なものである。DISCLOSURE OF INVENTION Problems to be Solved by the Invention As a result of earnest research to solve such problems of the conventional method, the present inventors have found that
It was found that a crosslinked polyethylene excellent in both heat resistance and impact strength can be obtained by irradiating an electron beam under a specific condition using polyethylene manufactured by a specific method, and completes the present invention. It came to. Furthermore, when cross-linking is performed using the method of the present invention,
Even if a resin in which a stabilizer such as an antioxidant is kneaded in advance before carrying out the crosslinking reaction is used, the crosslinking reaction can be carried out quickly,
The above properties of the crosslinked polyethylene are not impaired and are extremely useful in industry.
【０００６】[0006]
【課題を解決するための手段】本発明はマグネシウムと
チタンを含有する固体触媒成分および有機アルミニウム
化合物からなるチーグラー触媒の存在下、温度２０〜９
５℃において、エチレンまたはエチレンと少量の炭素数
３〜８のα−オレフィンを共重合させて得られる密度が
０．９４１ｇ／ｃｍ3 以上で、かつメルトインデックス
が０．０１〜１００ｇ／１０ｍｉｎのポリエチレンを比
較的高エネルギー型の電子線照射装置を用いて電子線照
射することを特徴とする電子線架橋ポリエチレンの製造
方法に関する。DISCLOSURE OF THE INVENTION The present invention provides a solid catalyst component containing magnesium and titanium and a Ziegler catalyst composed of an organoaluminum compound at a temperature of 20-9.
Polyethylene having a density of 0.941 g / cm 3 or more and a melt index of 0.01 to 100 g / 10 min, obtained by copolymerizing ethylene or a small amount of an α-olefin having 3 to 8 carbon atoms at 5 ° C. The present invention relates to a method for producing an electron beam cross-linked polyethylene, which comprises irradiating an electron beam with a relatively high energy type electron beam irradiation apparatus.
【０００７】本発明の方法で架橋ポリエチレンを製造し
た場合、使用する樹脂が高密度ポリエチレンの範疇に属
するものであるにもかかわらず、架橋速度が極めて速
く、通常の酸化防止剤の存在下においても架橋反応が速
やかに進行し、得られる架橋ポリエチレンは耐熱性が著
しく良好であるばかりでなく、耐衝撃性においても極め
て優れた性質を有している。When the crosslinked polyethylene is produced by the method of the present invention, the crosslinking rate is extremely high even though the resin used belongs to the category of high density polyethylene, and even in the presence of a usual antioxidant. The crosslinking reaction proceeds rapidly, and the obtained crosslinked polyethylene not only has extremely good heat resistance, but also has extremely excellent impact resistance.
【０００８】本発明における特定のポリエチレンとは、
マグネシウムとチタンとを含有する固体触媒成分と有機
アルミニウム化合物からなるチーグラー触媒の存在下、
温度２０〜９５℃において、エチレンまたはエチレンと
少量の炭素数３〜８のα−オレフィンを共重合させて得
られる密度が０．９４１ｇ／ｃｍ3 以上、好ましくは
０．９４６ｇ／ｃｍ3 以上で、かつメルトインデックス
が０．０１〜１００ｇ／１０ｍｉｎのポリエチレンであ
る。The specific polyethylene in the present invention is
In the presence of a Ziegler catalyst composed of a solid catalyst component containing magnesium and titanium and an organoaluminum compound,
At a temperature 20 to 95 ° C., density obtained ethylene or ethylene and a small amount of α- olefins having 3 to 8 carbon atoms are copolymerized is 0.941 g / cm 3 or more, preferably 0.946 g / cm 3 or more, It is a polyethylene having a melt index of 0.01 to 100 g / 10 min.
【０００９】ポリエチレンの製造に使用する触媒はマグ
ネシウムとチタンを含有する固体触媒成分および有機ア
ルミニウム化合物からなる。固体成分は金属マグネシウ
ム、有機または無機のマグネシウム化合物、あるいはこ
れをケイ素、アルミニウム等の化合物で処理して得られ
たものにチタン化合物を担持させたもの等が用いられる
が、特にグリニヤール試薬等の有機マグネシウム化合物
とヒドロポリシロキサン等の有機ケイ素化合物との反応
生成物を用いた場合、高性能で、しかも本発明の電子線
処理に適するポリエチレンが得られる。担持させるチタ
ン化合物としてはチタンの含ハロゲン化合物が好適であ
る。The catalyst used for producing polyethylene comprises a solid catalyst component containing magnesium and titanium and an organoaluminum compound. As the solid component, metal magnesium, an organic or inorganic magnesium compound, or a product obtained by treating it with a compound such as silicon or aluminum and carrying a titanium compound is used, and in particular organic such as Grignard reagent. When a reaction product of a magnesium compound and an organosilicon compound such as hydropolysiloxane is used, polyethylene having high performance and suitable for the electron beam treatment of the present invention can be obtained. As the titanium compound to be supported, a halogen-containing compound of titanium is suitable.
【００１０】もう一方の触媒成分である有機アルミニウ
ム化合物としては、トリアルキルアルミニウム、ジアル
キルアルミニウムクロライド、アルキルアルミニウムセ
スキクロライド等が挙げられる。Examples of the other organoaluminum compound which is a catalyst component include trialkylaluminum, dialkylaluminum chloride and alkylaluminum sesquichloride.
【００１１】上記重合触媒はきわめて高活性であるた
め、触媒の使用量は少量であり、本発明の電子線照射に
おいて触媒残渣の除去は全く必要ない。Since the above-mentioned polymerization catalyst is extremely highly active, the amount of the catalyst used is small, and it is not necessary to remove the catalyst residue in the electron beam irradiation of the present invention.
【００１２】本発明は前記のとおり酸化防止剤等の安定
剤配合処方のポリエチレンに対しても支障なく実施でき
るので各種の酸化防止剤を配合することができる。また
前記酸化防止剤以外に必要に応じて、滑剤、紫外線吸収
剤、帯電防止剤、難燃剤、老化防止剤、可塑剤、顔料な
どの各種添加剤を適宜配合することができる。As described above, the present invention can be carried out with no problem on polyethylene having a stabilizer compounding formulation such as an antioxidant, so that various antioxidants can be compounded. In addition to the antioxidant, various additives such as a lubricant, an ultraviolet absorber, an antistatic agent, a flame retardant, an antiaging agent, a plasticizer, and a pigment can be appropriately blended, if necessary.
【００１３】本発明で用いる電子線は、加速電圧が５０
０ＫｅＶ以上、好ましくは１ＭｅＶ以上１０ＭｅＶ以下
で、かつ電流値が１ｍＡ以上好ましくは３ｍＡ以上３０
ｍＡ以下の比較的高加速電圧で高電流値の能力を有する
照射装置を用いて行う。The electron beam used in the present invention has an accelerating voltage of 50.
0 KeV or more, preferably 1 MeV or more and 10 MeV or less, and a current value of 1 mA or more, preferably 3 mA or more 30
The irradiation is performed using an irradiation device having a relatively high acceleration voltage of mA or less and a high current value.
【００１４】本発明のような電子線照射による架橋ポリ
エチレンの製造においては、片側照射によって、材料の
内部にまで電子線が透過し、均一に改質されることが必
要であるが、加速電圧が５００ＫｅＶ以下では透過が不
充分であり、相対線量５０％の場合、せいぜい厚さ２ｍ
ｍの材料にしか適用できない。In the production of crosslinked polyethylene by electron beam irradiation as in the present invention, it is necessary that the electron beam penetrates into the material and is uniformly modified by one side irradiation. Transmission is insufficient at 500 KeV or less, and at a relative dose of 50%, the thickness is at most 2 m.
It is applicable only to the material of m.
【００１５】又本発明では電流値を特定の範囲以上にす
ることによって耐熱性と耐衝撃性の双方が優れたポリエ
チレンが得られる。電流値が１ｍＡ以下では充分な耐衝
撃強度が得られない。Further, according to the present invention, polyethylene having excellent heat resistance and impact resistance can be obtained by controlling the current value to be in a specific range or more. If the current value is 1 mA or less, sufficient impact strength cannot be obtained.
【００１６】電子線照射条件としては、照射温度は通常
−２０℃〜１２０℃、好ましくは０℃から７０℃の範囲
で行われる。また、照射雰囲気は通常空気存在下で充分
であるが、所望により窒素雰囲気下や真空中で行っても
なんら差し支えない。さらに、照射線量は１００Ｍｒａ
ｄ以下、特に１〜５０Ｍｒａｄの間で照射された時に最
適の結果が得られる。As the electron beam irradiation conditions, the irradiation temperature is usually from -20 ° C to 120 ° C, preferably from 0 ° C to 70 ° C. The irradiation atmosphere is usually sufficient in the presence of air, but if desired, the irradiation may be carried out in a nitrogen atmosphere or in a vacuum. Furthermore, the irradiation dose is 100 Mra
Optimal results are obtained when irradiated below d, especially between 1 and 50 Mrad.
【００１７】また、本発明においては、本発明の特定の
方法で製造されたポリエチレンに、他の方法で製造され
たポリオレフィンを適宜配合することは、本発明のポリ
エチレンの特性を損わない限りにおいては何等問題はな
い。これら他のポリオレフィンの例としては、高圧法ポ
リエチレン、中低圧法により製造されたポリエチレン、
ポリプロピレン、エチレン・酢酸ビニル共重合体などを
挙げることができる。これらの配合割合は本発明のポリ
エチレン１００重量部に対して１００重量部以下が望ま
しい。Further, in the present invention, it is appropriate to properly mix the polyethylene produced by the specific method of the present invention with the polyolefin produced by another method as long as the characteristics of the polyethylene of the present invention are not impaired. There is no problem. Examples of these other polyolefins include high-pressure polyethylene, polyethylene produced by the medium-low pressure method,
Examples thereof include polypropylene and ethylene / vinyl acetate copolymer. The mixing ratio of these is preferably 100 parts by weight or less with respect to 100 parts by weight of the polyethylene of the present invention.
【００１８】本発明のポリエチレンあるいは本発明のポ
リエチレンに他の方法で製造されたポリオレフィンおよ
び／または各種添加剤を配合した組成物を特定の照射方
法で電子線照射して得られる電子線架橋ポリエチレン
は、耐熱性が非常に高いばかりでなく、耐衝撃性が著し
くすぐれている等良好な性質を有している。Electron beam cross-linked polyethylene obtained by irradiating the polyethylene of the present invention or a composition of the polyethylene of the present invention with a polyolefin produced by another method and / or various additives by an electron beam by a specific irradiation method is used. It has good properties such as not only very high heat resistance but also extremely excellent impact resistance.
【００１９】[0019]
【実施例】以下に実施例を挙げて本発明を具体的に説明
するが、本発明はこれらに制限されるものではない。EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.
【００２０】なお、本発明における評価の試験方法は次
の通りである。 熱変形温度 加熱溶融プレスにより厚さ４ｍｍのシートを作り、所定
条件で電子線照射後ＪＩＳ Ｋ７２０２（Ｂ法）に従っ
て測定した。The test method for evaluation in the present invention is as follows. Heat distortion temperature A sheet having a thickness of 4 mm was prepared by a hot melt press, and after irradiation with an electron beam under predetermined conditions, measurement was performed according to JIS K7202 (method B).
【００２１】ＩＺＯＤ衝撃強度 加熱溶融プレスにより厚さ２ｍｍのシートを作り、所定
条件で電子線照射後ＪＩＳ Ｋ７１１０に従って測定し
た。IZOD Impact Strength A sheet having a thickness of 2 mm was prepared by a hot melt press, and after irradiation with an electron beam under predetermined conditions, measurement was performed according to JIS K7110.
【００２２】引張衝撃強度 加熱溶融プレスにより厚さ２ｍｍのシートを作り、所定
条件で電子線照射後ＡＳＴＭ Ｄ１８２２−６１Ｔに従
って測定した。Tensile Impact Strength A sheet having a thickness of 2 mm was prepared by a hot-melt press, and irradiated with an electron beam under predetermined conditions, and then measured according to ASTM D1822-61T.
【００２３】製造例１（ポリエチレンの製造） （ａ）反応生成物（Ａ）の調製 ｎ−ブチルマグネシウムクロライドのテトラヒドロフラ
ン溶液７５ｍＬに末端をトリメチルシリル基で封鎖して
あるメチルヒドロポリシロキサン（２５℃の粘度約３０
センチストークス）１０．５ｍＬを添加し、得られた反
応生成物（Ａ）の溶液を過剰のテトラヒドロフランを蒸
溜溜去した後、トルエンで稀釈し、Ｍｇ濃度０．５ｍｏ
ｌ／ｌのトルエン溶液３３４ｍｌを得た。 Production Example 1 (Production of Polyethylene) (a) Preparation of Reaction Product (A) Methylhydropolysiloxane having a terminal blocked with trimethylsilyl group in 75 mL of a tetrahydrofuran solution of n-butylmagnesium chloride (viscosity at 25 ° C.) About 30
Centistokes) 10.5 mL was added, and the obtained solution of the reaction product (A) was distilled off excess tetrahydrofuran and then diluted with toluene to obtain a Mg concentration of 0.5 mo.
334 ml of a 1 / l toluene solution was obtained.
【００２４】（ｂ）固体触媒成分（Ｂ）の製造 得られた反応生成物（Ａ）のトルエン溶液２００ｍｌを
０℃に冷却し、四塩化チタン２０ｍＬを滴下し、滴下後
０℃で２時間反応させた。この反応生成物にｎ−ヘキサ
ンを加え、傾斜濾過により可溶性成分を除去し、固体触
媒成分（Ｂ）１８．５ｇ／Ｌのｎ−ヘキサンスラリー１
Ｌを得た。(B) Production of solid catalyst component (B) 200 ml of a toluene solution of the obtained reaction product (A) was cooled to 0 ° C., 20 mL of titanium tetrachloride was added dropwise, and after the addition, the reaction was carried out at 0 ° C. for 2 hours. Let N-Hexane was added to this reaction product, and soluble components were removed by gradient filtration to obtain 18.5 g / L of solid catalyst component (B) n-hexane slurry 1
L was obtained.
【００２５】（ｃ）重合反応 内部を乾燥、窒素置換した撹拌、加熱冷却用ジャケット
を具備した内容１．２Ｌのステンレス製オートクレーブ
にｎ−ヘキサン６００ｍＬを仕込み、６０℃に加熱した
後、トリエチルアルミニウム０．５ｍｍｏｌ、上記
（ｂ）で得た固体触媒成分［Ｂ］４ｍｇを順次添加し
た。次に水素を２ｋｇ／ｃｍ2 導入し、８５℃に昇温し
た後、全圧が９ｋｇ／ｃｍ2 になるように連続的にエチ
レンを導入しながら１時間、重合を行った。冷却後、グ
ラスフィルターで溶媒との分離のみを行い、そのまま減
圧乾燥して粉末状ポリエチレンを得た。(C) Polymerization reaction 600 mL of n-hexane was charged into a 1.2 L stainless steel autoclave equipped with a jacket for stirring and heating / cooling, the inside of which was dried and purged with nitrogen. 0.5 mmol and 4 mg of the solid catalyst component [B] obtained in (b) above were sequentially added. Next, 2 kg / cm 2 of hydrogen was introduced, the temperature was raised to 85 ° C., and then polymerization was carried out for 1 hour while continuously introducing ethylene so that the total pressure was 9 kg / cm 2 . After cooling, only separation from the solvent was performed with a glass filter, and the product was dried under reduced pressure as it was to obtain powdery polyethylene.
【００２６】実施例１〜３ 生成したポリエチレン粉末は、ＭＦＲ０．９０ｇ／１０
ｍｉｎ、密度０．９６０ｇ／ｃｍ3 であった。このポリ
エチレン粉末を用いて、評価試験方法記載の方法により
それぞれの試験片を作製した。 Examples 1 to 3 The produced polyethylene powder has an MFR of 0.90 g / 10.
min and the density was 0.960 g / cm 3 . Using this polyethylene powder, each test piece was produced by the method described in the evaluation test method.
【００２７】次いで、この試験片に加圧電圧２．２Ｍｅ
Ｖ、電流値３ｍＡの条件で表１に示す線量を照射した
後、物性を測定した。結果を表１に示す。Then, a pressure voltage of 2.2 Me was applied to the test piece.
After irradiation with the dose shown in Table 1 under the conditions of V and current value of 3 mA, the physical properties were measured. The results are shown in Table 1.
【００２８】[0028]
【表１】 [Table 1]
【００２９】比較例１ 実施例１〜３の方法で得られたポリエチレン粉末から作
成した試験片に電子線照射を行わず、そのまま実施例１
〜３と同様にして物性を測定した。結果を表１に示す。
本発明方法による電子線照射により、何れの照射線量に
おいても、比較例１に示す電子線未照射の結果に比べ、
熱変形温度、ＩＺＯＤ衝撃強度、引張衝撃強度の高いも
のが得られる。 Comparative Example 1 A test piece prepared from the polyethylene powders obtained by the methods of Examples 1 to 3 was not subjected to electron beam irradiation, but was used as in Example 1
The physical properties were measured in the same manner as in ~ 3. The results are shown in Table 1.
By the electron beam irradiation according to the method of the present invention, at any irradiation dose, compared with the result of the electron beam non-irradiation shown in Comparative Example 1,
A material having high heat distortion temperature, IZOD impact strength, and tensile impact strength can be obtained.
【００３０】実施例４〜６ 電子線照射条件として、加速電圧２．２ＭｅＶ、電流値
２０ｍＡの条件で実施例１〜３と同様に照射を行い、物
性を測定した。結果を表２に示す。 Examples 4 to 6 As electron beam irradiation conditions, irradiation was performed in the same manner as in Examples 1 to 3 under the conditions of an acceleration voltage of 2.2 MeV and a current value of 20 mA, and the physical properties were measured. The results are shown in Table 2.
【００３１】[0031]
【表２】 [Table 2]
【００３２】何れの照射線量においても、上記比較例１
に比べ、各物性値共に大きな値を示している。At any irradiation dose, the above Comparative Example 1 was used.
Compared with, the physical property values are large.
【００３３】比較例２〜４ 実施例１〜３において、電子線照射条件を電流値０．１
ｍＡとした以外は実施例１〜３と同様に行った。結果を
表３に示す。得られた架橋ポリエチレンは本発明の実施
例１〜６と比較して、熱変形温度の値は同等であるが、
衝撃強度特に引張衝撃強度値が著しく小さいものであっ
た。 Comparative Examples 2 to 4 In Examples 1 to 3, electron beam irradiation conditions were set to a current value of 0.1.
It carried out like Examples 1-3 except having set it as mA. The results are shown in Table 3. The obtained crosslinked polyethylene has the same heat distortion temperature value as compared with Examples 1 to 6 of the present invention.
The impact strength, especially the tensile impact strength value, was extremely small.
【００３４】[0034]
【表３】 [Table 3]
【００３５】比較例５〜７ 実施例１〜３において、放射線照射装置として60Ｃｏ−
γ線照射装置（線源６０００キュリー）を用いた以外は
実施例１〜３と同様に行った。結果を表４に示す。 Comparative Examples 5 to 7 In Examples 1 to 3, 60 Co-- was used as a radiation irradiation device.
It carried out like Examples 1-3 except having used the gamma ray irradiation device (ray source 6000 Curie). The results are shown in Table 4.
【００３６】[0036]
【表４】 [Table 4]
【００３７】γ線照射による架橋ポリエチレンも本発明
の実施例１〜６と比較して、熱変形温度の値は同等であ
るが、衝撃強度特に引張衝撃強度値が著しく小さいもの
であった。The cross-linked polyethylene by γ-ray irradiation had the same heat distortion temperature as that of Examples 1 to 6 of the present invention, but the impact strength, especially the tensile impact strength, was remarkably small.
【００３８】実施例７〜９ 実施例１〜３において粉末状のポリエチレンを用いる代
りに、該ポリエチレン粉末１００重量部に対しステアリ
ン酸カルシウムを０．２重量部と商品名イルガノックス
１０１０（チバガイギー（株）製）を０．１重量部添加
し、押出機にて溶融混練したものを使用した以外は実施
例１〜３と同じ条件で電子線照射を行い、物性測定を行
った。結果を表５に示す。 Examples 7 to 9 In place of using powdered polyethylene in Examples 1 to 3, 0.2 parts by weight of calcium stearate and 100 parts by weight of polyethylene powder and Irganox 1010 (trade name, manufactured by Ciba Geigy Co., Ltd.) were used. 0.1 part by weight was added and the mixture was melt-kneaded in an extruder, and electron beam irradiation was performed under the same conditions as in Examples 1 to 3 to measure physical properties. The results are shown in Table 5.
【００３９】何れの照射線量においても、安定剤無添加
のポリエチレンに対する照射結果である実施例１〜３と
ほぼ同等の結果が得られており、安定剤配合ポリエチレ
ンに対しても架橋反応は阻害されないことがわかる。Irrespective of the irradiation dose, almost the same results as in Examples 1 to 3, which are the irradiation results for polyethylene without stabilizer added, were obtained, and the crosslinking reaction was not inhibited even with stabilizer-blended polyethylene. I understand.
【００４０】[0040]
【表５】 [Table 5]
【００４１】実施例１０〜１２ 実施例１〜３において粉末状のポリエチレンを用いる代
りに、該ポリエチレン粉末１００重量部に対しステアリ
ン酸カルシウムを０．２重量部と商品名ＤＳＴＰ「ヨシ
トミ」（吉富製薬（株）製）を０．１重量部添加し、押
出機にて溶融混練したものを使用した以外は実施例１〜
３と同じ条件で電子線照射を行い、物性測定を行った。
結果を表６に示す。この安定剤配合処方についても、安
定剤無添加のポリエチレンに対する照射結果である実施
例１〜３とほぼ同等の結果が得られた。 Examples 10 to 12 Instead of using powdered polyethylene in Examples 1 to 3, 0.2 parts by weight of calcium stearate and 100 parts by weight of polyethylene powder and DSTP "Yoshitomi" (Yoshitomi Pharmaceutical ( (Manufactured by K.K.) was used, and the melt-kneaded product was used in an extruder.
Electron beam irradiation was carried out under the same conditions as in No. 3, and physical properties were measured.
The results are shown in Table 6. With this stabilizer-containing formulation, almost the same results as in Examples 1 to 3, which are the irradiation results for polyethylene without a stabilizer, were obtained.
【００４２】[0042]
【表６】 [Table 6]
【００４３】比較例８〜１０ 実施例７〜９において用いた安定剤配合ポリエチレンに
対し、比較例２〜４で用いた電子線照射条件で照射を行
った。照射後のポリエチレンについての物性測定結果
は、表７に示すとうりである。 Comparative Examples 8 to 10 The stabilizer-containing polyethylene used in Examples 7 to 9 was irradiated with the electron beam irradiation conditions used in Comparative Examples 2 to 4. The results of measuring physical properties of polyethylene after irradiation are as shown in Table 7.
【００４４】[0044]
【表７】 [Table 7]
【００４５】[0045]
【発明の効果】本発明によれば特定の方法で製造された
ポリエチレンに、特定の範囲の加速電圧、電流値の電子
線で照射することにより、機械的、熱的および化学的性
質、特に耐熱性と衝撃強度がともに優れた電子線架橋ポ
リエチレンを製造することができる。また各種安定剤類
を配合させたポリエチレンに対する電子線架橋において
も、架橋反応が阻害されることなく、高性能の架橋ポリ
エチレンが得られる。INDUSTRIAL APPLICABILITY According to the present invention, polyethylene produced by a specific method is irradiated with an electron beam having an accelerating voltage and a current value in a specific range so that mechanical, thermal and chemical properties, particularly heat resistance It is possible to produce an electron beam crosslinked polyethylene excellent in both properties and impact strength. Further, in the electron beam cross-linking of polyethylene mixed with various stabilizers, a high-performance cross-linked polyethylene can be obtained without inhibiting the cross-linking reaction.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 池田 重利 東京都新宿区高田馬場４丁目40番13号 株 式会社レイテック内 (72)発明者 山本 繁治 千葉県市原市五井南海岸11−２ 丸善ポリ マー株式会社内 (72)発明者 中西 三徳 千葉県市原市五井南海岸11−２ 丸善ポリ マー株式会社内 (72)発明者 森永 博 東京都中央区八丁堀４丁目８番２号 丸善 ポリマー株式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Shigetoshi Ikeda 4-40-13 Takadanobaba, Shinjuku-ku, Tokyo Within RAITEC Co., Ltd. (72) Inventor Shigeharu Yamamoto 11-2 Goi Minamikaigan, Ichihara-shi, Chiba Maruzen Poly (72) Inventor Santoku Nakanishi 11-2 Goi Minamikaigan, Ichihara-shi, Chiba Maruzen Polymer Co., Ltd. (72) Inventor Hiroshi Morinaga 4-8 Hatchobori, Chuo-ku, Tokyo Maruzen Polymer Co., Ltd.
Claims (1)
媒成分および有機アルミニウム化合物からなるチーグラ
ー触媒を用いて製造され、かつ触媒残渣の除去工程を行
わずに得られたもので、密度が０．９４１ｇ／ｃｍ3 以
上、メルトフローレートが０．０１〜１００ｇ／１０分
のポリエチレンを、加速電圧が５００ＫｅＶ〜１０Ｍｅ
Ｖ、かつ電流値が１〜３０ｍＡの電子線で１〜１００Ｍ
ｒａｄの照射線量で照射することを特徴とする架橋ポリ
エチレンの製造方法。1. A product produced by using a Ziegler catalyst composed of a solid catalyst component containing magnesium and titanium and an organoaluminum compound, and obtained without performing a step of removing a catalyst residue, and having a density of 0.941 g / cm 3 or more, polyethylene having a melt flow rate of 0.01 to 100 g / 10 min, an acceleration voltage of 500 KeV to 10 Me
1 to 100M with electron beam of V and current value of 1 to 30mA
A method for producing crosslinked polyethylene, which comprises irradiating with a radiation dose of rad.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12987992A JPH05301971A (en) | 1992-04-24 | 1992-04-24 | Production of polyethylene cross-linked with electron beam |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12987992A JPH05301971A (en) | 1992-04-24 | 1992-04-24 | Production of polyethylene cross-linked with electron beam |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05301971A true JPH05301971A (en) | 1993-11-16 |
Family
ID=15020585
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12987992A Pending JPH05301971A (en) | 1992-04-24 | 1992-04-24 | Production of polyethylene cross-linked with electron beam |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05301971A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013080737A (en) * | 2011-09-30 | 2013-05-02 | Dainippon Printing Co Ltd | Rear surface protective sheet for solar cell module and method for manufacturing the same |
| US9663631B2 (en) | 2012-05-16 | 2017-05-30 | Autonetworks Technologies, Ltd. | Photosensitive thermoplastic resin composition and molded product using same |
| US11319417B2 (en) * | 2019-08-16 | 2022-05-03 | Exxonmobil Upstream Research Company | Methods of manufacturing highly crosslinked polymer particulate |
-
1992
- 1992-04-24 JP JP12987992A patent/JPH05301971A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013080737A (en) * | 2011-09-30 | 2013-05-02 | Dainippon Printing Co Ltd | Rear surface protective sheet for solar cell module and method for manufacturing the same |
| US9663631B2 (en) | 2012-05-16 | 2017-05-30 | Autonetworks Technologies, Ltd. | Photosensitive thermoplastic resin composition and molded product using same |
| US11319417B2 (en) * | 2019-08-16 | 2022-05-03 | Exxonmobil Upstream Research Company | Methods of manufacturing highly crosslinked polymer particulate |
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