JP2511623B2 - Method for producing antistatic ultrahigh molecular weight polyethylene resin composition - Google Patents
Method for producing antistatic ultrahigh molecular weight polyethylene resin compositionInfo
- Publication number
- JP2511623B2 JP2511623B2 JP31187192A JP31187192A JP2511623B2 JP 2511623 B2 JP2511623 B2 JP 2511623B2 JP 31187192 A JP31187192 A JP 31187192A JP 31187192 A JP31187192 A JP 31187192A JP 2511623 B2 JP2511623 B2 JP 2511623B2
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- molecular weight
- weight polyethylene
- powder
- ultrahigh molecular
- sas
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、帯電防止能を有する超
高分子量ポリエチレン樹脂組成物の製造方法に関する。TECHNICAL FIELD The present invention relates to a method for producing an ultrahigh molecular weight polyethylene resin composition having an antistatic ability.
【０００２】[0002]
【従来の技術】超高分子量ポリエチレン樹脂成形物は、
粘度法による平均分子量が４０万以上、光散乱法による
平均分子量が２００万以上の超高分子量ポリエチレンポ
リマーを成形して得られるものであり、平均分子量が粘
度法で３万程度まで、光散乱法で約６０万程度までの普
通のポリエチレンポリマーから得られるポリエチレン樹
脂成形物と比較して、耐摩耗性、耐衝撃性、低温特性、
ストレスクラッキングに対する抵抗性等の特性に優れ、
摩擦係数も小さいので、ホッパー、シュート等のライニ
ング材や、歯車、軸受、ローラー、ガイドレールなどに
使用されている。しかし、電気絶縁性が高いため摩擦に
より、容易に帯電するので、製造工程並びに製品使用上
種々の問題を有している。2. Description of the Related Art Ultrahigh molecular weight polyethylene resin moldings are
It is obtained by molding an ultrahigh molecular weight polyethylene polymer having an average molecular weight of 400,000 or more by a viscosity method and 2 million or more by a light scattering method. Abrasion resistance, impact resistance, low temperature characteristics, compared with polyethylene resin moldings obtained from ordinary polyethylene polymers up to about 600,000
Excellent properties such as resistance to stress cracking,
Since it has a low coefficient of friction, it is used for lining materials such as hoppers and chutes, as well as gears, bearings, rollers and guide rails. However, since it has a high electric insulation property, it is easily charged by friction, which causes various problems in the manufacturing process and use of the product.
【０００３】例えば、製造工程において、超高分子量ポ
リエチレン成形品と製造装置との摩擦により発生する静
電気によって、円滑な操作が妨げられ、極端な場合には
製品の品質低下がもたらされる。また、製品の使用時又
は保管時においても、塵埃の付着、静電気によるショッ
クなどの好ましくない減少を避けられず、表面汚損によ
る商品価値の低下、火花の発生による危険、あるいはそ
れを回避するために使用場所や用途が制限される等の問
題を有している。[0003] For example, in the manufacturing process, static electricity generated by friction between the ultrahigh molecular weight polyethylene molded product and the manufacturing apparatus hinders smooth operation and, in extreme cases, deteriorates product quality. In addition, during use or storage of the product, inadvertent reduction of dust adhesion, shock due to static electricity, etc. is unavoidable, and the product value is reduced due to surface contamination, the risk of spark generation, or to avoid it. There is a problem that the place of use and the application are limited.
【０００４】そのため、帯電防止能を付与するために従
来よりカーボンブラック、金属粉末等の導電剤や界面活
性剤を練り込んだり、あるいは界面活性剤を樹脂表面に
塗布する方法が取られている。Therefore, in order to impart antistatic ability, a method of kneading a conductive agent such as carbon black or metal powder or a surfactant or coating the surface of the resin with a surfactant has been conventionally used.
【０００５】[0005]
【発明が解決しようとする課題】しかしながら、界面活
性剤を塗布する方法は、帯電防止能が失われやすく、長
期間保持できない。また界面活性剤を樹脂中に練り込む
方法は、特に超高分子量ポリエチレンポリマーの場合、
十分な分散性が得られず満足する帯電防止効果が得られ
ず、さらに成型等の加工工程で受ける高熱によって界面
活性剤が劣化され、樹脂を黄色又は褐色に着色する等の
問題がある。カーボンブラックを練り込む方法では、前
述の着色をマスキングし、帯電防止性能を向上させるも
のであるが、樹脂製品の色が黒色に限定され、商品のバ
リエーションが低く、また金属粉末等の導電剤を練り込
む方法では、樹脂製品の色が金属色になるので、商品価
値的に好ましくなく、さらに摺動部材として用いると、
相手材料を汚損したり傷を付ける等の問題がある。However, in the method of applying a surfactant, the antistatic ability is easily lost and it cannot be maintained for a long period of time. Further, the method of kneading the surfactant into the resin, especially in the case of ultra-high molecular weight polyethylene polymer,
There is a problem that sufficient dispersibility cannot be obtained, a satisfactory antistatic effect cannot be obtained, and the surfactant is deteriorated by high heat received in a processing step such as molding, and the resin is colored yellow or brown. In the method of kneading carbon black, the above-mentioned coloring is masked and the antistatic performance is improved, but the color of the resin product is limited to black, the product variation is low, and the conductive agent such as metal powder is used. In the kneading method, the color of the resin product becomes a metallic color, which is not preferable in terms of commercial value, and when used as a sliding member,
There is a problem that the mating material is contaminated or scratched.
【０００６】本発明の目的は、前記の問題を解決するも
のであり、帯電防止能に優れたアルカンスルホン酸金属
塩の樹脂中への分散性を改善し、超高分子量ポリエチレ
ン樹脂が本来有する乳白色を損なうことなく、あるいは
所望の色彩に着色することが可能であり、かつ優れた帯
電防止性能を有する超高分子量ポリエチレン樹脂組成物
の製造方法を提供することにある。The object of the present invention is to solve the above-mentioned problems, to improve the dispersibility of an alkanesulfonic acid metal salt having excellent antistatic ability in a resin, and to obtain a milky white color which an ultrahigh molecular weight polyethylene resin originally has. It is an object of the present invention to provide a method for producing an ultrahigh molecular weight polyethylene resin composition which can be colored in a desired color without impairing the properties of the resin and has an excellent antistatic property.
【０００７】[0007]
【課題を解決するための手段】本発明者等は、特定の超
高分子量ポリエチレンにアルカンスルホン酸金属塩を混
合分散させることにより、その分散性が改良され、帯電
防止性能が向上し、このため着色性の導電剤等を用いる
必要がなくなるので、ポリエチレン樹脂が本来有してい
る乳白色を損なうことがなく、あるいは種々の色彩に自
在に着色することが可能であることを見出し、本発明を
完成するに至った。DISCLOSURE OF THE INVENTION The inventors of the present invention have improved the dispersibility and the antistatic performance by mixing and dispersing an alkanesulfonic acid metal salt in a specific ultrahigh molecular weight polyethylene. Since it is not necessary to use a coloring conductive agent or the like, the present invention has been completed by finding that it does not impair the milky white that the polyethylene resin originally has, or that it can be freely colored in various colors. Came to do.
【０００８】すなわち、本発明は、嵩密度０．３未満の
超高分子量ポリエチレンポリマー粉末１０〜１００重量
部と、嵩密度０．３以上の超高分子量ポリエチレンポリ
マー粉末９０〜０重量部と、前記２種類の超高分子量ポ
リエチレンポリマー粉末の合計１００重量部に対して、
アルカンスルホン酸金属塩０．５〜５．０重量部とを、
アルカンスルホン酸金属塩は予め有機溶媒に溶解した溶
液で、混合し、次いで得られた混合物から前記溶媒を除
去した後、成形してなる帯電防止性超高分子量ポリエチ
レン樹脂組成物の製造方法である。That is, the present invention comprises 10 to 100 parts by weight of an ultra high molecular weight polyethylene polymer powder having a bulk density of less than 0.3, and 90 to 0 parts by weight of an ultra high molecular weight polyethylene polymer powder having a bulk density of 0.3 or more, To 100 parts by weight in total of two kinds of ultra high molecular weight polyethylene polymer powder,
0.5 to 5.0 parts by weight of alkanesulfonic acid metal salt,
The alkanesulfonic acid metal salt is a method of producing an antistatic ultrahigh molecular weight polyethylene resin composition obtained by mixing a solution of a metal alkanesulfonic acid previously dissolved in an organic solvent, removing the solvent from the resulting mixture, and then molding the mixture. .
【０００９】本発明で使用する超高分子量ポリエチレン
は、嵩密度０．３未満の超高分子量ポリエチレンポリマ
ー（以下低嵩密度ポリマーという）粉末と、嵩密度０．
３以上の超高分子量ポリエチレンポリマー（以下通常の
ポリマーという）粉末の２種類である。The ultrahigh molecular weight polyethylene used in the present invention includes ultrahigh molecular weight polyethylene polymer (hereinafter referred to as low bulk density polymer) powder having a bulk density of less than 0.3 and a bulk density of 0.
There are two types of powder of 3 or more ultra high molecular weight polyethylene polymer (hereinafter referred to as ordinary polymer) powder.
【００１０】通常のポリマーは、最も一般的な超高分子
量ポリエチレンポリマーとして市販されているものであ
り、平均分子量が粘度法で約４０万以上、光散乱法で約
２００万以上、嵩密度約０．４０〜０．５０、平均粒径
約１００〜１６０μｍの白色粉末、あるいはこのペレッ
ト化したものである。具体的には、ヘキスト社製のホス
タレンＧＵＲ４１２、４１３、４１５、４１６、旭化成
工業社製のサンテックＵＨ９００、９５０、三井石油化
学社製のハイゼックスミリオン２４０Ｍ、３４０Ｍ、６
３０Ｍ、ＤＳＭ社製のスタミランＵＨ２１０、６１０な
どが挙げられ、本発明ではこれらの市販品を用いること
ができる。Ordinary polymers are commercially available as the most common ultrahigh molecular weight polyethylene polymers, and have an average molecular weight of about 400,000 or more by the viscosity method, about 2 million or more by the light scattering method, and a bulk density of about 0. 40 to 0.50, a white powder having an average particle size of about 100 to 160 μm, or a pelletized product thereof. Specifically, Hostalen GUR412, 413, 415, 416 manufactured by Hoechst, Suntech UH900, 950 manufactured by Asahi Kasei, and Hi-Zex Million 240M, 340M, 6 manufactured by Mitsui Petrochemical.
30M, Stamilan UH210, 610 manufactured by DSM, and the like, and commercially available products thereof can be used in the present invention.
【００１１】低嵩密度ポリマーは、平均分子量が粘度法
で約４０万以上、光散乱法で約２００万以上、嵩密度
０．３未満、粒径分布約１００〜４００μｍの白色粉末
であり、例えばヘキスト社からホスタレンＧＵＲ２１２
として市販されている。このポリマーの最も特徴的な点
は、比較的滑らかな球体状をしている通常のポリマーと
異なり、粒子の形状が不定形形状であり、その表面が通
常のポリマーと比較して大きく複雑な凹凸を有している
ことである。The low bulk density polymer is a white powder having an average molecular weight of about 400,000 or more by a viscosity method, about 2 million or more by a light scattering method, a bulk density of less than 0.3, and a particle size distribution of about 100 to 400 μm. Hoechst to Hostalen GUR212
Is marketed as. The most distinguishing feature of this polymer is that, unlike ordinary polymers, which have a relatively smooth spherical shape, the shape of the particles is irregular, and the surface has large and complex irregularities compared to ordinary polymers. Is to have.
【００１２】本発明で使用するアルカンスルホン酸金属
塩は、一般式（１） Ｒ−ＳＯ3Ｍ （１） で表わされる化合物である。式中、Ｒは炭素数８〜２２
の直鎖アルキル基であり、炭素数が８より小さい場合や
逆に２２より大きい場合は充分な帯電防止性能が得られ
ない。帯電防止性能をより高めるためには炭素数８〜１
５が好ましい。また、ＭはＬｉ，Ｎａ，Ｋなどのアルカ
リ金属、Ｂａ，Ｍｇ，Ｃａなどのアルカリ土類金属、及
びＺｎ，Ａｌなどの金属が挙げられ、なかでもＮａ，Ｌ
ｉが高い帯電防止性能を有しており、より好ましい。ま
た、−ＳＯ3ＭはＲの１級炭素原子又は２級炭素原子に
結合している。The alkanesulfonic acid metal salt used in the present invention is a compound represented by the general formula (1) R-SO 3 M (1). In the formula, R has 8 to 22 carbon atoms
When the number of carbon atoms is less than 8 or conversely more than 22, it is not a straight chain alkyl group, and sufficient antistatic performance cannot be obtained. 8 to 1 carbon atoms to improve antistatic performance
5 is preferred. Examples of M include alkali metals such as Li, Na and K, alkaline earth metals such as Ba, Mg and Ca, and metals such as Zn and Al. Among them, Na and L
i has high antistatic performance and is more preferable. Further, —SO 3 M is bonded to the primary carbon atom or secondary carbon atom of R.
【００１３】アルカンスルホン酸金属塩（以下、ＳＡＳ
と略す）は、水溶液、水溶液を濃縮したペースト、ペレ
ット、フレーク、粉末等の形状で市販されている。本発
明では有機溶媒に溶解してポリマーの粉末に混合して用
いるので、水分を極力含まないペレット、フレーク、粉
末が好ましく使用できる。中でも溶解速度の早い粉末が
作業効率の点から好ましい。Alkanesulfonic acid metal salt (hereinafter referred to as SAS
Is abbreviated as), and is commercially available in the form of an aqueous solution, a paste obtained by concentrating the aqueous solution, pellets, flakes, powder, or the like. In the present invention, since it is dissolved in an organic solvent and mixed with a polymer powder to be used, pellets, flakes and powders containing as little water as possible can be preferably used. Among them, powder having a high dissolution rate is preferable from the viewpoint of work efficiency.
【００１４】ＳＡＳは、樹脂１００重量部に対して０．
５〜５．０重量部の範囲で配合され、優れた帯電防止性
能を有する樹脂組成物を得ることができる。配合量が
０．５重量部未満では、満足する帯電防止性能を得るこ
とができず、逆に５．０重量部を超えると、増加量に見
合うほどの帯電防止性能の向上が得られないことに加
え、ＳＡＳが樹脂から激しくにじみだす（ブリード現
象）ので、好ましくない。SAS is 0.
A resin composition having an excellent antistatic property, which is compounded in the range of 5 to 5.0 parts by weight, can be obtained. If the blending amount is less than 0.5 parts by weight, satisfactory antistatic performance cannot be obtained, and conversely, if it exceeds 5.0 parts by weight, improvement in antistatic performance commensurate with the increased amount cannot be obtained. In addition, SAS exudes violently from the resin (bleed phenomenon), which is not preferable.
【００１５】本発明の帯電防止性超高分子量ポリエチレ
ン樹脂組成物の製造方法は、低嵩密度ポリマー粉末と、
通常のポリマー粉末と、ＳＡＳを溶解した有機溶媒溶液
とをそれぞれ所定量秤取り、ヘンシェルミキサ、スーパ
ーミキサなどの混合装置で混合し、得られた混合物から
有機溶媒を蒸発除去した後、通常の樹脂成型方法、例え
ば、圧縮成型、ラム押出成型、スクリュー押出成型、射
出成型などの方法にて成形加工して、本発明の帯電防止
性能に優れた超高分子量ポリエチレン樹脂組成物を得る
方法である。The method for producing an antistatic ultrahigh molecular weight polyethylene resin composition of the present invention comprises a low bulk density polymer powder,
A predetermined amount of a usual polymer powder and a solution of an organic solvent in which SAS is dissolved are weighed and mixed in a mixing device such as a Henschel mixer or a super mixer, and the organic solvent is removed from the obtained mixture by evaporation, and then a normal resin is used. It is a method for obtaining an ultrahigh molecular weight polyethylene resin composition of the present invention having excellent antistatic performance by performing a molding process such as compression molding, ram extrusion molding, screw extrusion molding, or injection molding.
【００１６】樹脂組成物に優れた帯電防止性能を付与す
るには、混合の際にＳＡＳが細分化されて、均一にポリ
エチレンポリマーと混ざりあうことが重要である。しか
し、ＳＡＳはポリエチレンポリマーとの相溶性が悪く、
通常の方法で微細化することは困難である。従って、粉
末同士で混合しても、マクロ的には均一に分散されても
ミクロ的には大きなＳＡＳ粒子とポリマー粒子が存在
し、満足する帯電防止性能が付与されない。また、ＳＡ
Ｓ粉末の粒径は約１〜２ｍｍとポリマー粉末よりも遥か
に大きく、ミキサにかけてもあまり微細化されない。大
きなＳＡＳ粒子が残存すると、樹脂の成形時ににじみだ
して金型を汚したり、成形樹脂の表面にまだら模様を浮
き出させるといった問題を生じ、かつ期待する帯電防止
性能が得られない。In order to impart excellent antistatic performance to the resin composition, it is important that the SAS be finely divided during mixing so that the SAS is uniformly mixed with the polyethylene polymer. However, SAS has poor compatibility with polyethylene polymers,
It is difficult to miniaturize by an ordinary method. Therefore, even if the powders are mixed with each other, or even if dispersed macroscopically, large SAS particles and polymer particles are present microscopically, and satisfactory antistatic performance is not provided. Also, SA
The particle size of the S powder is about 1 to 2 mm, which is much larger than that of the polymer powder, and the S powder is not pulverized so much even when it is mixed with a mixer. If large SAS particles remain, problems such as bleeding at the time of molding the resin and soiling of the mold, or a mottled pattern appearing on the surface of the molding resin, and the expected antistatic performance cannot be obtained.
【００１７】ところが、混合の際に、予め有機溶媒に溶
解したＳＡＳを用いることによって、ＳＡＳは、溶液と
ともにポリマー粉末空隙内や粒子の凹凸表面内に侵入し
付着するので、短時間で樹脂中に分子レベルで均一に効
率的に分散される。特に低嵩密度ポリマー粉末は、表面
が比較的大きな凹凸を有しているため、その効果は大き
い。しかもポリマー粒子同志が機械的にも絡み合ってＳ
ＡＳ粒子の配位数が大きくなり、ＳＡＳ粒子の連結層を
形成して帯電防止性能を発揮する。さらに、ポリマーの
不定形形状によって表面積が大きくなっているので、Ｓ
ＡＳ溶液中の溶媒は容易に蒸散される。However, when SAS is dissolved in an organic solvent in advance during the mixing, the SAS penetrates into the voids of the polymer powder and the uneven surface of the particles together with the solution and adheres to the resin. Dispersed uniformly and efficiently at the molecular level. Particularly, the low bulk density polymer powder has a large effect because its surface has relatively large irregularities. Moreover, the polymer particles are mechanically entangled with each other and S
The coordination number of the AS particles is increased, and a connecting layer of the SAS particles is formed to exhibit antistatic performance. Furthermore, since the surface area is large due to the amorphous shape of the polymer, S
The solvent in the AS solution is easily evaporated.
【００１８】さらに、通常のポリマー粉末だけでは、溶
液の吸収が悪く、ポリマー粉末１００重量部に対して塩
化メチレン溶液の場合、１５〜２０重量部程度添加する
だけで、混合物は湿潤状態となり、湿り方に差が生じ、
ＳＡＳが偏在して充分な均一分散効果を得られない。均
一な分散が得られるドライ状態でブレンドするために
は、ＳＡＳ溶液の添加量を少なくし、一旦溶媒を揮散、
除去させた後、再びＳＡＳ溶液を添加して混合する操作
を繰り返す必要があり、作業性が極めて悪い。一方、低
嵩密度ポリマー粉末では、塩化メチレン溶液を８０重量
部添加しても湿潤状態になることがなく、ドライ状態で
混合できる。低嵩密度ポリマー粉末を１０重量％含有す
るポリマー粉末の場合、ドライ状態で混合できる溶液の
添加量は約５０重量部である。当然低嵩密度ポリマー粉
末の配合量が多いほど溶液の添加可能量は多くなるが、
低嵩密度ポリマー粉末量が１０重量％を超えると溶液の
添加可能量の増加は緩やかになる。Further, the absorption of the solution is poor only with the ordinary polymer powder, and in the case of a methylene chloride solution with respect to 100 parts by weight of the polymer powder, the mixture becomes a wet state by adding about 15 to 20 parts by weight. Difference occurs,
SAS is unevenly distributed and a sufficient uniform dispersion effect cannot be obtained. In order to blend in a dry state where a uniform dispersion can be obtained, the amount of SAS solution added is reduced, and the solvent is evaporated once.
After the removal, it is necessary to repeat the operation of adding the SAS solution and mixing again, resulting in extremely poor workability. On the other hand, the low bulk density polymer powder does not become wet even when 80 parts by weight of the methylene chloride solution is added, and can be mixed in a dry state. In the case of the polymer powder containing 10% by weight of the low bulk density polymer powder, the amount of the solution that can be mixed in the dry state is about 50 parts by weight. Naturally, the larger the amount of low bulk density polymer powder compounded, the greater the amount that can be added to the solution,
When the amount of the low bulk density polymer powder exceeds 10% by weight, the increase in the addable amount of the solution becomes gradual.
【００１９】本発明では、低嵩密度ポリマー粉末量を１
０重量％以上含有するポリマー粉末を用いる。こうする
ことによって、前述の不均一分散の問題や湿潤状態での
混合は回避される。また、低嵩密度ポリマー粉末の配合
量は多くても特に問題はないが、混合時に飛散しやすい
ため作業性、ロスの観点から、またポリマー粉末が高価
であるので、７０重量％以下、特には５０重量％以下が
好ましい。In the present invention, the amount of low bulk density polymer powder is 1
A polymer powder containing 0% by weight or more is used. This avoids the aforementioned problems of non-uniform dispersion and wet mixing. Further, although there is no particular problem even if the blending amount of the low bulk density polymer powder is large, from the viewpoint of workability and loss because it is easily scattered during mixing, and since the polymer powder is expensive, 70% by weight or less, particularly It is preferably 50% by weight or less.
【００２０】本発明で使用する有機溶媒としては、ＳＡ
Ｓを良く溶解し、ポリエチレンや添加剤の特性を損なわ
ず、蒸散しやすいものが好ましく、例えば、トルエン、
メタノール、エタノール、イソプロパノール、エチレン
グリコール、酢酸ノルマルブチル、メタクリル酸メチ
ル、エチルセロソルブ、塩化メチレン、クロロホルム、
四塩化炭素、トリクロロエチレン、１，１，１−トリク
ロロエタン、１，１，２−トリクロロ−１，２，２−ト
リフルオロエタン、トリクロルベンゼン、クロロブロモ
メタン、臭化イソプロピル、臭化ｎ−イソプロピル、臭
化ブチルなどが挙げられる。引火性、爆発の危険性の低
いハロゲン系のものが好ましく、中でも環境規制の少な
い塩化メチレンが好ましい。The organic solvent used in the present invention is SA
It is preferable that it dissolves S well, does not impair the properties of polyethylene and additives, and easily evaporates, for example, toluene,
Methanol, ethanol, isopropanol, ethylene glycol, normal butyl acetate, methyl methacrylate, ethyl cellosolve, methylene chloride, chloroform,
Carbon tetrachloride, trichloroethylene, 1,1,1-trichloroethane, 1,1,2-trichloro-1,2,2-trifluoroethane, trichlorobenzene, chlorobromomethane, isopropyl bromide, n-isopropyl bromide, odor Butyl chloride and the like. Halogen-based compounds having low flammability and low risk of explosion are preferable, and among them, methylene chloride, which has less environmental regulations, is preferable.
【００２１】ＳＡＳ溶液中のＳＡＳの濃度は、用いる溶
媒のＳＡＳの溶解度によって異なるので、ＳＡＳが析出
せず、長期間安定な溶液状態を保持できる範囲内にすれ
ばよい。ちなみに、塩化メチレンでのＳＡＳの溶解度は
約２０重量％である。また、ＳＡＳは、ポリマー１００
重量部に対して０．５〜５．０重量部添加するが、溶液
のＳＡＳ濃度が濃いと溶液の添加量は少なくてすむ利点
があるものの、ポリマー全体に十分に行き渡らない危険
があり、逆に薄いと溶液の添加量を多くする必要が生じ
てウェットな状態で混合することとなり、前記したよう
にＳＡＳの分散が不均一となる危険があると共に、多く
の溶剤を蒸発除去する必要がある。このような危険や無
駄を回避するため、ポリマー１００重量部に対して溶液
としての添加量は、２０〜４０重量部となるようにＳＡ
Ｓ濃度を調整して用いることが好ましい。Since the concentration of SAS in the SAS solution varies depending on the solubility of SAS in the solvent used, it may be set within a range where SAS does not precipitate and a stable solution state can be maintained for a long period of time. Incidentally, the solubility of SAS in methylene chloride is about 20% by weight. In addition, SAS is a polymer 100
Although 0.5 to 5.0 parts by weight is added to parts by weight, if the SAS concentration of the solution is high, there is an advantage that the addition amount of the solution can be small, but there is a risk that it will not be sufficiently distributed in the whole polymer. If it is too thin, it is necessary to increase the addition amount of the solution, which results in mixing in a wet state, and as described above, there is a risk that the SAS dispersion becomes non-uniform, and it is necessary to evaporate and remove many solvents. . In order to avoid such dangers and waste, the amount of the solution added should be 20 to 40 parts by weight based on 100 parts by weight of the polymer.
It is preferable to adjust the S concentration before use.
【００２２】このようにして得られた樹脂組成物は、Ｓ
ＡＳが、樹脂中に薄層となって均一に分散されるため、
優れた帯電防止性能を発揮する。The resin composition thus obtained contains S
Since AS becomes a thin layer in the resin and is uniformly dispersed,
Exhibits excellent antistatic performance.
【００２３】従って、熱、空気と接触して起る変質劣化
による変色がなく、また黒色系統の導電剤を併用する必
要がないので、ポリエチレン樹脂が本来有する乳白色を
保持できる。このため、従来の黒色の超高分子量ポリエ
チレン樹脂組成物とは異なり、商品価値が格段に向上す
る。Therefore, there is no discoloration due to deterioration due to deterioration caused by contact with heat or air, and since it is not necessary to use a black conductive agent together, the milky white originally possessed by the polyethylene resin can be maintained. Therefore, unlike the conventional black ultrahigh molecular weight polyethylene resin composition, the commercial value is remarkably improved.
【００２４】なお、本発明では有機過酸化剤などの架橋
剤、湿潤剤、顔料、紫外線吸収剤、無機充填剤などを本
発明の効果を損なわない範囲で、適宜添加することがで
き、特に種々の色彩の顔料を選定して用いることによっ
て樹脂成形物を望む色に着色することができる。In the present invention, a cross-linking agent such as an organic peroxide, a wetting agent, a pigment, an ultraviolet absorber, an inorganic filler and the like can be appropriately added within a range not impairing the effects of the present invention, and particularly various kinds. The resin molded product can be colored in a desired color by selecting and using a pigment of the above color.
【００２５】[0025]
【実施例】以下、実施例によって本発明をさらに詳細に
説明する。The present invention will be described in more detail with reference to the following examples.
【００２６】実施例で原材料としては、次のものを用い
た。In the examples, the following raw materials were used.
【００２７】通常のポリマー粉末として、ヘキスト社製
の超高分子量ポリエチレンポリマー粉末（ホスタレンＧ
ＵＲ４１２）、低嵩密度ポリマー粉末として、ヘキスト
社製の低嵩密度超高分子量ポリエチレンポリマー粉末
（ホスタレンＧＵＲ２１２）の２種類のポリマー粉末を
用いた。これらの物性を表１に示す。As an ordinary polymer powder, an ultrahigh molecular weight polyethylene polymer powder (Hostalen G manufactured by Hoechst Co., Ltd.
UR412), and two types of low bulk density polymer powders, low bulk density ultra high molecular weight polyethylene polymer powder (Hostalen GUR212) manufactured by Hoechst Co. were used. Table 1 shows these physical properties.
【００２８】[0028]
【表１】 [Table 1]
【００２９】ＳＡＳとしては、日鉱石油化学社製のアル
カンスルホン酸ナトリウム塩を用い、その物性を表２に
示す。As the SAS, alkanesulfonic acid sodium salt manufactured by Nikko Petrochemical Co., Ltd. is used, and its physical properties are shown in Table 2.
【００３０】[0030]
【表２】 [Table 2]
【００３１】有機溶媒としては、旭硝子社製の塩化メチ
レン（工業用、純度９９％以上）を用いた。As the organic solvent, methylene chloride manufactured by Asahi Glass Co., Ltd. (industrial use, purity 99% or more) was used.
【００３２】実施例１〜５，比較例１〜４ 先ずアルカンスルホン酸ナトリウム塩２０重量％の塩化
メチレン溶液を調製し、次いで、表３に示す割合で、超
高分子量ポリエチレンポリマー粉末、及びアルカンスル
ホン酸ナトリウム塩粉末あるいは前記の塩化メチレン溶
液（表３はアルカンスルホン酸ナトリウム塩としての換
算値を表示している）をヘンシェルミキサー（三井三池
化工機社製、ＦＭ１５０）に投入し、１３８０ｒｐｍで
１５分間混合する。得られた混合物を６０℃のオーブン
にて塩化メチレンを蒸発除去し、次いで金型に仕込み、
プレス成型機により面圧１００ｋｇ／ｃｍ2に加圧し、
金型温度を２００℃に昇温して９０分間保持した後、面
圧１００ｋｇ／ｃｍ2を保ちながら加熱を停止し、金型
を６０分間冷却し、超高分子量ポリエチレン樹脂組成物
の試料片（厚さ１５ｍｍ×幅２００ｍｍ×長さ３００ｍ
ｍ）を得た。Examples 1 to 5 and Comparative Examples 1 to 4 First, a solution of 20% by weight of alkanesulfonic acid sodium salt in methylene chloride was prepared, and then ultrahigh molecular weight polyethylene polymer powder and alkane sulfone were added in the proportions shown in Table 3. Acid sodium salt powder or the above methylene chloride solution (Table 3 shows the conversion value as alkanesulfonic acid sodium salt) was charged into a Henschel mixer (FM150, manufactured by Mitsui Miike Kakoki Co., Ltd.), and the mixture was rotated at 1380 rpm for 15 minutes. Mix. The resulting mixture was evaporated in a 60 ° C. oven to remove methylene chloride, and then charged into a mold,
Pressurized to a surface pressure of 100 kg / cm 2 with a press molding machine,
After the mold temperature was raised to 200 ° C. and held for 90 minutes, heating was stopped while maintaining a surface pressure of 100 kg / cm 2 , the mold was cooled for 60 minutes, and a sample piece of the ultrahigh molecular weight polyethylene resin composition ( Thickness 15 mm x width 200 mm x length 300 m
m) was obtained.
【００３３】なお、表３中の混合方法において、乾はア
ルカンスルホン酸ナトリウム塩粉末での混合を示し、温
は該ナトリウム塩の塩化メチレン溶液での混合を示す。In the mixing method shown in Table 3, dry means mixing with alkanesulfonic acid sodium salt powder, and warm means mixing with sodium chloride solution of the sodium salt.
【００３４】前記の試験片をさらに評価試験用の試験片
に加工して、電気特性、機械特性の試験を行い評価し
た。また、混合工程での混合性、ブリード現象の有無に
ついても評価した。その結果を表３に示す。The above-mentioned test piece was further processed into a test piece for an evaluation test, and the electrical and mechanical characteristics were tested and evaluated. In addition, the mixing property in the mixing process and the presence or absence of the bleeding phenomenon were also evaluated. Table 3 shows the results.
【００３５】なお前記評価に用いた試験の概要は次のと
おりである。The outline of the test used for the evaluation is as follows.
【００３６】表面抵抗率 試料片を２５℃、相対湿度５０％の雰囲気下に７２時間
放置後、三菱油化製のハイレスタＩＰで５００Ｖの電圧
を印加し、表面固有抵抗率（Ω／□）を測定した。 Surface resistivity After the sample piece was left in an atmosphere of 25 ° C. and 50% relative humidity for 72 hours, a voltage of 500 V was applied with a Hiresta IP manufactured by Mitsubishi Petrochemical to determine the surface resistivity (Ω / □). It was measured.
【００３７】帯電半減期 ２３℃、相対湿度５０％の雰囲気下において、試料片に
１０ｋＶの電圧を１分間印字した後、宍戸商会製のスタ
チックオネストメータで帯電圧が半分になる時間（秒）
を測定した。After charging a voltage of 10 kV on the sample piece for 1 minute in an atmosphere having a charging half-life of 23 ° C. and a relative humidity of 50%, the time (second) at which the electrification voltage is halved with a static onest meter manufactured by Shishido Shokai
Was measured.
【００３８】引張り強さ（降伏、破断及び伸び） ＪＩＳＫ７１１３に準拠し、インストロン式万能試験機
で、厚さ２ｍｍに加工した試料を打ち抜きダンベル２号
形試験片をつくり、この試験片に引張荷重を５０ｍｍ／
分の速さで加え、降伏強さ（ｋｇ／ｃｍ2）、破断強さ
（ｋｇ／ｃｍ2）、及び破断時の伸び率（％）を測定し
た。 Tensile Strength (Yield, Fracture and Elongation) In accordance with JIS K7113, a sample processed into a thickness of 2 mm was punched out with an Instron universal testing machine to form a dumbbell No. 2 type test piece, and a tensile load was applied to this test piece. 50 mm /
In addition, the yield strength (kg / cm 2 ), the breaking strength (kg / cm 2 ), and the elongation at break (%) were measured at a speed of minutes.
【００３９】摩耗（サンドスラリー法） 試験片（７ｍｍ×２５ｍｍ×７５ｍｍ）の最大面積面の
中心に１０ｍｍ径の孔を穿ち、この孔で試験片を回転ス
ピンドルの先端に固定し、硅砂２ｋｇ、水３．５ｋｇを
混合した２０℃のスラリー中に試験片を浸漬し、前記ス
ピンドルを１０００ｒｐｍで２０時間回転し、試験片の
摩耗減量（ｍｇ）を測定した。 Abrasion (sand slurry method) A 10 mm diameter hole was drilled in the center of the maximum area surface of a test piece (7 mm x 25 mm x 75 mm), and the test piece was fixed to the tip of a rotary spindle with this hole, 2 kg of silica sand, water. The test piece was immersed in a slurry of 3.5 kg mixed at 20 ° C., and the spindle was rotated at 1000 rpm for 20 hours to measure the wear loss (mg) of the test piece.
【００４０】混合工程での混合性 超高分子量ポリエチレンポリマー粉末とアルカンスルホ
ン酸ナトリウム塩の塩化メチレン溶液とをヘンシェルミ
キサにかけて、約１５分後における混合状態をのぞき窓
より目視で観察し、及びミキサ停止後の混合物の排出状
態を目視で観察した。In the mixing step, the mixing ultra-high molecular weight polyethylene polymer powder and a solution of sodium alkane sulfonate in methylene chloride were applied to a Henschel mixer, and after about 15 minutes, the mixed state was visually observed through a sight glass, and the mixer was stopped. The discharged state of the subsequent mixture was visually observed.
【００４１】なお、評価は次の基準による。The evaluation is based on the following criteria.
【００４２】○：粉末状態の混合物が全体的にミキサ中
心に向かって流動混合されている。サラサラした粉末が
均一なドライ状態で排出され、混合物がミキサ内にほと
んど残らない。◯: The mixture in the powder state is entirely fluidized and mixed toward the center of the mixer. The dry powder is discharged in a uniform dry state, leaving almost no mixture in the mixer.
【００４３】×：ミキサの遠心力で側壁にドライ粉末と
ウエット粉末が付着し、ミキサ内で混合物は滑らかな流
動状態を示さない。排出がスムースでなく、混合物がミ
キサ内に残存する。X: Dry powder and wet powder adhere to the side wall due to the centrifugal force of the mixer, and the mixture does not show a smooth flow state in the mixer. The discharge is not smooth and the mixture remains in the mixer.
【００４４】ブリード現象 金型から成形物を取り出した際、金型面にアルカンスル
ホン酸ナトリウム塩の付着の有無を目視で観察するとと
もに、成形物の表面状態を目視で観察した。 Bleed phenomenon When the molded product was taken out from the mold, the presence or absence of sodium alkane sulfonate adhering to the mold surface was visually observed, and the surface condition of the molded product was visually observed.
【００４５】なお、評価は次の基準による。The evaluation is based on the following criteria.
【００４６】〇：金型表面が鏡面光沢を保持し、全く曇
りが認められない。◯: The surface of the mold retains a mirror gloss, and no fog is observed.
【００４７】成形物表面に全く曇りが認められない。No cloudiness is observed on the surface of the molded product.
【００４８】×：金型表面に全面あるいはまだらに曇り
が認められる。X: Fogging is observed on the entire surface of the mold or in a mottled pattern.
【００４９】成形物表面に全面あるいはまだらに曇りが
認められる。Haze is observed on the entire surface of the molded product or in mottle.
【００５０】[0050]
【表３】 [Table 3]
【００５１】表３より、本発明の実施例１〜５は表面低
効率が１０8〜１０11Ω／□台、半減期が１秒以下と、
電気的特性に優れ、また、機械的強度や混合性に全く問
題なく、さらにブリード現象も発現せず、総合的に極め
て優れていることが分かる。一方、比較例１はＳＡＳを
粉末で混合したためブリード現象が現れ、電気的特性も
やや劣っている。ＳＡＳの添加量の少ない比較例２は電
気的特性が悪く、逆にＳＡＳの添加量の多い比較例３は
電気特性は良いが、ブリード現象が現れ、機械的強度が
低下し好ましくない。また、低嵩密度ポリマーの配合割
合が少ない比較例４は混合性が悪く、均一な混合物が得
られない。From Table 3, Examples 1 to 5 of the present invention have a low surface efficiency of 10 8 to 10 11 Ω / □ and a half-life of 1 second or less.
It can be seen that the electrical properties are excellent, there is no problem in the mechanical strength and the mixing property, and the bleeding phenomenon does not appear. On the other hand, in Comparative Example 1, SAS was mixed in the form of powder, so that the bleeding phenomenon appeared and the electrical characteristics were slightly inferior. Comparative Example 2 in which the amount of SAS added is small has poor electric characteristics, and conversely, Comparative Example 3 in which the amount of SAS added is large has good electric characteristics, but a bleeding phenomenon appears and mechanical strength decreases, which is not preferable. Further, Comparative Example 4 in which the blending ratio of the low bulk density polymer is small has poor mixability, and a uniform mixture cannot be obtained.
【００５２】実施例６ ホスタレンＧＵＲ４１２を２８０重量部、ホスタレンＧ
ＵＲ２１２を７０重量部、アルカンスルホン酸ナトリウ
ム塩を２０％含有する塩化メチレン溶液５２．５重量
部、ステアリン酸カルシウム（堺化学工業社製）０．７
重量部、及び着色剤としてフタロシアニングリーン（東
洋インキ製造社製）０．５６重量部をヘンシェルミキサ
に投入し、２０分間混合して、グリーンに着色した混合
粉末を得、以降前記実施例と同様にして６０℃のオーブ
ン中で該混合粉末から塩化メチレンを蒸発除去し、次い
で金型に仕込みプレス成型機で成形して、明るい緑色に
着色された成形物を得た。 Example 6 280 parts by weight of Hostalene GUR412, Hostalene G
70 parts by weight of UR212, 52.5 parts by weight of a methylene chloride solution containing 20% of alkanesulfonic acid sodium salt, calcium stearate (manufactured by Sakai Chemical Industry Co., Ltd.) 0.7
By weight, phthalocyanine green (manufactured by Toyo Ink Mfg. Co., Ltd.) as a coloring agent was added to a Henschel mixer and mixed for 20 minutes to obtain a green-colored mixed powder. Then, methylene chloride was removed from the mixed powder by evaporation in an oven at 60 ° C., and then charged into a mold and molded by a press molding machine to obtain a molded product colored bright green.
【００５３】[0053]
【発明の効果】本発明は、特定の超高分子量ポリエチレ
ンにアルカンスルホン酸金属塩を有機溶媒に溶解した溶
液の形態で混合分散させるため、その分散性が格段に改
良されるので、帯電防止性能が向上し、しかもその性能
は持続的であり、またポリエチレン樹脂成形物はそれが
本来有している乳白色を損なうことがなく、あるいは種
々の色彩に着色が自在にできるという格別の効果を示
す。INDUSTRIAL APPLICABILITY The present invention mixes and disperses a metal salt of alkanesulfonic acid in a specific ultrahigh molecular weight polyethylene in the form of a solution dissolved in an organic solvent, so that the dispersibility thereof is remarkably improved. In addition, the polyethylene resin molded article has a remarkable effect that it does not impair the milky white that it originally has, or that it can be freely colored in various colors.
Claims (1)
ポリエチレンポリマー粉末１０〜１００重量部と、嵩
密度０．３以上の超高分子量ポリエチレンポリマー粉末
９０〜０重量部と、 （ｂ）前記（ａ）の超高分子量ポリエチレンポリマー粉
末の合計１００重量部に対して、アルカンスルホン酸金
属塩０．５〜５．０重量部とを、 アルカンスルホン酸金属塩は予め有機溶媒に溶解した溶
液で、混合し、次いで得られた混合物から前記溶媒を除
去した後、成形することを特徴とする帯電防止性超高分
子量ポリエチレン樹脂組成物の製造方法。1. (a) 10 to 100 parts by weight of ultra-high molecular weight polyethylene polymer powder having a bulk density of less than 0.3; 90 to 0 parts by weight of ultra-high molecular weight polyethylene polymer powder having a bulk density of 0.3 or more; ) 0.5 to 5.0 parts by weight of the metal salt of alkane sulfonic acid was dissolved in advance in an organic solvent with respect to 100 parts by weight of the ultra high molecular weight polyethylene polymer powder of (a). A method for producing an antistatic ultrahigh molecular weight polyethylene resin composition, which comprises mixing with a solution, removing the solvent from the obtained mixture, and then molding.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31187192A JP2511623B2 (en) | 1992-11-20 | 1992-11-20 | Method for producing antistatic ultrahigh molecular weight polyethylene resin composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31187192A JP2511623B2 (en) | 1992-11-20 | 1992-11-20 | Method for producing antistatic ultrahigh molecular weight polyethylene resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06157773A JPH06157773A (en) | 1994-06-07 |
| JP2511623B2 true JP2511623B2 (en) | 1996-07-03 |
Family
ID=18022421
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31187192A Expired - Lifetime JP2511623B2 (en) | 1992-11-20 | 1992-11-20 | Method for producing antistatic ultrahigh molecular weight polyethylene resin composition |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2511623B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20130023616A1 (en) * | 2009-12-02 | 2013-01-24 | Saudi Basic Industries Corporation | Process for the addition of additives to ultra high molecular weight polyethylene |
-
1992
- 1992-11-20 JP JP31187192A patent/JP2511623B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06157773A (en) | 1994-06-07 |
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